Aggarwal, J.K., Palmer, M.R., Bullen, T.D., Arnorsson, S. and Ragnarsdottir, K.V., 2000, The boron isotope systematics of Icelandic geothermal waters: 1. Meteoric water charged systems: Geochimica et Cosmochimica Acta, v. 64, no. 4, p. 579-585.
We have measured the boron isotope composition and boron and chloride concentrations of 27 Icelandic geothermal fluids from both high- and low-temperature systems. The d11B values range from -6.70/00 in the Krafla system, to +25.00/00 in a warm spring from the Southern Lowlands. In addition, we have also determined the d11B values of basaltic glass from Nesjavellir (-5.3 ± 1.40/00) and travertine from Snaefellsnes (-22 ± 0.50/00). The B isotope and Cl/B systematics of the high-temperature systems are dominated by the composition of the local basalts. The lower temperature systems show evidence for mixing with B and Cl of a marine origin, together with some uptake of B into secondary mineral phases. The data from the Snaefellsnes geothermal system indicate that the fluids have undergone interaction with basalts that have undergone significant low-temperature alteration by seawater.
Metals transport in the Sacramento River, northern California, from July 1996 to June 1997 was evaluated in terms of metal loads from samples of water and suspended colloids that were collected on up to six occasions at 13 sites in the Sacramento River Basin. Four of the sampling periods (July, September, and November 1996; and May-June 1997) took place during relatively low-flow conditions, respectively. This study focused primarily on loads of cadmium, copper, lead, and zinc, with secondary emphasis on loads of aluminum, iron, and mercury.
Trace metals in acid mine drainage from abandoned and inactive base-metal mines, in the East and West Shasta mining districts, enter the Sacramento River system in predominantly dissolved form both Shasta Lake and Keswick Reservoir. The proportion of trace metals that was dissolved (as opposed to colloidal) in samples collected at Shasta and Keswick dams decreased in the order zinc » cadmium > copper > lead. At four sampling sites on the Sacramento River -- 71, 256, 360, and 412 kilometers downstream of Keswick Dam -- trace-metal loads were predominantly colloidal during both high- and low-flow conditions. The proportion of total cadmium, copper, lead, and zinc loads transported to Sacramento-San Joaquin Delta estuary (referred to as the Bay-Delta) that is associated with mineralized areas was estimated by dividing loads at Keswick Dam by loads 412 kilometers downstream at Freeport and the Yolo Bypass. During moderately high flows in December 1996, mineralization-related total (dissolved + colloidal) trace-metal loads to the Bay-Delta (as a percentage of total loads measured downstream) were cadmium, 87 percent; copper, 35 percent; lead, 10 percent; and zinc, 51 percent. During flood conditions in January 1997 loads were cadmium, 22 percent; copper, 11 percent; lead, 2 percent; and zinc, 15 percent. During irrigation drainage season from rice fields (May-June 1997) loads were cadmium, 53 percent; copper, 42 percent; lead, 20 percent; and zinc, 75 percent. These estimates must be qualified by the following factors: (1) metal loads at Colusa in December 1996 and at Verona in May-June 1997 generally exceeded those determined at Freeport during those sampling periods. Therefore, the above percentages represent maximum estimates of the apparent total proportion of metals from mineralized areas upstream of Keswick Dam; and (2) for logistics reasons, the Sacramento River was sampled at Tower Bridge instead of at Freeport during January 1997.
Available data suggest that trace metal loads from agricultural drainage may be significant during certain flow conditions in areas where metals such as copper and zinc are added as agricultural amendments. Copper loads for sampling periods in July and September 1996 and in May-June 1997 show increases of dissolved and colloidal copper and in colloidal zinc between Colusa and Verona, the reach of the Sacramento River along which the Colusa Basin Drain, the Sacramento Slough, and other agricultural return flows are tributaries. Monthly sampling of these agricultural drains by the USGS National Water-Quality Assessment Program shows seasonal variations in metal concentrations, reaching maximum concentrations of 4 to 6 micrograms per liter in "dissolved" (0.45-micrometer filtrate) copper concentrations in May 1996, December 1996, and June 1997. The total (dissolved plus colloidal) load of copper from the Colusa Basin Drain in June 1997 was 18 kilograms per day, whereas the copper load in Spring Creek, which drains the inactive mines on Iron Mountain, was 20 kilograms per day during the same sampling period. For comparison, during the January 1997 flood, the copper load in Spring Creek was about 1,100 kilograms per day and the copper load in the Yolo Bypass was about 7,300 kilograms per day. The data clearly indicate that most copper and zinc loads during the January 1997 flood entered the Sacramento River upstream of Colusa, and upstream of the influence of the most intense agricultural drainage return flows in the Sacramento River watershed.
This study has demonstrated that some trace metals of environmental significance (cadmium, copper, and zinc) in the Sacramento River are transported largely in dissolved form at upstream sites (below Shasta Dam, below Keswick Dam, and at Bend Bridge) proximal to the mineralized areas of the West Shasta and East Shasta mining districts. In contrast, these trace metals are transported largely in colloidal form at downstream sites (Colusa, Verona, Freeport, and Yolo Bypass). Aluminum, iron, and lead were observed to be transported predominantly in the colloidal phase at all mainstem Sacramento River sampling sites during all sampling periods in this study. Despite continuous water treatment, which has removed 85 to 90 percent of the cadmium, copper, and zinc from the mine drainage at Iron Mountain, Spring Creek remains a significant source of these metals to the Sacramento River system.
Metals transport in the Sacramento River, northern California, was evaluated on the basis of samples of water, suspended colloids, streambed sediment, and caddisfly larvae that were collected on one to six occasions at 19 sites in the Sacramento River Basin from July 1996 to June 1997. Four of the sampling periods (July, September, and November 1996; and May-June 1997) took place during relatively low-flow conditions and two sampling periods (December 1996 and January 1997) took place during high-flow and flooding conditions; respectively. Tangential-flow ultrafiltration with 10,000 nominal molecular weight limit, of daltons (0.005 micrometer equivalent), pore-size membranes was used to separate metals in streamwater into ultrafiltrate (operationally defined dissolved fraction) and retentate (colloidal fraction) components, respectively. Conventional filtration with capsule filters (0.45 micrometer pore-size) and membrane filters (0.40 micrometer pore-size) and total-recoverable analysis of unfiltered (whole-water) samples were done for comparison at all sites. Because the total-recoverable analysis involves an incomplete digestion of particulate matter, a more reliable measurement of whole-water concentrations is derived from the sum of the dissolved component that is based on the ultrafiltrate plus the suspended component that is based on a total digestion of colloid concentrates from the ultrafiltration retentate. Metals in caddisfly larvae were determined for whole-body samples and cytosol extracts, which are intercellular solutions that provide a more sensitive indication of the metals that have been bioaccumulated.
Trace metals in acidic, metal-rich drainage from abandoned and inactive sulfide mines were observed to enter the Sacramento River system (specifically, into both Shasta Lake and Keswick Reservoir) in predominantly dissolved form, as operationally defined using ultrafiltrates. The predominant source of acid mine drainage to Keswick Reservoir is Spring Creek, which drains the Iron Mountain mine area. Copper concentrations in filtered samples from Spring Creek taken during December 1996, January 1997, and May 1997 ranged from 420 to 560 micrograms per liter. Below Keswick Dam, copper concentrations in conventionally filtered samples ranged from 0.5 micrograms per liter during September 1996 to 9.4 micrograms per liter during January 1997; the latter concentration exceeded the applicable water-quality standard. The proportion of trace metals that was dissolved (versus colloidal) in samples collected at Shasta and Keswick dams decreased in the order cadmium » zinc > copper > aluminum » iron » lead » mercury. At four sampling sites on the Sacramento River at various distances downstream of Keswick Dam (Bend Bridge, 71 kilometers; Colusa, 256 kilometers; Verona, 360 kilometers; and Freeport, 412 kilometers) concentrations of these seven metals were predominantly colloidal during both high- and low-flow conditions.
Because copper compounds are used extensively as algaecides in rice farming, agricultural drainage at the Colusa Basin Drain was sampled in June 1997 during a period shortly after copper applications to newly planted rice fields. Copper concentrations ranged from 1.3 to 3.0 micrograms per liter in filtered samples and from 12 to 13 micrograms per liter in whole-water samples (total recoverable analysis). These results are consistent with earlier work by the U.S. Geological Survey indicating that copper in rice-field drainage likely represents a detectable, but relatively minor source of copper to the Sacramento River.
Lead isotope data from suspended colloids and streambed sediments collected during October and November 1996 indicate that lead from acid mine drainage sources became a relatively minor component of the total lead at the site located 71 kilometers downstream of Keswick Dam and beyond. Cadmium, copper, and zinc concentrations in caddisfly larvae were elevated at several sites downstream of Keswick Dam, but concentrations of aluminum, iron, lead, and mercury were relatively low, especially in the cytosol extracts. Cadmium showed the highest degree of bioaccumulation in whole-body and cytosol analyses, relative to an unmineralized control site (Cottonwood Creek). Cadmium bioaccumulation persisted in samples collected as far as 118 kilometers downstream of Keswick Dam, consistent with transport in a form more bioavailable than lead.
Anderman, E.R., and Hill, M.C., 2000, MODFLOW-2000, the U.S. Geological Survey modular ground-water model -- Documentation of the hydrologic-unit flow (HUF) package: U.S. Geological Survey Open-File Report 00-342.
The Colorado Plateau is a distinct physiographic province in western North America, which presently straddles the transition between summer-wet and summer-dry climatic regimes to the south and northwest, respectively. In addition to climate, the diversity of environments and plant communities on the Colorado Plateau has resulted from extreme topographic diversity. Desert lowlands as low as 360 m elevation are surrounded by forested plateaus, and even higher peaks greater than 3800 m elevation. This environmental diversity provides a unique opportunity to study the history of biotic communities in an arid region of North America. Although the Colorado Plateau harbours numerous potential sites, the paleoecological record of the Plateau is poorly known. Potential deposits for analysis include packrat middens, alluvial and cave sites at lower elevations, and lake, bog and wetland sites at higher elevations. Forty-six sites have been analysed across the nearly 337,000 km2 region, of which 27 contain records that span Marine Oxygen Isotope Stage (IS) 2 data, with IS 3 information coming from only 12 sites. Most IS 2 and 3 sites are clustered along the lowland regions of the Colorado River corridor and the uplands of the Mogollon Rim area. We compiled selected data from long paleoecological records to examine patterns of vegetation and climate change across the southern Colorado Plateau for the middle and late Wisconsin. During the middle Wisconsin, mixed conifers covered middle-elevations presently dominated by ponderosa pine (Pinus ponderosa), and juniper (Juniperus) woodland grew at elevations today covered by blackbrush (Coleogyne) and sagebrush (Artemisia) desert. During the late Wisconsin, boreal conifers, primarily Engelmann spruce (Picea engelmannii), replaced the mixed conifer association. Estimates of mean annual temperatures (MAT) during IS 3 were at least 3-4 degrees C cooler than today, whereas IS 2 MAT estimates are at least 5 degrees C colder. Our investigation of millennial-scale climatic variability within the region provided equivocal results. The packrat midden sequence could not distinguish vegetation changes that might be associated with Heinrich events in the North Atlantic. From the lake records, however, many Heinrich events were associated with generally drier intervals, often with elevated sagebrush pollen concentrations. Future paleoecological investigations should concentrate on the northern Colorado Plateau, as well as the eastern and western margins. Additional sites, along with closer-spaced sampling in regions already studied, will be important in determining the history of important climatic phenomena such as the timing of the Arizona monsoon.
Andrews, E.D., 2000, Bed material transport in the Virgin River, Utah: Water Resources Research, v. 36, no. 2, p. 585-596.
Detailed information concerning the rate and particle size distribution of bed material transport by streamflows can be very difficult and expensive to obtain, especially where peak streamflows are brief and bed material is poorly sorted, including some very large boulders. Such streams, however, are common in steep, arid watersheds. Any computational approach must consider that (1) only the smaller particle sizes present on the streambed move even during large floods and (2) the largest bed particles exert a significant form drag on the flow. Conventional methods that rely on a single particle size to estimate the skin friction shear stress acting on the mobile fraction of the bed material perform poorly. Instead, for this study, the skin friction shear stress was calculated for the observed range of streamflows by calculating the form drag exerted on the reach-averaged flow field by all particle sizes. Suspended and bed load transported rates computed from reach-averaged skin friction shear stress are in excellent agreement with measured transport rates. The computed mean annual bed material load, including both bed load and suspended load, of the East Fork Virgin River for the water years 1992-1996 was approximately 1.3 x 105 t. A large portion of the bed material load consists of sand-sized particles, 0.062-1.0 mm in diameter, that are transported in suspension. Such particles, however, constituted only 10% of the surface bed material and less than 25% of the subsurface bed material. The mean annual quantity of bed load transported was 1060 t/yr with a median size of 15 mm.
A method has been developed for separating the Cr dissolved in natural water from matrix elements and determination of its stable isotope ratios using solid-source thermal-ionization mass spectrometry (TIMS). The separation method takes advantage of the existence of the oxidized form of Cr as an oxyanion to separate it from interfering cations using anion-exchange chromatography, and of the reduced form of Cr as a positively charged ion to separate it from interfering anions such as sulfate. Subsequent processing of the separated sample eliminates residual organic material for application to a solid source filament. Ratios for 53Cr/52Cr for National Institute of Standards and Technology Standard Reference Material 979 can be measured using the silica gel-boric acid technique with a filament-to-filament standard deviation in the mean 53Cr/52Cr ratio for 50 replicates of 0.00005 or less.
The U.S. Geological Survey (USGS) is working closely with other Federal and State agencies in a comprehensive program to evaluate and restore the south Florida ecosystem. Within the USGS South Florida Ecosystem Program, a project entitled ?Coupling Models for Canal and Wetland Flow/Transport Interaction? is focused on analysis and numerical simulation of flow and potential transport of constituents between canal C-111 and wetlands adjacent to Everglades National Park. In support of this project, comprehensive sets of flow, vegetation, and water-quality data were collected in September 1997 and 1999. The flow-velocity data are compiled, summarized, and tabulated in this report. The flow, vegetation, and water-quality data are available for downloading from the World Wide Web.
We have measured U(VI) adsorption on hematite using EXAFS spectroscopy and electrophoresis under conditions relevant to surface waters and aquifers (0.01 to 10 µM dissolved uranium concentrations, in equilibrium with air, pH 4.5 to 8.5). Both techniques suggest the existence of anionic U(VI)-carbonato ternary complexes. Fits to EXAFS spectra indicate that U(VI) is simultaneously coordinated to surface FeO6 octahedra and carbonate (or bicarbonate) ligands in bidentate fashions, leading to the conclusion that the ternary complexes have an inner-sphere metal bridging (hematite-U(VI)-carbonato) structure. Greater than or equal to 50% of adsorbed U(VI) was comprised of monomeric hematite-U(VI)-carbonato ternary complexes, even at pH 4.5. Multimeric U(VI) species were observed at pH greater than or equal to 6.5 and aqueous U(VI) concentrations approximately an order of magnitude more dilute than the solubility of crystalline b-UO2(OH)2. Based on structural constraints, these complexes were interpreted as dimeric hematite-U(VI)-carbonato ternary complexes. These results suggest that Fe-oxide-U(VI)-carbonato complexes are likely to be important transport-limiting species in oxic aquifers throughout a wide range of pH values.
Analytical step-response functions, developed in the companion paper (see abstract for Moench and Barlow, below) for several cases of transient hydraulic interaction between a fully penetrating stream and a confined, leaky, or water-table aquifer, are used in the convolution integral to calculate aquifer heads, streambank seepage rates, and bank storage that occur in response to stream-stage fluctuations and basinwide recharge or evapotranspiration. Two computer programs developed on the basis of these stepresponse functions and the convolution integral are applied to the analysis of hydraulic interaction of two alluvial stream-aquifer systems in the northeastern and central United States. These applications demonstrate the utility of the analytical functions and computer programs for estimating aquifer and streambank hydraulic properties, recharge rates, streambank seepage rates, and bank storage. Analysis of the water-table aquifer adjacent to the Blackstone River in Massachusetts suggests that the very shallow depth of water table and associated thin unsaturated zone at the site cause the aquifer to behave like a confined aquifer (negligible specific yield). This finding is consistent with previous studies that have shown that the effective specific yield of an unconfined aquifer approaches zero when the capillary fringe, where sediment pores are saturated by tension, extends to land surface. Under this condition, the aquifer's response is determined by elastic storage only. Estimates of horizontal and vertical hydraulic conductivity, specific yield, specific storage, and recharge for a water-table aquifer adjacent to the Cedar River in eastern Iowa, determined by the use of analytical methods, are in close agreement with those estimated by use of a more complex, multilayer numerical model of the aquifer. Streambank leakance of the semipervious streambank materials also was estimated for the site. The streambank-leakance parameter may be considered to be a general (or lumped) parameter that accounts not only for the resistance of flow at the river-aquifer boundary, but also for the effects of partial penetration of the river and other near-stream flow phenomena not included in the theoretical development of the step-response functions.
Extended tailing of tracer breakthrough is often observed in pulse injection tracer tests conducted in fractured geologic media. This behavior has been attributed to diffusive exchange of tracer between mobile fluids traveling through channels in fractures and relatively stagnant fluid between fluid channels, along fracture walls, or within the bulk matrix. We present a field example where tracer breakthrough tailing apparently results from nondiffusive transport. Tracer tests were conducted in a fractured crystalline rock using both a convergent and weak dipole injection and pumping scheme. Deuterated water, bromide, and pentafluorobenzoic acid were selected as tracers for their wide range in molecular diffusivity. The late time behavior of the normalized breakthrough curves were consistent for all tracers of varying diffusivity indicates that strong breakthrough tailing in fractured geologic media may be caused by advective transport processes. This finding has implications for the interpretation of tracer tests designed to measure matrix diffusion in situ and the prediction of contaminant transport in fractured rock.
Fossil rodent middens and wetland deposits from the central Atacama Desert (22 degree to 24 degree S) indicate increasing summer precipitation, grass cover, and groundwater levels from 16.2 to 10.5 calendar kiloyears before present (ky B.P.). Higher elevation shrubs and summer-flowering grasses expanded downslope across what is now the edge of Absolute Desert, a broad expanse now largely devoid of rainfall and vegetation. Paradoxically, this pluvial period coincided with the summer insolation minimum and reduced adiabatic heating over the central Andes. Summer precipitation over the central Andes and central Atacama may depend on remote teleconnections between seasonal insolation forcing in both hemispheres, the Asian monsoon, and Pacific sea surface temperature gradients. A less pronounced episode of higher groundwater levels in the central Atacama from 8 to 3 ky B.P. conflicts with an extreme lowstand of Lake Titicaca, indicating either different climatic forcing or different response times and sensitivities to climatic change.
The effects of agriculture on the isotope geochemistry of Sr were investigated in two small watersheds in the Atlantic coastal plain of Maryland. Stratified shallow oxic groundwaters in both watersheds contained a retrievable record of increasing recharge rates of chemicals including NO3-, Cl, Mg, Ca and Sr that were correlated with increasing fertilizer use between about 1940 and 1990. The component of Sr associated with recent agricultural recharge was relatively radiogenic (87Sr/86Sr=0.715) and it was overwhelming with respect to Sr acquired naturally by water-rock interactions in the oxidized, non-calcareous portion of the saturated zone. Agricultural groundwaters that penetrated relatively unoxidized calcareous glauconitic sediments at depth acquired an additional component of Sr from dissolution of early Tertiary marine CaCO3 (87Sr/86Sr=0.708) while undergoing O2 reduction and denitrification. Ground-water discharge contained mixtures of waters of various ages and redox states. Two streams draining the area are considered to have higher 87Sr/86S ratios and NO3- concentrations than they would in the absence of agriculture; however, the streams have consistently different 87Sr/86Sr ratios and NO3- concentrations because the average depth to calcareous reducing (denitrifying) sediments in the local groundwater flow system was different in the two watersheds. The results of this study indicate that agriculture can alter significantly the isotope geochemistry of Sr in aquifers and streams and that the effects could vary depending on the types, sources and amounts of fertilizers added, the history of fertilizer use and groundwater residence times.
A comparative assessment of two reactive-transport models, PHREEQC and HYDROGEOCHEM (HGC), was done to determine the suitability of each for simulating the movement of acidic contamination in alluvium. For simulations that accounted for aqueous complexation, precipitation and dissolution, the breakthrough and rinseout curves generated by each model were similar. The differences in simulated equilibrium concentrations between models were minor and were related to (1) different units in model output, (2) different activity coefficients, and (3) ionic-strength calculations. When adsorption processes were added to the models, the rinseout pH simulated by PHREEQC using the diffuse double-layer adsorption model rose to a pH of 6 after pore volume 15, about 1 pore volume later than the pH simulated by HGC using the constant-capacitance model. In PHREEQC simulation of a laboratory column experiment, the inability of the model to match measured outflow concentrations of selected constituents was related to the evident lack of local geochemical equilibrium in the column. The difference in timing and size of measured and simulated breakthrough of selected constituents indicated that the redox and adsorption reactions in the column occurred slowly when compared with the modeled reactions. MINTEQA2 and PHREEQC simulations of the column experiment indicated that the number of surface sites that took part in adsorption reactions was less than that estimated from the measured concentration of Fe hydroxide in the alluvium.
Sulfur hexafluoride (SF6) is primarily of anthropogenic origin but also occurs naturally. The troposphere concentration of SF6 has increased from a steady state value of 0.054 ± 0.009 to more than 4 parts per trillion volume during the past 40 years. An analytical procedure was developed for measuring concentrations of SF6 to less than 0.01 fmol/L in water. Groundwater can be dated with SF6 if it is in equilibrium with atmospheric SF6 at the time of recharge and does not contain significant SF6 from other sources. The dating range of SF6 is currently 0 to 30 years. The tracer wsa successfully used to date shallow groundwater of the Atlantic Coastal Plain sand aquifers of the United States and springs issuing near the top of the Blue Ridge Mountains of Virginia. Significant concentrations of naturally occurring SF6 were found in some igneous, volcanic, and sedimentary rocks and in some hydrothermal fluids.
From May 1994 through May 1997, the U.S. Geological Survey, in cooperation with the U.S. Department of Energy, collected water samples from 86 wells completed in the Snake River Plain aquifer at and near the Idaho National Engineering and Environmental Laboratory. The samples were analyzed for a variety of chemical constituents including all major elements and 22 trace elements. Concentration of scandium, yttrium, and the lanthanide series were measured in samples from 11 wells and 1 hot spring. The data will be used to determine the fraction of young water in the ground water. The fraction of young water must be known to calculate the ages of the ground water using chlorofluorocarbons. The concentrations of the isotopes deuterium, oxygen-18, carbon-13, carbon-14, and tritium were measured in many ground water, surface-water and spring samples. The isotopic composition will provide clues to the origin and sources of water in the Snake River Plain aquifer. Concentrations of helium-3, helium-4, total helium, and neon were measured in most ground-water samples, and the results will be used to determine the recharge temperature, and to date the ground waters.
The molecular weight of humic substances influences their proton and metal binding, organic pollutant partitioning, adsorption onto minerals and activated carbon, and behavior during water treatment. We propose a log-normal model for the molecular weight distribution in aquatic fulvic acids to provide a conceptual framework for studying these size effects. The normal curve mean and standard deviation are readily calculated from measured Mn and Mw and vary from 2.7 to 3 for the means and from 0.28 to 0.37 for the standard deviations for typical aquatic fulvic acids. The model is consistent with several types of molecular weight data, including the shapes of high-pressure size-exclusion chromatography (HP-SEC) peaks. Applications of the model to electrostatic interactions, pollutant solubilization, and adsorption are explored in illustrative calculations.
A biomonitoring technique was employed to complement studies of metal transport in the upper Sacramento River affected by acid mine drainage. Metals (Al, Cd, Cu, Fe, Hg, Pb, and Zn) were determined in a resident invertebrate, Hydropsyche californica (Insecta: Trichoptera), and streambed sediments (<62 µm) to assess metal contamination within a 111-km section of the river downstream of the mining area. Metals in H. californica also were interpreted to be broadly indicative of metal exposure in fish. Total Hg was determined in the whole body of the insect, whereas Al, Cd, Cu, Fe, Pb, and Zn were additionally separated into operationally defined cytosolic (used as an indicator of exposure to bioavailable metal) and particulate fractions. Total concentrations of Cd, Cu, Hg, Pb, and Zn in sediments were consistent with documented upstream sources of acid mine drainage. Metal distribution patterns in H. californica and sediments were generally consistent for Cd, Cu, and Pb but inconsistent for Hg and Zn. Concentrations in H. californica indicated that bioavailable Cd, Cu, Pb, and Zn was transported at least 120 km downstream of the mine sources. Zinc in H. californica was elevated, but unlike sediments, did not decrease downstream. Mercury in H. californica was not elevated.
Callender, E., 2000, Geochemical effects of rapid sedimentation in aquatic systems: minimal diagenesis and the preservation of historical metal signatures: Journal Paleolimnology, v. 23, p. 243-260.
Rapid sedimentation exerts a pronounced influence on early sedimentary diagenesis in that there is insufficient time for a sediment particle to equilibrate in any one sediment layer before that layer may be displaced vertically by another layer. These sedimentation patterns are common in surface-water reservoirs whose sedimentation rates (1-10 cm/yr) are several orders of magnitude greater than those for natural lakes (0.01-0.5 cm/yr).Two examples of the effects of rapid sedimentation on geochemical metal signatures are presented here. Interstitial-water data (Fe) from two sites in the Cheyenne River Embayment of Lake Oahe on the Missouri River illustrate the effects of changing sedimentation rates on dissolved species. Rapid burial during high-flow yrs appears to limit early sedimentary diagenesis to aerobic respiration. Solid-phase metal data (Pb) from a site in Pueblo Reservoir on the upper Arkansas River in Colorado appear to record historical releases by flooding of abandoned mine sites upstream in Leadville, Colorado. Interstitial-water ammonia and ferrous Fe data indicate that at least one interval at depth in the sediment where solid metal concentrations peak is a zone of minimal diagenesis.The principal diagenetic reactions that occur in these sediments are aerobic respiration and the reduction of Mn and Fe oxides. Under slower sedimentation conditions, there is sufficient time for particulate organic matter to decompose and create a diagenetic environment where metal oxides may not be stable. The quasi-steady-state interstitial Fe profiles from Tidal Potomac River sediments are an example of such a situation. This occurs primarily because the residence time of particles in the surficial sediment column is long enough to allow benthic organisms and bacteria to perform their metabolic functions. When faster sedimentation prevails, there is less time for these metabolic reactions to occur since the organisms do not occupy a sediment layer for any length of time. Also, the quantity and quality of the organic matter input to the sediment layer is important in that reservoirs often receive more terrestrial organic matter than natural lakes and this terrestrial organic matter is generally more refractory than autochthonous aquatic organic matter.
Urban settings are a focal point for environmental contamination due to emissions from industrial and municipal activities and the widespread use of motor vehicles. As part of the National Water-Quality Assessment Program of the U.S. Geological Survey, streambed-sediment and dated reservoir-sediment samples were collected from the Chattahoochee River Basin and analyzed for total lead (Pb) and zinc (Zn) concentrations. The sampling transect extends from northern Georgia, through Atlanta, to the Gulf of Mexico and reflects a steep gradient in population density from nearly 1000 people/km2 in the Atlanta Metropolitan Area to fewer than 50 people/km2 in rural areas of southern Georgia and northern Florida. Correlations among population density, traffic density, and total and anthropogenic Pb and Zn concentrations indicate that population density is strongly related to traffic density and is a predictor of Pb and Zn concentrations in the environment derived from anthropogenic activities. Differences in the distributions of total Pb and Zn concentrations along the urban-suburban-rural gradient from Atlanta to the Florida Panhandle are related to temporal and spatial processes. That is, with the removal of leaded gasoline starting in the late 1970s, peak Pb concentrations have decreased to the present. Conversely, increased vehicular usage has kept Zn concentrations elevated in runoff from population centers, which is reflected in the continued enrichment of Zn in aquatic sediments. Sediments from rural areas also contain elevated concentrations of Zn, possibly in response to substantial power plant emissions for the region, as well as vehicular traffic.
Benthic macroinvertebrates were collected during May 1997 from riffle habitats located in 7 streams within the Santa Clara Valley area. A total of 261 taxa were identified from 44 sites. In general, total taxon richness decreased from upstream to downstream sites. Sites located in most upland areas contained more taxa and higher percentage composition of the Orders Ephemeroptera, Plecoptera, and Trichoptera than sites from lowland areas. Sites located in lowland areas contained more taxa and higher percentage composition of taxa contained within the Chironomidae and Oligochaeta.
Broad-band acoustic Doppler current profilers (BB-ADCPs), in high resolution modes, have been shown to be very effective for studies of turbulent mean flow properties in the marine bottom boundary layer. The BB-ADCP is capable of measuring the velocity distribution in the bottom boundary layer, providing about 20-30 velocity points within 1.5 m from the sediment-water interface at a sampling rate slightly above 1 Hz. In this study, the potential of the high frequency sampling scheme of the BB-ADCP is explored. By saving single-ping velocity measurements, the turbulence properties of the bottom layer can be extracted from these measurements. Specifically, the high frequency velocity profiles are analyzed leading to direct measurements of turbulence properties of a bottom boundary layer in South San Francisco Bay, California. The objectives of this study are: 1) to explore techniques of measuring turbulence properties by a BB-ADCP; 2) to determine the Reynolds stress distribution in the bottom boundary layer from correlation of high frequency velocity components; 3) to compare the Reynolds stress with the bottom boundary layer properties deduced by conventional methods; and 4) to characterize the rate of vertical mixing in the water column based on these measurements. This investigation is moderately successful; some limitations of this approach have been identified for future consideration of improvements.
Rapid industrialization since the mid-19th century has produced a large quantity and a wide variety of chemical wastes. Many relatively non-biodegradable chemicals originating from these wastes have spread throughout the environment, into water, soil, and sediment. These chemicals may persist for indefinite periods, depending on their chemical properties and their interactions with the environment. Some of these chemicals are known to be harmful to humans and other species, either by direct exposure or by intake of contaminated water and food. Soils and sediments are important "sinks" for such contaminants because of their enormous quantities and their abilities to pick up, or sorb, large amounts of a wide variety of contaminants. It is essential to understand the mechanism by which the contaminant is sorbed to soil and sediment.
The sorption isotherms of ethylene dibromide (EDB), diuron (DUN), and 3,5-dichlorophenol (DCP) from water on the humic acid and humin fractions of a peat soil and on the humic-acid of a muck soil have been measured. The data were compared with those of the solutes with the whole peat from which the humic-acid (HA) and humin (HM) fractions were derived and on which the sorption of the solutes exhibited varying extents of nonlinear capacities at low relative concentrations (Ce/Sw). The HA fraction as prepared by the density-fractionated method is relatively pure and presumably free of high-surface-area carbonaceous material (HSACM) that is considered to be responsible for the observed nonlinear sorption for nonpolar solutes (e.g., EDB) on the peat; conversely, the base-insoluble HM fraction as prepared is presumed to be enriched with HSACM, as manifested by the greatly higher BET-(N2) surface area than that of the whole peat. The sorption of EDB on HA exhibits no visible nonlinear effect, whereas the sorption on HM shows an enhanced nonlinearity over that on the whole peat. The sorption of polar DUN and DCP on HA and HM display nonlinear effects comparable with those on the whole peat; the effects are much more significant than those with nonpolar EDB. These results conform to the hypothesis that adsorption onto a small amount of strongly adsorbing HSACM is largely responsible for the nonlinear sorption of nonpolar solutes on soils and that additional specific interactions with the active groups of soil organic matter are responsible for the generally higher nonlinear sorption of the polar solutes.
Developing a more thorough understanding of water and chemical budgets in wetlands depends in part on our ability to quantify time-varying interactions between ground water and surface water. We used a combined water and solute mass balance approach to estimate time-varying ground-water discharge and recharge in the Everglades Nutrient Removal project (ENR), a relatively large constructed wetland (1544 hectare) built for removing nutrients from agricultural drainage in the northern Everglades in South Florida, USA. Over a 4-year period (1994 through 1998), ground-water recharge averaged 13.4 hectare-meter per day (ha-m/day) or 0.9 cm/day, which is approximately 31% of surface water pumped into the ENR for treatment. In contrast, ground-water discharge was much smaller (1.4 ha-m/day, or 0.09 cm/day, or 2.8% of water input to ENR for treatment). Using a water-balance approach alone only allowed net ground-water exchange (discharge-recharge) to be estimated (-12±2.4 ha-m/day). Discharge and recharge were individually determined by combining a chloride mass balance with the water balance. For a variety of reasons, the ground-water discharge estimated by the combined mass balance approach was not reliable (1.4±37 ha-m/day). As a result, ground-water interactions could only be reliably estimated by comparing the mass-balance results with other independent approaches, including direct seepage-meter measurements and previous estimates using ground-water modeling. All three independent approaches provided similar estimates of average ground-water recharge, ranging from 13 to 14 ha-m/day. There was also relatively good agreement between ground-water discharge estimates for the mass balance and seepage meter methods, 1.4 and 0.9 ha-m/day, respectively. However, ground-water -flow modeling provided an average discharge estimate that was approximately a factor of four higher (5.4 ha-m/day) than the other two methods. Our study developed an initial understanding of how the design and operation of the ENR increases interactions between ground water and surface water. A considerable portion of recharged ground water (73%) was collected and returned to the ENR by a seepage canal. Additional recharge that was not captured by the seepage canal only occurred when pumped inflow rates to ENR (and ENR water levels) were relatively high. Management of surface water in the northern Everglades therefore clearly has the potential to increase interactions with ground water.
The fate of contaminants in streams and rivers is affected by exchange and biogeochemical transformation in slowly moving or stagnant flow zones that interact with rapid flow in the main channel. In a typical stream, there are multiple types of slowly moving flow zones in which exchange and transformation occur, such as stagnant or recirculating surface water as well as subsurface hyporheic zones. However, most investigators use transport models with just a single storage zone in their modeling studies, which assumes that the effects of multiple storage zones can be lumped together. Our study addressed the following question: Can a single-storage zone model reliably characterize the effects of physical retention and biogeochemical reactions in multiple storage zones? We extended an existing stream transport model with a single storage zone to include a second storage zone. With the extended model we generated 500 data sets representing transport of nonreactive and reactive solutes in stream systems that have two different types of storage zones with variable hydrologic conditions. The one storage zone model was tested by optimizing the lumped storage parameters to achieve a best fit for each of the generated data sets. Multiple storage processes were categorized as possessing I, additive; II, competitive; or III, dominant storage zone characteristics. The classification was based on the goodness of fit of generated data sets, the degree of similarity in mean retention time of the two storage zones, and the relative distributions of exchange flux and storage capacity between the two storage zones. For most cases (>90%) the one storage model described either the effect of the sum of multiple storage processes (category I) or the dominant storage process (category III). Failure of the one storage zone model occurred mainly for category II, that is, when one of the storage zones had a much longer mean retention time (ts ratio > 5.0) and when the dominance of storage capacity and exchange flux occurred in different storage zones. We also used the one storage zone model to estimate a "single" lumped rate constant representing the net removal of a solute by biogeochemical reactions in multiple storage zones. For most cases the lumped rate constant that was optimized by one storage zone modeling estimated the flux-weighted rate constant for multiple storage zones. Our results explain how the relative hydrologic properties of multiple storage zones (retention time, storage capacity, exchange flux, and biogeochemical reaction rate constant) affect the reliability of lumped parameters determined by one storage zone transport model. We conclude that stream transport models with a single storage compartment will in most cases reliably characterize the dominant physical processes of solute retention and biogeochemical reactions in streams with multiple storage zones.
An analysis of the pilot point method for automated calibration of an ensemble of conditionally simulated transmissivity fields was conducted on the basis of the simplifying assumption that the flow model is a linear function of log transmissivity. The analysis shows that the pilot point and conditional simulation method of model calibration and uncertainty analysis can produce accurate uncertainty measures if it can be assumed that errors of unknown origin in the differences between observed and model-computed water pressures are small. When this assumption is not met, the method could yield significant errors from overparameterization and the neglect of potential sources of model inaccuracy. The conditional simulation part of the method is also shown to be a variant of the percentile bootstrap method, so that when applied to a nonlinear model, the method is subject to bootstrap errors. These sources of error must be considered when using the method.
Increasingly, hydrologic studies require information on the isotopic composition of natural waters. This report presents stable hydrogen (d2H) and oxygen isotope ratios (d18O) of precipitation samples from seven selected sites of the National Oceanic and Atmospheric Administration's Atmospheric Integrated Research Monitoring Network (AIRMoN) collected during the years 1992-1994.
This report describes an experiment to make a completely non-contact open-channel discharge measurement. A van-mounted, pulsed Doppler (10 GHz) radar collected surface-velocity data across the 183-m wide Skagit River, Washington at a USGS streamgaging station using Bragg scattering from short waves produced by turbulent boils on the surface of the river. Surface velocities were converted to mean velocities for 25 sub-sections by assuming a normal open-channel velocity profile (surface velocity times 0.85). Channel cross-sectional area was measured using a 100 MHz ground-penetrating radar antenna suspended from a cableway car over the river. Seven acoustic Doppler current profiler discharge measurements and a conventional current-meter discharge measurement were also made. Three non-contact discharge measurements completed in about a 1-hour period were within 1% of the gaging station rating curve discharge values. With further refinements, it is thought that open-channel flow can be measured reliably by non-contact methods.
A combined geochemical and microbiological approach was needed to delineate the biogeochemical processes occurring in an aquifer contaminated by landfill leachate in Norman, OK, where the important microbially mediated reactions in an anoxic plume were iron reduction, sulfate reduction, and methanogenesis. The highest rates of sulfate reduction (13.2 µM/day) were detected near the water table where sulfate levels were maximal (up to 4.6 mM). The enrichment of 34S in the sulfate pools (d34S of SO4 2- was 67-690/00), and dissolved hydrogen measurements provided additional support for the importance of sulfate reduction near the water table. Methane was detected in the center of the plume where sulfate was depleted. Microbial incubations demonstrated concomitant sulfate reduction and methanogenesis in the anoxic portion of the plume. Although high concentrations of soluble reduced iron were detected throughout the aquifer and H2 levels were indicative of iron reduction under steady-state conditions, microbiological experiments showed that iron reduction was active only at the edges of the sulfate-depleted portion of the plume. This study demonstrates the benefits of using a combined geochemical and microbiological approach to elucidate the spatial distribution of biogeochemical processes in contaminated aquifers.
A field investigation of multispecies reactive transport was conducted in a well-characterized, sand and gravel aquifer on Cape Cod, Massachusetts. The aquifer is characterized by regions of differing chemical conditions caused by the disposal of secondary sewage effluent. Ten thousand liters of groundwater with added tracers (Br, Cr(VI), and EDTA complexed with Pb, Zn, Cu, and Ni) were injected into the aquifer and distributions of the tracers were monitored for 15 months. Most of the tracers were transported more than 200 m; transport was quantified using spatial moments computed from the results of a series of synoptic samplings. Cr(VI) transport was retarded relative to Br; the retardation factor varied from 1.1 to 2.4 and was dependent on chemical conditions. At 314 days after the injection, dissolved Cr(VI) mass in the tracer cloud had decreased 85%, with the likely cause being reduction to Cr(III) in a suboxic region of the aquifer. Transport of the metal-EDTA complexes was affected by aqueous complexation, adsorption, and dissolution-precipitation reactions of Fe oxyhydroxide minerals in the aquifer sediments. Dissolved Pb-EDTA complexes disappeared from the tracer cloud within 85 days, probably due to metal exchange reactions with Fe and adsorbed Zn (present prior to the injection from contamination by the sewage effluent). About 30% of the Cu-EDTA complexes remained within the tracer cloud 314 days after injection, even though the thermodynamic stability of the Pb-EDTA complex is greater than Cu-EDTA. It is hypothesized that stronger adsorption of Pb2+ to the aquifer causes the Pb-EDTA complex to disassociate to a greater degree than the Cu-EDTA complex. The mass of dissolved Zn-EDTA increased during the first 175 days of the tracer test to 140% of the mass injected, with the increase due to the desorption of sewage-derived Zn.
A new approach is presented to condition geostatistical simulation of high-permeability zones in fractured rock to hydraulic-connection data. A simulated-annealing algorithm generates three-dimensional (3-D) realizations conditioned to borehole data, inferred hydraulic connections between packer-isolated borehole intervals, and an indicator (fracture zone of background-K bedrock) variogram model of spatial variability. We apply the method to data from the U.S. Geological Survey Mirror Lake Site in New Hampshire, where connected high-permeability fracture zones exert a strong control on fluid flow at the hundred-meter scale. Single-well hydraulic-packer tests indicate the degree of hydraulic connection between boreholes. Borehole intervals connected by a fracture zone exhibit similar hydraulic responses, whereas intervals not connected by a fracture zone exhibit different responses. Our approach yields valuable insights into the 3-D geometry of fracture zones at Mirror Lake. Statistical analysis of the realizations yields maps of the probabilities of intersecting specific fracture zones with additional wells. Inverse flow modeling based on the assumption of equivalent porous media is used to estimate hydraulic conductivity and specific storage and to identify those fracture-zone geometries that are consistent with hydraulic test data.
Field experiments were conducted from 1992 to 1995 to estimate ground water recharge rates at two sites located within a 2.7-hectare agricultural field. The field lies in a sand plain setting in central Minnesota and is cropped continuously in field corn. The sites are located at a topographically high (upland) site and a topographically low (lowland) site in an effort to quantify the effects of depression focusing of recharge. Three site-specific methods were used to estimate recharge rates: well hydrograph analysis, chlorofluorocarbon age dating, and an unsaturated zone water balance. All three recharge methods indicated that recharge rates at the lowland site (annual average of all methods of 29 cm) exceeded those at the upland site (annual average of 18 cm). On an annual basis, estimates by the individual methods ranged from 12 to 44 percent of precipitation at the upland site and from 21 to 83 percent at the lowland site. The difference in recharge rates between the sites is primarily attributed to depression focusing of surface water runon at the lowland site. However, two other factors were also important: the presence of thin lamellae at the upland site, and coarser textured soils below a depth of 1.5 m at the lowland site.
Dettinger, M.D., Cayan, D.R., McCabe, G.J., and Marengo, J.A., 2000, Multiscale streamflow variability associated with El Niño/Southern Oscillation in Diaz, H.F., and Markgraf, V., eds., El Niño and the Southern Oscillation: New York, Cambridge University Press, p. 114-147.
Streamflow responses to the El Niño/Southern Oscillation (ENSO) phenomenon in the tropical Pacific are detectable in many regions. During warm-tropical El Niño and cool-tropical La Niña episodes, streamflows are affected throughout the Americas and Australia, in northern Europe, and in parts of Africa and Asia. In North and South America, correlations between peak-flow season streamflows and seasonal Southern Oscillation Indices (SOIs) show considerable persistence. In South America, correlations between flows in other seasons with December-February SOIs also are notably persistent, whereas, in North America, correlations are smaller when other, non-peak season time periods are considered.
At least two modes of streamflow response to ENSO are present in the Western Hemisphere. When interannual North and South American streamflow variations are analyzed together in a single principal components analysis, two of the leading components are found to be associated with ENSO climate variability. The more powerful of these modes corresponds mostly to ENSO responses by the rivers of tropical South America east of the Andes, along with rivers in southern South America and the southwestern United States, with Brazil experiencing less runoff during El Niños and the other regions experiencing more runoff. This streamflow mode is correlated globally with ENSO-like sea surface temperature (SST) patterns on both interannual and interdecadal timescales; indeed, the tropical South American rivers east of the Andes are coherent with SOI on virtually all historical timescales. The second ENSO-related streamflow mode characterizes other parts of extratropical streamflow variation, emphasizing the north-south differences in streamflows in North America during ENSO extremes and (less robustly) streamflow variations along the central Andes.
During more than 60 years, sedimentation on the Palos Verdes Shelf has been dominated by time-varying inputs of municipal wastewater from the Los Angeles County Sanitation Districts (LACSD) and debris from the Portuguese Bend Landslide (PBL). The present study examines the depositional history of wastewater-derived organic contaminants at a site approximately 6-8 km downcurrent from the outfall system. Sediments at this location are impacted by contributions from both sources, but the relative influence of the sources has changed over time. Two classes of hydrophobic organic contaminants (chlorinated hydrocarbons, long-chain alkylbenzenes) were determined in sediment cores collected in 1981 and 1992. Using molecular stratigraphy, we determined average sedimentation rates (cm/year) and mass accumulation rates (g cm-2year-1) for the following periods: 1955-1965, 1965-1971, 1971-1981 and 1981-1992. The results show that sedimentation and mass accumulation rates increased from 1955 to 1971 and decreased from 1971 to 1981. These trends are consistent with historical information on the emission of suspended solids from the outfall system, indicating that the discharge of wastes dominated sedimentation at the site during this period. In the 1980s and early 1990s, however, mass accumulation rates increased in spite of continually decreasing emissions of wastewater solids. Several lines of evidence indicate that this increase was due to mobilization of debris from the PBL during and after unusually strong winter storms in the 1980s. As a result, heavily contaminated sediments deposited during the years of greatest waste emissions (i.e., 1950-1970) have been buried to greater sub-bottom depths, thereby reducing their availability for mobilization to the overlying water column. These results highlight the dynamic nature of sedimentation in contaminated coastal ecosystems and its importance to the long-term fate and effects of toxic substances.
Municipal wastes discharged through deepwater submarine outfalls since 1937 have contaminated sediments of the Palos Verdes Shelf. A site approximately 6-8 km downcurrent from the outfall system was chosen for a study of the diagenetic fate of organic contaminants in the waste-impacted sediments. Concentrations of three classes of hydrophobic organic contaminants (DDT+metabolites, polychlorinated biphenyls (PCBs), and the long-chain alkylbenzenes) were determined in sediment cores collected at the study site in 1981 and 1992. Differences between the composition of effluent from the major source of DDT (Montrose Chemical) and that found in sediments suggests that parent DDT was transformed by hydrolytic dehydrochlorination during the earliest stages of diagenesis. As a result, p,p'-DDE is the dominant DDT metabolite found in shelf sediments, comprising 60-70% of Sigma DDT. The p,p-DDE/p,p'-DDMU concentration ratio decreases with increasing sub-bottom depth in sediment cores, indicating that reductive dechlorination of p,p'-DDE is occurring. Approximately 9-23% of the DDE inventory in the sediments may have been converted to DDMU since DDT discharges began ca. 1953. At most, this is less than half of the decline in p,p'-DDE inventory that has been observed at the study site for the period 1981-1995. Most of the observed decrease is attributable to remobilization by processes such as sediment mixing coupled to resuspension, contaminant desorption, and current advection. Existing field data suggest that the in situ rate of DDE transformation is 102 -103 times slower than rates determined in recent laboratory microcosm experiments (Quensen, J.F., and others, 1998, Reductive dechlorination of DDE to DDMU in marine sediment microcosms, Science, 280, 722-724). This explains why the DDT composition (that is, o,p'-, p,p'-isomers of DDE, DDD, DDT) of sediments from this site have not changed significantly since at least 1972. Congener-specific PCB compositions in shelf sediments are highly uniform and show no evidence of diagenetic transformation. Apparently, the agents /factors responsible for reductive dechlorination of DDE are not also effecting alteration of the PCBs. Two types of long-chain alkylbenzenes were found in the contaminated sediments. Comparison of chain length and isomer distributions of the linear alkylbenzenes in wastewater effluent and surficial sediment samples indicate that these compounds undergo biodegradation during sedimentation. Further degradation of the linear alkylbenzenes occurs after burial despite relatively invariant isomer compositions. The branched alkylbenzenes are much more persistent than the linear alkylbenzenes, presumably due to extensive branching of the alkyl side chain. Based on these results, p,p'-DDE, PCBs, and selected branched alkylbenzenes are sufficiently persistent for use in molecular stratigraphy. The linear alkylbenzenes may also provide information on depositional processes. However, their application as quantitative molecular tracers should be approached with caution.
In five tributary streams (four inflowing and one outflowing) of 1600-ha Trout Lake in northern Wisconsin, USA, we examined factors that can affect the magnitude of stream flow and transport of dissolved organic and inorganic carbon (DOC and DIC) through the streams to the lake. One catchment, the Allequash Creek basin, was investigated in more detail to describe the dynamics of carbon flow and to identify potential carbon sources. Stream flows and carbon loads showed little or no relation to surface-water catchment area. They were more closely related to ground-water watershed area because ground-water discharge, from both local and regional sources, is a major contributor to the hydrologic budgets of these catchments. An important factor in determining carbon influx to the stream is the area of peatland in the catchment. Peatland porewaters contain DOC concentrations up to 40 mg/l and are a significant potential carbon source. Ground-water discharge and lateral flow through peat are the suspected mechanisms for transport of that carbon to the streams. Carbon and nitrogen isotopes suggested that the sources of DOC in Allequash Creek above Allequash Lake were wetland vegetation and peat and that the sources below Allequash Lake were filamentous algae and wild rice. Catchments with high proportions of peatland, including the Allequash Creek catchment, tended to have elevated DOC loads in outflowing stream water. Respiration and carbon mineralization in lakes within the system tend to produce low DOC and low DOC/DIC in lake outflows, especially at Trout Lake. In Allequash Lake, however, the shallow peat island and vegetation-filled west end were sources of DOC. Despite the vast carbon reservoir in the peatlands, carbon yields were very low in these catchments. The small yields were attributable to low stream flows due to lack of significant overland runoff and very limited stream channel coverage of the total catchment area.
Significant uptake of dissolved metals occurred by interaction of groundwater and surface water with hyporheic-zone sediments during transport in Pinal Creek, AZ. The extent of trace metal uptake was calculated by mass balance measurements made directly within the hyporheic zone. A conservative solute tracer injected into the stream was used to quantify hydrologic exchange with the stream and groundwater. Fractional reactive uptake of dissolved metals entering the hyporheic zone was determined at 29 sites and averaged 52 ± 25, 27 ± 19, and 36 ± 24% for Co, Ni, and Zn, compared with Mn uptake of 22 ±19%. First-order rate constants (lh)of metal uptake in the hyporheic zone were determined at seven sites using the exchange rate of water derived from tracer arrival in the streambed. Reaction-time constants (1/lh) averaged 0.41, 0.84, and 0.38 h for Co, Ni, and Zn, respectively, and 1.3 h for Mn. In laboratory experiments with streambed sediments, metal uptake increased with preexisting Mn oxide concentration, supporting our interpretation that Mn oxides in the hyporheic zone enhance trace metal uptake. Reach-scale mass-balance calculations that include groundwater metal inputs indicated that decreases in metal loads ranged from 12 to 68% over the 7-km perennial reach depending on the metal. The decreases in metal loads are attributed to uptake of trace metals by Mn oxides in the hyporheic zone that is enhanced because of ongoing Mn oxide formation. Analysis of dissolved-metal streambed profiles and conservative solute tracers provide a valuable tool for quantifying metal uptake or release in the hyporheic zone of contaminated streams.
Three long-range forecasting methods have been evaluated for prediction and downscaling of seasonal and intraseasonal precipitation statistics in California. Full-statistical, hybrid-dynamical-statistical and full-dynamical approaches have been used to forecast El Niño-Southern Oscillation (ENSO)-related total precipitation, daily precipitation frequency, and average intensity anomalies during the January-March season. For El Niño winters, the hybrid approach emerges as the best performer, while La Niña forecasting skill is poor. The full-statistical forecasting method features reasonable forecasting skill for both La Niña and El Niño winters. The performance of the full-dynamical approach could not be evaluated as rigorously as that of the other two forecasting schemes. Although the full-dynamical forecasting approach is expected to outperform simpler forecasting schemes in the long run, evidence is presented to conclude that, at present, the full-dynamical forecasting approach is the least viable of the three, at least in California. The authors suggest that operational forecasting of any intraseasonal temperature, precipitation, or streamflow statistic derivable from the available records is possible now for ENSO-extreme years.
The effect of simultaneous competitive speciation of dissolved rare earth elements (REEs) in acidic waters (pH 3.3 to 5.2) has been evaluated by applying the PHREEQE code to the speciation of water analyses from Spain, Brazil, USA, and Canada. The main ions that might affect REE are Al3+, F-, SO42-, and PO43-. Fluoride, normally a significant complexer of REEs, is strongly associated with Al3+ in acid waters and consequently has little influence on REEs. The inclusion of aluminum concentrations in speciation calculations for acidic waters is essential for reliable speciation of REEs. Phosphate concentrations are too low (10-4 to 10-7 m) to affect REE speciation. Consequently, SO42- is the only important complexing ligand for REEs under these conditions. According to Millero [Millero, F.J., 1992. Stability constants for the formation of rare earth inorganic complexes as a function of ionic strength: Geochimica et Cosmochimica Acta, v. 56, p. 3123-3132], the lanthanide sulfate stability constants are nearly constant with increasing atomic number so that no REE fractionation would be anticipated from aqueous complexation in acidic waters. Hence, REE enrichments or depletions must arise from mass transfer reactions.
A series of experiments was performed to evaluate the extent to which Cd, Co, Ag, Se, Cr, and Zn bound to sediments with different geochemical properties could be assimilated by the mussel Mytilus edulis and the clam Macoma balthica. Oxidized and reduced radiolabeled sediments were fed to suspension-feeding animals, the depuration patterns of the individuals were followed by gamma -spectrometry, and the assimilation efficiencies (AEs) of ingested metals were determined. AEs from geochemically diverse sediments typically varied less than 2-fold and ranged from 1% for Cr to 42% for Zn. Metals were assimilated from anoxic sediment by both animals; Ag, Cd, and Co AEs in M. balthica were 9-16%, 2-fold lower than from oxic sediment, but in M. edulis AEs were about two times greater from anoxic sediment for all metals but Ag. For oxic sediment, Cd and Co AEs in M. edulis decreased 3-4-fold with increased sediment exposure time to the metals with smaller but significant effects also noted for Zn and Se but not Ag. A less pronounced decrease in AE for M. balthica was evident only after 6 months exposure time. Sequential extractions of the oxidized sediments showed a transfer of metals into more resistant sediment components over time, but the rate did not correlate with a decrease in metal AEs. Comparing the two bivalves, TOC concentrations had an inconsistent effect on metal AEs. AEs of metals from bacteria-coated glass beads were slightly higher than from humic acid-coated beads, which were comparable with whole-sediment AEs. There was correspondence of AE with desorption of Ag, Cd, Co, and Se (but not Zn) from sediments into pH 5 seawater, measured to simulate the gut pH of these bivalves. The results imply that metals associated with sulfides and anoxic sediments are bioavailable, that the bioavailability of metals from sediments decreases over exposure time, that organic carbon content generally has a small effect on AEs, and that AEs of sediment-bound metals differ among species.
Efficient biodegradation of subsurface contaminants requires two elements: (1) microbial populations with the necessary degradative capabilities, and (2) favorable subsurface geochemical and hydrological conditions. Practical constraints on experimental design and interpretation in both the hydrogeological and microbiological sciences have resulted in limited knowledge of the interaction between hydrogeological and microbiological features of subsurface environments. These practical constraints include: (1) inconsistencies between the scales of investigation in the hydrogeological and microbiological sciences, and (2) practical limitations on the ability to accurately define microbial populations in environmental samples. However, advances in application of small-scale sampling methods and interdisciplinary approaches to site investigations are beginning to significantly improve understanding of hydrogeological and microbiological interactions. Likewise, culture-based and molecular analyses of microbial populations in subsurface contaminant plumes have revealed significant adaptation of microbial populations to plume environmental conditions. Results of recent studies suggest that variability in subsurface geochemical and hydrological conditions significantly influences subsurface microbial-community structure. Combined investigations of site conditions and microbial-community structure provide the knowledge needed to understand interactions between subsurface microbial populations, plume geochemistry, and contaminant biodegradation.
Haeni, F.P., Buursink, M.L., Costa, J.E., Melcher, N.B., Cheng, R.T., Plant, W.J., 2000, Ground-penetrating radar methods used in surface-water discharge measurements, in Noon, D.A., Stickley, G.F., Longstaff, D., eds., Eighth International Conference On Ground Penetrating Radar: SPIE, v. 4084, p. 494-500.
The U.S. Geological Survey (USGS) operates a network of about 7,000 streamflow-gaging stations that monitor open-channel water discharge at locations throughout the United States. The expense, technical difficulties, and concern for the safety of operational personnel under some field conditions have led to the search for alternate measurement methods. Ground-penetrating radar (GPR) has been used by the USGS in hydrologic, geologic, environmental, and bridge-scour studies by floating antennas on water or mounting antennas in boats. GPR methods were developed to measure and monitor remotely the cross-sectional area of rivers by suspending a 100-megahertz (MHz) radar antenna from a cableway car or bridge at four unstable streams that drained the slopes of Mount St. Helens in Washington. Based on the success of these initial efforts, an experiment was conducted in 1999 to see if a combination of complementary radar methods could be used to calculate the discharge of a river without having any of the measuring equipment in the water. The cross-sectional area of the 183-meter (m) wide Skagit River in Washington State was measured using a GPR system with a single 100-MHz antenna suspended 0.5 to 3 m above the water surface from a cableway car. A van-mounted, side-looking pulsed-Doppler (10 gigahertz) radar system was used to collect water-surface velocity data across the same section of the river. The combined radar data sets were used to calculate the river discharge and the results compared closely to the discharge measurement made by using the standard in-water measurement techniques. The depth to the river bottom, which was determined from the GPR data by using a radar velocity of 0.04 meters per nanosecond in water, was about 3 m, which was within 0.25 m of the manually measured values. Upon the successful completion of this experiment, the USGS designed two additional experiments to measure surface-water discharge remotely. One planned experiment will be conducted in the eastern United States using a multi-frequency mono-static radar system located on one bank of the river. The other planned experiment will be conducted in the western United States using a multi-frequency bi-static radar system with the transmitter on one riverbank and the receiver on the opposite bank.
The data presented in this report are products of an investigation that quantified interactions between ground water and surface water in Taylor Slough in Everglades National Park. Determining the extent of hydrologic interactions between wetland surface water and ground water in Taylor Slough is important because the balance of freshwater flow in the lower part of the Slough is uncertain. Although freshwater flows through Taylor Slough are quite small in comparison to Shark Slough (the larger of the two major sloughs in Everglades National Park), flows through Taylor Slough are especially important to the ecology of estuarine mangrove embayments of northeastern Florida Bay. Also, wetland and ground-water interactions must be quantified if their role in affecting water quality is to be determined. In order to define basic hydrologic characteristics of the wetland, depth of wetland peat was mapped, and hydraulic conductivity and vertical hydraulic gradients in peat were determined. During specific time periods representing both wet and dry conditions in the area, the distribution of major ions, nutrients, and water stable isotopes throughout the slough were determined. The purpose of chemical measurements was to identify an environmental tracer could be used to quantify ground-water discharge.
Simulated daily precipitation, temperature, and runoff time series were compared in three mountainous basins in the United States: (1) the Animas River basin in Colorado, (2) the East Fork of the Carson River basin in Nevada and California, and (3) the Cle Elum River basin in Washington State. Two methods of climate scenario generation were compared: delta change and statistical downscaling. The delta change method uses differences between simulated current and future climate conditions from the Hadley Centre for Climate Prediction and Research (HadCM2) General Circulation Model (GCM) added to observed time series of climate variables. A statistical downscaling (SDS) model was developed for each basin using station data and output from the National Center for Environmental Prediction/National Center for Atmospheric Research (NCEP/NCAR) reanalysis regridded to the scale of HadCM2. The SDS model was then used to simulate local climate variables using HadCM2 output for current and future conditions. Surface climate variables from each scenario were used in a precipitation-runoff model. Results from this study show that, in the basins tested, a precipitation-runoff model can simulate realistic runoff series for current conditions using statistically downscaled NCEP output. But, use of downscaled HadCM2 output for current or future climate assessments are questionable because the GCM does not produce accurate estimates of the surface variables needed for runoff in these regions. Given the uncertainties in the GCMs ability to simulate current conditions based on either the delta change or downscaling approaches, future climate assessments based on either of these approaches must be treated with caution.
Reduction of selenium oxyanions by microorganisms is an important process in the biogeochemical cycling of selenium. Numerous bacteria can reduce Se oxyanions, which are used as electron acceptors during the oxidation of organic matter in anoxic environments. In this study, we used a double spike (82Se and 74Se) thermal ionization mass spectrometry technique to quantify the isotopic fractionation achieved by three different species of anaerobic bacteria capable of accomplishing growth by respiratory reduction of selenate [SeO42- or Se(VI)] or selenite [SeO32- or Se(IV)] to Se(IV) or elemental selenium [Se(0)] coupled with the oxidation of lactate. Isotopic discrimination in these closed system experiments was evaluated by Rayleigh fractionation equations and numerical models. Growing cultures of Bacillus selenitireducens, a haloalkaliphile capable of growth using Se(IV) as an electron acceptor, induced a 80Se/76Se fractionation of -8.0 ± 0.40/00 (instantaneous e value) during reduction of Se(IV) to Se(0). With Bacillus arsenicoselenatis, a haloalkaliphile capable of growth using Se(VI) as an electron acceptor, fractionations of -5.0 ± 0.50/00 and -6.0 ± 1.00/00 were observed for reduction of Se(VI) to Se(IV) and reduction of Se(IV) to Se(0), respectively. In growing cultures of Sulfurospirillum barnesii, a freshwater species capable of growth using Se(VI), fractionation was small initially, but near the end of the log growth phase, it increased to -4.0 ± 1.00/00 and -8.4 ± 0.40/00 for reduction of Se(VI) to Se(IV) and reduction of Se(IV) to Se(0), respectively. Washed cell suspensions of S. barnesii induced fractionations of -1.1 ± 0.40/00 during Se(VI) reduction, and -9.1 ± 0.5% for Se(IV) reduction, with some evidence for smaller values (e.g., -1.70/00) in the earliest-formed Se(0) results. These results demonstrate that dissimilatory reduction of selenate or selenite induces significant isotopic fractionation, and suggest that significant Se isotope ratio variation will be found in nature.
The crystallization of calcium carbonate minerals plays an integral role in the water chemistry of terrestrial ecosystems. Humic substances, which are ubiquitous in natural waters, have been shown to reduce or inhibit calcite crystal growth in experiments. The purpose of this study is to quantify and understand the kinetic effects of hydrophobic organic acids isolated from the Florida Everglades and a fulvic acid from Lake Fryxell, Antarctica, on the crystal growth of calcite (CaCO3). Highly reproducible calcite growth experiments were performed in a sealed reactor at constant pH, temperature, supersaturation (W = 4.5), PCO2 (10-3.5atm), and ionic strength (0.1 M) with various concentrations of organic acids. Higher plant-derived aquatic hydrophobic acids from the Everglades were more effective growth inhibitors than microbially derived fulvic acid from Lake Fryxell. Organic acid aromaticity correlated strongly with growth inhibition. Molecular weight and heteroatom content correlated well with growth inhibition, whereas carboxyl content and aliphatic nature did not.
Hoch, A.R., Reddy, M.M., and Heymans, M.J., 2000, Transient calcite fracture fillings in a welded tuff, Snowshoe Mountain, Colorado: Applied Geochemistry, v. 15, no.10, p.1495-1504.
The core from two boreholes (13.1 and 19.2 m depth) drilled 500 m apart in the fractured, welded tuff near the summit of the Snowshoe Mountain, Colorado (47o30'N, 106o55'W) had unique petrographic and hydrodynamic properties. Borehole SM-4 had highly variable annual water levels, in contrast to SM-1a, whose water level remained near the land surface. Core samples from both boreholes (n = 10 and 11) were examined petrographically in thin sections impregnated with epoxy containing rhodamine to mark the pore system features, and were analyzed for matrix porosity and permeability. Core from the borehole sampling the vadose zone was characterized by open fractures with enhanced porosity around phenocrysts due to chemical weathering. Fractures within the borehole sampling the phreatic zone were mineralized with calcite and had porosity characteristics similar to unweathered and unfractured rock. At the top of the phreatic zone petrography indicates that calcite is dissolving, thereby changing the hydrogeochemical character of the rock (i.e. permeability, porosity, reactive surface area, and mineralogy). Radiocarbon ages and C and O stable isotopes indicate that calcite mineralization occurred about 30 to 40 ka ago and that there was more than one mineralization event. Results of this study also provide some relationships between primary porosity development from 3 types of fracture in a welded tuff.
Hornberger, M.I., Luoma, S.N., Cain, D., Parchaso, F., Brown, C., Bouse, R., Wellise, C., and Thompson, J., 2000, Linkage of bioaccumulation and biological effects to changes in polutant loads in South San Francisco Bay: Environmental Science and Technology, v. 34, p. 2401-2409.
The developed world had invested billions of dollars in waste treatment since the 1970s; however, changes in ecological of biological responses are rarely associated with reductions in metal pollutants. Here we present a novel, 23-yr time series of environmental change from a San Francisco Bay mudflat located 1 km from the discharge of a suburban domestic sewage treatment plant. Samples of surface sediment, the bioindicator Macoma balthica, and metals loading data were used to establish links between discharge, bioaccumulation, and effects. Mean annual Ag concentrations in M. balthica were 106 mg/g in 1978 and 3.67mg/g in 1998. Concentrations of Cu declined from 287 mg/g in 1980 to a minimum of 24 mg/g in 1991. Declining Cu bioaccumulation was strongly correlated with decreasing Cu loads from the plant between 1977 and 1998. Relationships with bioaccumulation and total annual precipitation suggested that inputs from nonpoint sources were most important in controlling Zn bioavailability during the same period. Ecoepidemiological criteria were used to associate failed gamete production in M. balthica to a metals-enriched environment. Reproduction persistently failed between the mid-1970s and mid-1980s; it recovered after metal contamination declined. Other potential environmental causes such as food availability, sediment chemistry, or seasonal salinity fluctuations were not related to the timing of the change in reproductive capability. The results establish an associative link, suggesting that it is important to further investigate the chemical interference of Cu and/or Ag with invertebrate reproduction at relatively moderate levels of environmental contamination.
Huntington, T.G., Hooper, R.P., Johnson, C.E., Aulenbach, B.T., Cappellato, R., and Blum, A.E., 2000, Calcium depletion in a Southeastern United States forest ecosystem: Soil Science Society of America Journal, v. 64, no. 5, p. 1845-1858.
Forest soil Ca depletion through leaching and vegetation uptake may threaten long-term sustainability of forest productivity in the southeastern USA. This study was conducted to assess Ca pools and fluxes in a representative southern Piedmont forest to determine the soil Ca depletion rate. Soil Ca storage, Ca inputs in atmospheric deposition, and outputs in soil leaching and vegetation uptake were investigated at the Panola Mountain Research Watershed (PMRW) near Atlanta, GA. Average annual outputs of 12.3 kg ha-1 yr-1 in uptake into merchantable wood and 2.71 kg ha-1 yr-1 soil leaching exceeded inputs in atmospheric deposition of 2.24 kg ha-1 yr-1. The annual rate of Ca uptake into merchantable wood exceeds soil leaching losses by a factor of more than five. The potential for primary mineral weathering to provide a substantial amount of Ca inputs is low. Estimates of Ca replenishment through mineral weathering in the surface 1 m of soil and saprolite was estimated to be 0.12 kg ha-1 yr-1. The weathering rate in saprolite and partially weathered bedrock below the surface 1 m is similarly quite low because mineral Ca is largely depleted. The soil Ca depletion rate at PMRW is estimated to be 12.7 kg ha-1 yr-1. At PMRW and similar hardwood-dominated forests in the Piedmont physiographic province, Ca depletion will probably reduce soil reserves to less than the requirement for a merchantable forest stand in 80 yr. This assessment and comparable analyses at other southeastern USA forest sites suggests that there is a strong potential for a regional problem in forest nutrition in the long term.
Rivers of the coastal plain of the south-eastern USA are characteristically low-gradient meandering systems that develop broad floodplains subjected to frequent and prolonged flooding. These floodplains support a relatively unique forested wetland (bottomland hardwoods), which have received considerable ecological study, but distinctly less hydrogeomorphological study. The hydroperiod, or annual period of inundation, largely controls the development of characteristic fluvial landforms, sediment deposition and vegetation distribution patterns. Order-of-magnitude differences in wetted perimeter, width/depth, suspended sediment load and hydraulic roughness may exist between dry in-channel seasons and the hydroperiod. Substantial sediment (and adsorbed contaminants) retention and storage through lateral and vertical accretion is common (where not heavily impacted by flow regulation) along these Coastal Plain rivers. The present chapter summarizes our current understanding of the hydrology, fluvial geomorphology, general and local sedimentation patterns, and related plant ecological patterns of these Coastal Plain bottomlands.
Hutchinson, G.L., Livingston, G.P., Healy, R.W., and Striegl, R.G., 2000, Chamber measurement of surface-atmosphere trace gas exchange: Numerical evaluation of dependence on soil interfacial layer, and source/sink products: Journal of Geophysical Research, v. 105, no. D7, p. 8865-8875.
We employed a three-dimensional finite difference gas diffusion model to simulate the performance of chambers used to measure surface-atmosphere trace gas exchange. We found that systematic errors often result from conventional chamber design and deployment protocols, as well as key assumptions behind the estimation of trace gas exchange rates from observed concentration data. Specifically, our simulations showed that (1) when a chamber significantly alters atmospheric mixing processes operating near the soil surface, it also nearly instantaneously enhances or suppresses the postdeployment gas exchange rate, (2) any change resulting in greater soil gas diffusivity, or greater partitioning of the diffusing gas to solid or liquid soil fractions, increases the potential for chamber-induced measurement error, and (3) all such errors are independent of the magnitude, kinetics, and/or distribution of trace gas sources, but greater for trace gas sinks with the same initial absolute flux. Finally, and most importantly, we found that our results apply to steady state as well as non-steady-state chambers, because the slow rate of gas diffusion in soil inhibits recovery of the former from their initial non-steady-state condition. Over a range of representative conditions, the error in steady state chamber estimates of the trace gas flux varied from -30 to +32%, while estimates computed by linear regression from non-steady-state chamber concentrations were 2 to 31% too small. Although such errors are relatively small in comparison to the temporal and spatial variability characteristic of trace gas exchange, they bias the summary statistics for each experiment as well as larger scale trace gas flux estimates based on them.
This report presents data on the physical properties of unsaturated alluvial deposits and on the chemical and isotopic composition of soil water and soil gas collected at 12 monitoring sites in the western part of the Mojave Desert, near Victorville, California. Sites were installed using the ODEX air-hammer method. Seven sites were located in the active channels of Oro Grande and Sheep Creek Washes. The remaining five sites were located away from the active washes. Most sites were drilled to a depth of about 100 feet below land surface; two sites were drilled to the water table almost 650 feet below land surface. Drilling procedures, lithologic and geophysical data, and site construction and instrumentation are described. Core material was analyzed for water content, bulk density, water potential, particle size, and water retention. The chemical composition of leachate from almost 1,000 subsamples of cores and cuttings was determined. Water extracted from selected subsamples of cores was analyzed for tritium and the stable isotopes of oxygen and hydrogen. Water from suction-cup lysimeters and soil-gas samples also were analyzed for chemical and isotopic composition. In addition, data on the chemical and isotopic composition of bulk precipitation from five sites and on ground water from two water-table wells are reported.
Previous studies indicated that small amounts of recharge occur as infiltration of intermittent streamflow in washes in the upper Mojave River basin, in the western Mojave Desert, near Victorville, California. These washes flow only a few days each year after large storms. To reach the water table, water must pass through an unsaturated zone that is more than 130 m thick. Results of this study, done in 1994-1998, show that infiltration to depths below the root zone did not occur at control sites away from the wash. At these sites, volumetric water contents were as low as 0.01 and water potentials (measured as the combination of solute and matric potentials using a water activity meter) were as negative as -14,000 kPa. Water-vapor movement was controlled by highly negative solute potentials associated with the accumulation of soluble salts in the unsaturated zone. Highly negative matric potentials above and below the zone of maximum solute accumulation result from movement of water vapor toward the highly negative solute potentials at that depth. The d18O and dD isotopic composition of water in coarse-grained deposits plots along a Rayleigh distillation line consistent with removal of water in coarse-grained layers by vapor transport. Beneath Oro Grande Wash, water moved to depths below the root zone and, presumably, to the water table about 130 m below land surface. Underneath Oro Grande Wash, volumetric water contents were as high as 0.27 and water potentials (measured as matric potential using tensiometers) were between -1.8 and -50 kPa. On the basis of tritium data, water requires at least 180-260 years to infiltrate to the water table. Clay layers impede the downward movement of water. Seasonal changes in water vapor composition underneath the wash are consistent with the rapid infiltration of a small quantity of water to great depths and subsequent equilibration of vapor with water in the surrounding material. It may be possible to supplement natural recharge from the wash with imported water. Recharge to the wash may be advantageous because the unsaturated zone is not as dry as most areas in the desert and concentrations of soluble salts are generally lower underneath the wash.
In the past decade, there has been a growing interest of dam safety officials to incorporate a risk-based analysis for design-flood hydrology. Extreme or rare floods, with probabilities in the range of about .01 to .000001 chance of occurrence per year, are of continuing interest to the hydrologic and engineering communities for purposes of planning and design of structures such as dams [National Research Council, 1988]. The National Research Council stresses that as much information as possible about floods needs to be used for evaluation of the risk and consequences of any decision. A regional interdisciplinary paleoflood approach was developed to assist dam safety officials and flood plain managers in their assessments of the risk of large floods. The interdisciplinary components included documenting maximum paleofloods and a regional analyses of contemporary extreme rainfall and flood data to complement a site-specific probable maximum precipitation study [Tomlinson and Solak, 1997]. The cost-effective approach, which can be used in many other hydrometeorologic settings, was applied to Elkhead Reservoir in Elkhead Creek (531 km2) in northwestern Colorado; the regional study area was 10,900 km2. Paleoflood data using bouldery flood deposits and noninundation surfaces for 88 streams were used to document maximum flood discharges that have occurred during the Holocene. Several relative dating methods were used to determine the age of paleoflood deposits and noninundation surfaces. No evidence of substantial flooding was found in the study area. The maximum paleoflood of 135 m3s-1 for Elkhead Creek is about 13% of the site-specific probable maximum flood of 1020 m3s-1. Flood-frequency relations using the expected moments algorithm, which better incorporates paleoflood data, were developed to assess the risk of extreme floods. Envelope curves encompassing maximum rainfall (181 sites) were developed for northwestern Colorado to help define maximum contemporary and Holocene flooding in Elkhead Creek and in a regional frequency context. Study results for Elkhead Reservoir were accepted by the Colorado State Engineer for dam safety certification.
Jassby, A.D., and Cloern, J.E., 2000, Primary food resources in the Sacramento-San Joaquin Delta: Newsletter, Interagency Ecological Program for the Sacremento-San Joaquin Estuary, Summer 2000, p. 21-25.
A look at temporal and spatial variability, points out sources differ with water year and season. Spatial heterogeneity implies that the relative importance of various sources will differ among subregions of the Delta. The results demonstrate that flow management has profound effects on the supply of organic matter to Suisun Bay, an important nursery area for larval fish. Results indicate that restoration efforts need a better understanding of Delta ecology and the underlying processes.
Selenium stable isotope ratios can serve as indicators of Se sources and reduction of Se oxyanions, much as sulfur and nitrogen isotope ratios do in sulfur and nitrogen biogeochemical studies. A new analytical method, which allows precise Se isotope ratio measurements on 500 ng of Se, greatly enhances analysis of environmental samples. This paper presents the first environmental study to use Se stable isotopes. 80Se/76Se ratios, relative to a provisional standard, were measured in water, oil refinery wastewater, total sediment digests, and sediment extracts from the Carquinez area in the San Francisco Bay Estuary. Se isotope ratios in total sediment Se and in extracts designed to recover Se0 are slightly (about 20/00) enriched in the lighter isotope relative to local bay water Se. This difference is smaller than the isotopic fractionations expected upon reduction of Se(VI) or Se(IV) to Se(0) and suggests that reduction of soluble selenium from the overlying waters is not the dominant process by which Se is incorporated into the sediments. Consistent isotopic differences between riverine and refinery inputs with Se isotopes are not possible in this system.
Preferential flow paths are expected in many groundwater systems and must be located because they can greatly affect contaminant transport. The fundamental characteristics of radiogenic isotope ratios in chemically evolving waters make them highly effective as preferential flow path indicators. These ratios tend to be more easily interpreted than solute-concentration data because their response to water-rock interaction is less complex. We demonstrate this approach with groundwater 87Sr/86Sr ratios in the Snake River Plain aquifer within and near the Idaho National Engineering and Environmental Laboratory. These data reveal slow-flow zones as lower 87Sr/86Sr areas created by prolonged interaction with the host basalts and a relatively fast flowing zone as a high 87Sr/86Sr area.
Two types of regional-scale seawater circulation have been proposed to explain the formation of Enewetak Atoll dolomites: geothermal and reflux circulation. We have used a finite element groundwater flow model to examine the pattern, magnitude and dynamic interaction of these two different circulation mechanisms in Enewetak Atoll. Geothermal circulation is concentrated around the atoll-margin whereas refluxing mesosaline brines flow from the atoll interior towards the margin to restrict and eventually shut off geothermal circulation. Refluxing brines of 36-80 per mil can account for the salinity signature recorded in dolomite fluid inclusions. Distributions of fluid flux and Mg mass-balance calculations suggest that both geothermal and reflux circulation mechanisms could account for the observed distribution of dolomite in Enewetak Atoll. Furthermore, the atoll interior may be extensively dolomitized as observed in other atolls.
Norris-Mammoth corridor is a complex subsidence structure that extends approximately 40 km northward from the 0.6 Ma Yellowstone caldera, and contains many hydrothermal features with high fluid discharges totaling approximately 1000 l/s. About 150-250 l/s of hydrothermal water, which attains boiling temperature at surface and 360 oC at depth, discharge from the Norris Geyser Basin, adjacent to the caldera. The highest thermal water and gas discharges in the corridor are from Mammoth Hot Springs, where 500-600 l/s thermal water with surface temperatures of up to 73 oC and calculated subsurface temperatures of approximately 100 oC issue from approximately 100 hot springs scattered over a score of step-like travertine terraces that range in age from approximately 0.4 Ma to recent. All the thermal water is meteoric, likely recharged in the Gallatin Range at 2.5-3.0 km elevations. The isotopic and chemical compositions of thermal waters and solutes can be interpreted to indicate a common magmatic source for heat and volatile solutes located near Norris. However, the chemical and isotopic compositions of gases, especially the He/4He ratios, provide strong evidence for a separate magmatic source for the Mammoth system.
Calcite crystal growth experiments were undertaken to test a recently proposed model that relates crystal growth mechanisms to the shapes of crystal size distributions (CSDs). According to this approach, CSDs for minerals have three basic shapes: (1) asymptotic, which is related to a crystal growth mechanism having constant-rate nucleation accompanied by surface-controlled growth; (2) lognormal, which results from decaying-rate nucleation accompanied by surface-controlled growth; and (3) a theoretical, universal, steady-state curve attributed to Ostwald ripening. In addition, there is a fourth crystal growth mechanism that does not have a specific CSD shape, but which preserves the relative shapes of previously formed CSDs. This mechanism is attributed to supply-controlled growth.
All three shapes were produced experimentally in the calcite growth experiments by modifying nucleation conditions and solution concentrations. The asymptotic CSD formed when additional reactants were added stepwise to the surface of solutions that were supersaturated with respect to calcite (initial W = 20, where W = 1 represents saturation), thereby leading to the continuous nucleation and growth of calcite crystals. Lognormal CSDs resulted when reactants were added continuously below the solution surface, via a submerged tube, to similarly supersaturated solutions (initial W = 22 to 41), thereby leading to a single nucleation event followed by surface-controlled growth. The Ostwald CSD resulted when concentrated reactants were rapidly mixed, leading initially to high levels of supersaturation (W >100), and to the formation and subsequent dissolution of very small nuclei, thereby yielding CSDs having small crystal size variances.
The three CSD shapes likely were produced early in the crystallization process, in the nanometer crystal size range, and preserved during subsequent growth. Preservation of the relative shapes of the CSDs indicates that a supply-controlled growth mechanism was established and maintained during the constant-composition experiments. CSDs having shapes intermediate between lognormal and Ostwald also were generated by varying the initial levels of supersaturation (initial W = 28.2 to 69.2) in rapidly mixed solutions.
Lognormal CSDs were observed for natural calcite crystals that are found in septarian concretions occurring in southeastern Colorado. Based on the model described above, these CSDs indicate initial growth by surface control, followed by supply-controlled growth. Thus, CSDs may be used to deduce crystal growth mechanisms from which geologic conditions early in the growth history of a mineral can be inferred. Conversely, CSD shape can be predicted during industrial crystallization by applying the appropriate conditions for a particular growth mechanism.
The influence of the presence of humic, fulvic, and polyacrylic acid on the nucleation and crystal growth of calcium carbonate in aqueous supersaturated solutions was investigated in batch reactors at 250C and pH =8.50. The nucleation of calcium carbonate was investigated by free drift methods, and the crystal growth was investigated with seeded crystal growth experiments at constant supersaturation. In all cases calcite was found to form exclusively, and the presence of all tested compounds at concentrations between 0.1 - 1.0 ppm prolonged the induction time preceding the spontaneous formation of calcite. Humic acid at concentration up to 0.5 ppm inhibited the growth of calcite seeds up to 95% and polyacrylic acid at concentrations up to 0.1 ppm gave the same degree of inhibition. Polyacrylic acid was found to be stronger inhibitor. A concentration of 0.25 ppm of polyacrylic acid completely stopped crystal growth of calcite. Humic acid at concentration 1.0 ppm completely stopped crystal growth of calcite seed crystals. The retardation was explained by the adsorption of the polyelectrolytes onto the active growth sites of the crystals. Application of a Langmuir-type adsorption model on the kinetics data obtained in the presence of the inhibitors tested yielded a higher affinity constant of polyacrylic acid for the calcite seed crystals.
Tar residues are common on the coastline of the Monterey Bay National Marine Sanctuary. These coastal tar residues have been washed ashore and usually occur on headlands near the high-tide line. In this study, 18 coastal tar residues were collected and analyzed to determine their carbon isotopic compositions and the values of selected biomarker ratios. All of the residues have very heavy (13C-enriched) carbon isotopic compositions spanning a narrow range (d13C = -22.2 to -23.4%), and 28,30-bisnorhopane is present in all samples. These same geochemical characteristics are found in Monterey Formation oils from which the coastal tar residues were likely derived. These coastal residues could result from natural seeps or from accidental spills. Statistically the coastal tar residues can be organized into three groups, each of which may represent different spill or seep events. Seven samples of potential local representative sources for the tar residues were examined, but none could account for the coastal tars.
Much attention in the radiological health community has recently focused on the management and regulation of naturally occurring radioactive materials. Although uranium-bearing minerals are present in a variety of fluorspar deposits, their potential consideration as naturally occurring radioactive materials has received only limited recognition. The uranium content of 28 samples of acid- and cryolite-grade (>97% CaF2) fluorspar from the National Defense Stockpile was found to range from 120 to 24,200 mg kg-1, with a mean of 2,145 mg kg-1. As a point of comparison, the average concentration of uranium in the upper crust of the earth is about 2,500 mg kg-1. Leachability of this uranium was assessed by means of the Toxicity Characteristic Leaching Procedure (TCLP). The TCLP extractable fraction ranged from 1 to 98%, with a mean of 24% of the total uranium. The typically low concentrations of uranium seen in these materials probably reflects the removal of uranium-bearing mineral phases during the beneficiation of the crude fluorspar ore to achieve industrial specifications. Future NORM studies should examine crude fluorspar ores and flotation tailings.
Understanding how animals are exposed to the large repository of metal pollutants in aquatic sediments is complicated and is important in regulatory decisions. Experiments with four types of invertebrates showed that feeding behavior and dietary uptake control bioaccumulation of cadmium, silver, nickel, and zinc. Metal concentrations in animal tissue correlated with metal concentrations extracted from sediments, but not with metal in porewater, across a range of reactive sulfide concentrations, from 0.5 to 30 micromoles per gram. These results contradict the notion that metal bioavailability in sediments is controlled by geochemical equilibration of metals between porewater and reactive sulfides, a proposed basis for regulatory criteria for metals.
Lee, B.-G., Lee, J.-S., Luoma, S.N., Choi, H.J., and Koh, C.-H., 2000, Influence of acid volatile sulfides and metal concentrations on metal bioavailability to marine invertebrates in contaminated sediments: Environmental Science and Technology, v. 34, p. 4517-4523.
An 18-day microcosm study was conducted to evaluate the influence of acid volatile sulfides (AVS) and metal additions on bioaccumulation from sediments of Cd, Ni, and Zn in two clams (Macoma balthica and Potamocorbula amurensis) and three marine polychaetes (Neanthes arenaceodentata, Heteromastus filiformis, and Spiophanes missionensis). Manipulation of AVS by oxidation of naturally anoxic sediments allowed use of metal concentrations typical of nature and evaluation of processed important to chronic metal exposure. A vertical sediment column similar to that often found in nature was used to facilitate realistic biological behavior. Results showed that AVS or porewater (PW) metals conrolled biaccumulation in only 2 of 15 metal-animal combinations. Bioaccumulation of all three metals by the bivalves was related significantly to metal concentrations extracted from sediments (SEM) but not to [SEM - AVS] of PW metals. SEM predominantly influenced bioaccumulation of Ni and Zn in N. arenaceodenata, but Cs bioaccumulation followed PW Cd concentrations. SEM controlled tissue concentrations of all three metals in H. filiformis and S. missionensis, with minor influences from metal-sulfide chemistry. Significant bioaccumulation occurred when SEM was only a small fraction of AV in several treatments. Three factors appeared to contribute to the differences between these bioaccumulation results and the results from toxicity tests reported previously: differences in experimental design, dietary uptake, and biological attributes of the species, including mode and depth of feeding.
The influence of acid volatile sulfide (AVS) on the partitioning of Cd, Ni, and Zn in porewater (PW) and sediment as reactive metals (SEM, simultaneously extracted metals) was investigated in laboratory microcosms. Two spiking procedures were compared, and the effects of vertical geochemical gradients and infaunal activity were evaluated. Sediments were spiked with a Cd-Ni-Zn mixture (0.06, 3, 7.5 mmol/g, respectively) containing four levels of AVS (0.5, 7.5, 15, 35 mmol/g). A vertical redox gradient was generated in each treatment by an 18-d incubation with an oxidized water column. [AVS] in the surface sediments decreased by 65-95% due to oxidation during incubation; initial [AVS] was maintained at 0.5-7.5 cm depth. PW metal concentrations were correlated with [SEM-AVS] among all data. But PW metal concentrations were variable, causing the distribution coeffiecient, Kdpw (the ratio of [SEM] to PW metal concentrations) to vary 2-3 orders of magnitude at a given {SEM-AVS]. One reason for the variability was that vertical profiles in PW metal concentrations appeared to be influenced by diffusion as well as [SEM-AVS]. The presence of animals appeared to enhance the diffusion of at least Zn. The generalization that PW metal concentrations are controlled by [SEM-AVS] is subject to some important qualifications if vertical gradients are complicated, metal concentrations vary, or equilibrium times differ.
U.S. Geological Survey (USGS) hydrologists and ecologist are conducting studies to quantify vegetative flow resistance in order to improve numerical models of surface-water flow in the Florida Everglades. Water-surface slope is perhaps the most difficult of the flow resistance parameters to measure in the Everglades due to the very low gradients of the topography and flow. In an effort to measure these very small slopes, a unique pipe manometer was developed for the local measurement of water-surface slopes on the order of 1 centimeter per kilometer (cm/km). According to theory, a very precise measurement of centerline velocity obtained inside the pipe manometer should serve as a unique proxy for water-surface slope in the direction of the pipe axis. In order to confirm this theoretical relationship and calibrate the pipe manometer, water-surface elevation and pipe centerline velocity data were simultaneously measured in a set of experiments carried out in the tilting flume at the USGS Hydraulic Laboratory Facility at Stennis Space Center, Mississippi. A description of the instrumentation and methods used to evaluate this technique for measuring water-surface slope as well as a summary of the entire data set is presented.
Historic fire suppression efforts have increased the likelihood of large wildfires in much of the western U.S. Post-fire soil erosion and sedimentation risks are important concerns to resource managers. In this paper we develop and apply procedures to predict post-fire erosion and sedimentation risks on a pixel-, catchment-, and landscape-scale in central and western Colorado.
Our model for predicting post-fire surface erosion risk is conceptually similar to the Revised Universal Soil Loss Equation (RUSLE). One key addition is the incorporation of a hydrophobicity risk index (HYRISK) based on vegetation type, predicted fire severity, and soil texture. Post-fire surface erosion risk was assessed for each 90-m pixel by combining HYRISK, slope, soil erodibility, and a factor representing the likely increase in soil wetness due to removal of the vegetation. Sedimentation risk was a simple function of stream gradient. Composite surface erosion and sedimentation risk indices were calculated and compared across the 72 catchments in the study area.
When evaluated on a catchment scale, two-thirds of the catchments had relatively little post-fire erosion risk. Steeper catchments with higher fuel loadings typically had the highest post-fire surface erosion risk. These were generally located along the major north-south mountain chains and, to a lesser extent, in west-central Colorado. Sedimentation risks were usually highest in the eastern part of the study area where a higher proportion of streams had lower gradients. While data to validate the predicted erosion and sedimentation risks are lacking, the results appear reasonable and are consistent with our limited field observations. The models and analytic procedures can be readily adapted to other locations and should provide useful tools for planning and management at both the catchment and landscape scale.
We examined microbial methylmercury (MeHg) degradation in sediment of the Florida Everglades, Carson River (NV), and San Carlos Creek (CA), three freshwater environments that differ in the extent and type of mercury contamination, and sediment biogeochemistry. Degradation rate constant (kdeg) values increased with total mercury (Hgt) contamination both among and within ecosystems. The highest kdeg's (2.8-5.8 d-1) were observed in San Carlos Creek, at acid mine drainage impacted sites immediately downstream of the former New Idria mercury mine, where Hgt ranged from 4.5-21.3 ppm (dry wt.). A reductive degradation pathway (presumably mer-detoxification) dominated degradation at these sites, as indicated by the nearly exclusive production of 14CH4 from 14C-MeHg, under both aerobic and anaerobic conditions. At the upstream control site, and in the less contaminated ecosystems (e.g. the Everglades), kdeg's were low (less than or equal to 0.2 d-1) and oxidative demethylation (OD) dominated degradation, as evident from 14CO2 production. kdeg increased with microbial CH4 production, organic content and reduced sulfur in the Carson River system, and increased with decreasing pH in San Carlos Creek. OD associated CO2 production increased with pore-water SO4-2 in Everglades samples, but was not attributable to anaerobic methane oxidation, as has been previously proposed. This ecosystem comparison indicates that severely contaminated sediments tend to have microbial populations that actively degrade MeHg via mer-detoxification, whereas OD occurs in heavily contaminated sediments as well, but dominates in those less contaminated.
Two extensive plumes (combined area >1000 km2) have been delineated within the Ogallala aquifer in the Southern High Plains, TX, USA. Salinity varies within the plumes spatially and increases with depth; Cl ranges from 50 to >500 mg/l. Variable-density flow modeling using SUTRA has identified three broad regions of upward cross-formational flow from the underlying evaporite units. The upward discharge within the modeled plume area is in the range of 10-4 to 10-5 m3/day, and the TDS concentrations are typically >3000 mg/l . Regions of increased salinity, identified within the Whitehorse Group (evaporite unit) underlying the Ogallala aquifer, are controlled by the structure and thickness variations relative to the recharge areas. Distinct flow paths, on the order of tens of km to >100 km in length, and varying flow velocities indicate that the salinization of the Ogallala aquifer has been a slow, ongoing process and may represent circulation of waters recharged during Pleistocene or earlier times. On-going pumping has had negligible impact on the salinity distribution in the Ogallala aquifer, although simulations indicate that the velocity distribution in the underlying units may have been affected to depths of 150 m after 30 years of pumping. Because the distribution of saline ground water in this region of the Ogallala aquifer is heterogeneous, careful areal and vertical characterization is warranted prior to any well-field development.
Sulphur 35, a cosmogenically produced radioisotope with a short half-life (87 days), was measured in snowpack during 1993-1997 and at four locations within the Loch Vale watershed during 1995-1997. The four sites include the two main drainages in the watershed, Andrews Creek and Icy Brook, a small south facing catchment flowing into Andrews Creek (Andrews Spring I), and a similar north facing catchment flowing out of a scree field into Icy Brook (Spring 19). Concentrations ranged from a high of almost 50 mBq/L for a sample from Spring 19 in June 1996 to a concentration near the detection limit for a sample from Andrews Creek in April 1997. Sulphur 35 concentrations were normalized to sulphate (as mBq/mg SO4-2) and were decay-corrected to a Julian day of 90 (April 1) for each year. Snowpack had the highest 35S concentration with an average concentration of 53 mBq/mg SO4-2. Concentrations in the streams were much lower, even when corrected for decay relative to JD 90. The large 35S concentrations found in Spring 19 were the result of increases in concentration due to sublimation and/or evapotranspiration and were lower than snowpack when normalized to sulphate. Using 35S concentrations found in snowpack as of JD 90 as a beginning concentration, the fraction of sulphate in streamflow that was derived from atmospheric deposition within the prior water year was estimated. For Icy Brook and Andrews Creek the fraction of the sulphate in streamflow derived from that year?s snowpack and precipitation was low prior to the beginning of the main spring melt, reached a maximum during the period of maximum flow, and decreased as the summer progressed. A calculation of the seasonal flux indicated that about 40% of the sulphate that flowed out of the watershed was derived from atmospheric sulphate deposited during the previous year. This suggests that more than half of the sulphate deposited in the watershed by atmospheric processes during the previous year was removed during the following summer. Thus sulphate retention in alpine watersheds like Loch Vale is very limited, and changes in sulphate deposition should be quickly reflected in stream chemistry.
Laplace transform step-response functions are presented for various homogeneous confined and leaky aquifer types and for anisotropic, homogeneous unconfined aquifers interacting with perennial streams. Flow is one-dimensional, perpendicular to the stream in the confined and leaky aquifers, and two-dimensional in a plane perpendicular to the stream in the water-table aquifers. The stream is assumed to penetrate the full thickness of the aquifer. The aquifers may be semi-infinite or finite in width and may or may not be bounded at the stream by a semipervious streambank. The solutions are presented in a unified manner so that mathematical relations among the various aquifer configurations are clearly demonstrated. The Laplace transform solutions are inverted numerically to obtain the real-time step-response functions for use in the convolution (or superposition) integral. To maintain linearity in the case of unconfined aquifers, fluctuations in the elevation of the water table are assumed to be small relative to the saturated thickness, and vertical flow into or out of the zone above the water table is assumed to occur instantaneously. Effects of hysteresis in the moisture distribution above the water table are therefore neglected. Graphical comparisons of the new solutions are made with known closed-form solutions. (also see abstract for Barlow, DiSimone, and Moench, above)
Moody, J.A., Sullivan, J.F., and Taylor, H.E., 2000, Effects of the flood of 1993 on the chemical characteristics of bed sediments in the Upper Mississippi River: Water, Air, and Soil Pollution, v. 117, p. 329-351.
Concentrations of pollutants stored in the surficial bed sediments in the navigation pools of the Upper Mississippi River showed a general decrease after the record flood of 1993. Percent clay and total organic carbon in the surficial sediments decreased as a result of an increase in the proportion of coarser sediment. Decreases in pollutant concentration may have been a result of the dilution by coarser and relatively less polluted sediment that was mobilized and transported into the Upper Mississippi River from its tributaries or from mainstem locations upstream but outside of the sampling area.
The acoustic televiewer is a geophysical logging instrument that is deployed in a water-filled borehole and operated while trolling. It generates a digital, magnetically oriented image of the borehole wall that is developed from the amplitudes and transit times of acoustic waves emitted from the tool and reflected at the water-wall interface. The transit-time data are also converted to radial distances, from which cross-sectional views of the borehole shape can be constructed. Because the televiewer is equipped with both a three-component magnetometer and a two-component inclinometer, the borehole?s trajectory in space is continuously recorded as well. This instrument is routinely used in mining and hydrogeologic applications, but in this investigation it was deployed in two boreholes drilled into Upper Fremont Glacier, Wyoming, USA. The acoustic images recorded in this glacial setting are not as clear as those typically obtained in rocks, due to a lower reflection coefficient for water and ice than for water and rock. Results indicate that the depth and orientation of features intersecting the boreholes can be determined, but that interpreting their physical nature is problematic and requires corroborating information from inspection of cores. Nevertheless, these data can provide some insight into englacial structural characteristics. Additional information derived from the cross-sectional geometry of the borehole, as well as from its trajectory, may also be useful in studies concerned with stress patterns and deformation processes.
The Brunswick Group and the underlying Lockatong Formation are composed of lithified Mesozoic sediments that constitute part of the Newark Basin in southeastern Pennsylvania. These fractured rocks form an important regional aquifer that consists of gradational sequences of shale, siltstone, and sandstone, with fluid transport occurring primarily in fractures. An extensive suite of geophysical logs was obtained in seven wells located at the borough of Lansdale, Pennsylvania, in order to better characterize the areal hydrogeologic system and provide guidelines for the refinement of numerical ground water models. Six of the seven wells are approximately 120 m deep and the seventh extends to a depth of 335 m. Temperature, fluid conductivity, and flowmeter logs are used to locate zones of fluid exchange and to quantify transmissivities. Electrical resistivity and natural gamma logs together yield detailed stratigraphic information, and digital acoustic televiewer data provide magnetically oriented images of the borehole wall from which almost 900 fractures are identified. Analyses of the geophysical data indicate that the aquifer penetrated by the deep well can be separated into two distinct structural domains, which may, in turn, reflect different mechanical responses to basin extension by different sedimentary units: 1. In the shallow zone (above 125 m), the dominant fracture population consists of gently dipping bedding plane partings that strike N46 degree E and dip to the northwest at about 11 degrees. Fluid flow is concentrated in the upper 80 m along these subhorizontal fractures, with transmissivities rapidly diminishing in magnitude with depth. 2. The zone below 125 m marks the appearance of numerous high-angle fractures that are orthogonal to the bedding planes, striking parallel but dipping steeply southeast at 77 degrees. This secondary set of fractures is associated with a fairly thick (approximately 60 m) high-resistivity, low-transmissivity sandstone unit that is abruptly terminated by a thin shale bed at a depth of 190 m. This lower contact effectively delineates the aquifer's vertical extent at this location because no detectable evidence of ground water movement is found below it. Thus, fluid flow is controlled by fractures, but fracture type and orientation are related to lithology. Finally, a transient thermal-conduction model is successfully applied to simulate observed temperature logs, thereby confirming the effects of ground-surface warming that occurred in the area as a result of urbanization at the turn of the century. The systematic warming of the upper 120 m has increased the transmissivity of this aquifer by almost 10%, simply due to changes in fluid viscosity and density.
Qualitative and quantitative methods to process benthic macroinvertebrate (BMI) samples have been developed and tested by the U.S. Geological Survey's National Water Quality Laboratory Biological Group. The qualitative processing method is based on visually sorting a sample for up to 2 hours. Sorting focuses on attaining organisms that are likely to result in taxonomic identifications to lower taxonomic levels (for example, Genus or Species). Immature and damaged organisms are also sorted when they are likely to result in unique determinations. The sorted sample remnant is scanned briefly by a second person to determine if obvious taxa were missed. The quantitative processing method is based on a fixed-count approach that targets some minimum count such as 100 or 300 organisms. Organisms are sorted from randomly selected 5.1- by 5.1-centimeter parts of a gridded subsampling frame. The sorted remnant from each sample is resorted by a second individual for at least 10 percent of the original sort time. A large-rare organism search is performed on the unsorted remnant to sort BMI taxa that were not likely represented in the sorted grids. After either qualitatively or quantitatively sorting the sample, BMIs are identified by using one of three different types of taxonomic assessment. The Standard Taxonomic Assessment is comparable to the U.S. Environmental Protection Agency Rapid Bioassessment Protocol III and typically provides Genus- or Species-level taxonomic resolution. The Rapid Taxonomic Assessment is comparable to the U.S. Environmental Protection Agency Rapid Bioassessment Protocol II and provides Family-level and higher taxonomic resolution. The Custom Taxonomic Assessment provides Species-level resolution whenever possible for groups identified to higher taxonomic levels by using the Standard Taxonomic Assessment. The consistent use of standardized designations and notes facilitates the interpretation of BMI data within and among water-quality studies. Taxonomic identifications are quality assured by verifying all referenced taxa and randomly reviewing 10 percent of the taxonomic identifications performed weekly by Biological Group taxonomists. Taxonomic errors discovered during this review are corrected. BMI data are reviewed for accuracy and completeness prior to release. BMI data are released phylogenically in spreadsheet format and unprocessed abundances are corrected for laboratory and field subsampling when necessary.
Molecular weight (MW) of humic materials is a key factor controlling proton and metal binding and organic pollutant partitioning. Several studies have suggested preferential adsorption of higher MW, more aromatic moieties to mineral surfaces; quantification of such processes is fundamental to development of predictive models. We used high pressure size exclusion chromatography (HPSEC) to quantify MW changes upon adsorption of a muck fulvic acid (MFA) extracted from a peat deposit to kaolinite and goethite, at pH 3.7, 6, and 8 at 22 8C, I 5 0.01 (NaCl), 24-h reaction time. MFA adsorption affinity was greater for goethite than for kaolinite. At concentrations less than the adsorption maximum (Amax) for both adsorbents, the weight-average MW (Mw) of MFA remaining in solution decreased by as much as several hundred Daltons relative to control samples, indicating preferential adsorption of the higher MW components. At concentrations more than Amax, Mw of MFA in solution did not change appreciably. Although total adsorption decreased significantly as pH increased, fractionation as measured by change in Mw remained similar, perhaps indicating greater selectivity for higher MW components at higher pH.
We collected samples monthly, from April to August 1998, to measure the abundance of autotrophic picoplankton in San Francisco Bay. Samples taken along a 160-km transect showed that picocyanobacteria (Synechococcus sp.) was a persistent component of the San Francisco Bay phytoplankton in all the estuarine habitats, from freshwater to seawater and during all months of the spring-summer transition. Abundance ranged from 4.6 ± 106 to 5.2 ± 108 cells L-1, with peak abundance during the spring bloom (April and May) and during July with a persistent spatial pattern of smallest abundance near the coastal ocean and highest abundance in the landward domains of the estuary. The picocyanobacterial component (as estimated percentage of chlorophyll a concentration) was, on average, 15% of total phytoplankton biomass during the summer-autumn nonbloom periods and only 2% of chlorophyll biomass during the spring bloom. This result is consistent with the emerging concept of a gradient of increasing importance of picocyanobacteria along the gradient of decreasing nutrient concentrations from estuaries to the open ocean.
The last decade has witnessed a plethora of research related to the hydrogeochemistry and microbiology of acid mine waters and associated tailings and waste-rock waters. Numerous books, reviews, technical papers, and proceedings have been published that examine the complex biogeochemical process of sulfide mineral oxidation, develop and apply geochemical models to site characterization, and characterize the microbial ecology of these environments. This review summarizes many of these recent works, and provides references for those investigating this field. Comparisons of measured versus calculated Eh and measured versus calculated pH for water samples from several field sites demonstrate the reliability of some current geochemical models for aqueous speciation and mass balances. Geochemical models are not, however, used to predict accurately time-dependent processes but to improve our understanding of these systems and to constrain possible processes that contribute to actual or potential water quality issues. Microbiological studies are demonstrating that there is much we have yet to learn about the types of different microorganisms and their function and ecology in mine-waste environments. A broad diversity of green algae, bacteria, arcaea, yeasts, and fungi are encountered in acid mine waters, and a better understanding of their ecology and function may potentially enhance remediation possibilities as well as our understanding of the evolution of life.
Nordstrom, D.K., 2000, An overview of arsenic mass-poisoning in Bangladesh and West Bengal, India, in Young, C., ed., Minor elements 2000, processing and environmental aspects of As, Sb, Se, Te, and Bi: Society for Mining, Metallurgy, and Exploration, p. 21-30.
The largest mass poisoning in the world, perhaps in history, is happening in West Bengal, India, and Bangladesh. Many thousands of people suffer from arsenic skin disorders and are dying from cancer. About 19 million are estimated to be at risk. The discovery of the arsenic poisoning from tubewell drinking water was made in 1983, but it took about 10 years to be formally recognized as a large-scale problem. The source of the arsenic is natural and three hypotheses have been proposed for its mobilization: oxidation of arsenian pyrite, reductive iron dissolution with release of adsorbed arsenic, and competitive adsorption from phosphate. The processes causing arsenic mobilization in the Bengal Delta are still poorly understood and further research is needed to design long-term remediation strategies.
Extremely acidic mine waters with pH values as low as -3.6, total dissolved metal concentrations as high as 200 g/L, and sulfate concentrations as high as 760 g/L, have been encountered underground in the Richmond Mine at Iron Mountain, CA. These are the most acidic waters known. The pH measurements were obtained by using the Pitzer method to define pH for calibration of glass membrane electrodes. The calibration of pH below 0.5 with glass membrane electrodes becomes strongly nonlinear but is reproducible to a pH as low as -4. Numerous efflorescent minerals were found forming from these acid waters. These extreme acid waters were formed primarily by pyrite oxidation and concentration by evaporation with minor effects from aqueous ferrous iron oxidation and efflorescent mineral formation. In this paper, it is demonstrated that pH can be defined and measured below 0.0 and that waters of such low pH exist in nature.
The stratified (meromictic) water column of alkaline and hypersaline Mono Lake, California, contains high concentrations of dissolved inorganic arsenic (approximately 200 mmol/L). Arsenic speciation changes from arsenate [As (V)] to arsenite [As (III)] with the transition from oxic surface waters (mixolimnion) to anoxic bottom waters (monimolimnion). A radioassay was devised to measure the reduction of 73(V) to 73As (III) and tested using cell suspensions of the As (V)-respiring Bacillus selenitireducens, which completely reduced the 73As (V). In field experiments, no significant activity was noted in the aerobic mixolimnion waters, but reduction of 73As (V) to 73As (III) was observed in all the monimolimnion samples. Rate constants ranged from 0.02 to 0.3/day, with the highest values in the samples from the deepest depths (24 and 28 m). The highest activities occurred between 18 and 21 m, where As (V) was abundant (rate, approximately 5.9 mmol/L per day). In contrast, sulfate reduction occurred at depths below 21 m, with the highest rates attained at 28 m (rate, approximately 2.3 mmol/L per day). These results indicate that As (V) ranks second in importance, after sulfate, as an electron acceptor for anaerobic bacterial respiration in the water column. Annual arsenate respiration may mineralize as much as 14.2% of the pelagic photosynthetic carbon fixed during meromixis. When combined with sulfate-reduction data, anaerobic respiration in the water column can mineralize 32-55% of this primary production. As lakes of this type approach salt saturation, As (V) can become the most important electron acceptor for the biogeochemical cycling of carbon
.Osterkamp, W.R., 2000, Earth-surface processes, materials use , and urban development -- a case study of the San Juan metropolitan area, northeastern Puerto Rico, in Scanlon K.M., and Briere, P.R., eds., Puerto Rico marine sediments, terrestrial and seafloor imagery and tectonic interpretations: U.S. Geological Survey Open-File Report 00-006 (CD).
A joint SCOPE-IUGS project, ESPROMUD, sets out to evaluate the effects of urbanisation and extractive industries on earth surface processes and landforms, critically appraise existing knowledge and identify gaps in understanding of these transformations. This project will establish the spatial extent and volume of landforms deliberately being created by human action and the volumes of sediment directly or indirectly produced by people's activities. The major contributors to these increases in earth surface transformation, which are now comparable in rate with those created by natural processes, are the extractive activities and mineral processing, as well as construction activities linked to urban and infrastructure development. To define the nature and assess the effects of those changes an approach based on the use of a generalized conceptual model, two "activities models", mining and urbanization, and two "systems models", fluvial and coastal, will be used. The general aim of this project is thus to quantify and describe the magnitude of these direct and indirect people-driven changes; to evaluate their influence on the work of geomorphological processes; to assess their consequences for the environment and people; and to make recommendations concerning advisable practices in order to improve the sustainability of urban and extractive activities. In brief, to establish the environmental footprint of cities and extractive activities and to define guidelines to reduce it. The background of the project will be presented, as well as its objectives and the methodology and models used.
A numerical model is used to predict flow along intervals between producing zones in open boreholes for comparison with measurements of borehole flow. The model gives flow under quasi-steady conditions as a function of the transmissivity and hydraulic head in an arbitrary number of zones communicating with each other along open boreholes. The theory shows that the amount of inflow to or outflow from the borehole under any one flow condition may not indicate relative zone transmissivity. A unique inversion for both hydraulic-head and transmissivity values is possible if flow is measured under two different conditions such as ambient and quasi-steady pumping, and if the difference in open-borehole water level between the two flow conditions is measured. The technique is shown to give useful estimates of water levels and transmissivities of two or more water-producing zones intersecting a single interval of open borehole under typical field conditions. Although the modeling technique involves some approximation, the principle limit on the accuracy of the method under field conditions is the measurement error in the flow log data. Flow measurements and pumping conditions are usually adjusted so that transmissivity estimates are most accurate for the most transmissive zones, and relative measurement error is proportionately larger for less transmissive zones. The most effective general application of the borehole-flow model results when the data are fit to models that systematically include more production zones of progressively smaller transmissivity values until model results show that all accuracy in the data set is exhausted.
Paillet, F. L., and Hanscomb, H., 2000, Borehole geophysical characterinzation of hydraulic stimulation of fractured bedrock aquifers, in Powers, M.H., Ibrahim, A-B., and Cramer, L., eds., Proceedings of the symposium on the application of geophysics to engineerng and environmental problems, Feb 20-24, 2000: Wheat Ridge, Colo., Environmental and Engineering Geophysical Society, p. 567-576.
Changes induced by typical hydraulic stimulation procedures were monitored in two adjacent boreholes at a site in northeastern Maine by comparing geophysical well logs run before and after stimulation. Caliper and acoustic televiewer logs run before stimulation indicated a few faint, impermeable-looking horizontal and vertical fractures, but inflow before treatment was too weak to detect with a heat-pulse flowmeter. Caliper and televiewer logs run after stimulation showed no significant differences compared to the pre-stimulation logs. Flow logs run after stimulation demonstrate that inflow in both boreholes is associated with a faint horizontal fracture on the televiewer logs near 60 m in depth, which appears no different from several other similar fractures. A cross-borehole flow experiment confirms that the stimulated zone is a single horizontal fracture connecting the two boreholes. These results demonstrate that the hydraulic stimulation produced at least a 10-fold increase in well capacity from less than 0.5 to more than 5.0 liters per minute. The results also agree with previous studies where fractures affected by timulation: 1) were present before treatment; 2) showed no obvious changes in the immediate vicinity of the borehole after stimulation; and 3) experienced a 10 to 20 fold increase in permeability attributed to the treatment.
Caliper, gamma, normal resistivity, fluid column temperature and resistivity, and televiewer logs were combined borehole flow logs to infer the nature of water-producing intervals in six observation boreholes at sites in southeastern Minnesota. Flow profiles were obtained with either the electromagnetic or heat-pulse flowmeters, depending upon equipment availability at the time of logging. Gamma and resistivity logs were used to determine the stratigraphic position of open intervals in each of the boreholes. Water-producing intervals identified using the flowmeter logs were characterized as permeable coarse-clastic beds, solution openings along bedding planes, fractures, or karstic horizons on the basis of gamma, caliper, and televiewer logs. Flow log interpretation theory demonstrates that the hydraulic head and transmissivity of water-producing intervals intersecting an open borehole can be estimated if flow logs are obtained under two different quasi-steady conditions, and if the difference in open-borehole water level between the two conditions can be measured. If logistical conditions prevent flow logging under more than one condition, water-producing zones can be identified but relative transmissivity values cannot be estimated. If flow logs are obtained under two different flow conditions, but the drawdown between the two conditions cannot be measured, relative transmissivity can be estimated where the zone transmissivity values are given in percent of total borehole transmissivity. Of the six boreholes logged in this study, two different flow logs could be obtained at four sites, and drawdown could be measured at two sites. Thus, quantitative estimates of zone transmissivity and hydraulic head were obtained at the Faribault and Rochester sites, relative permeability profiles were obtained at the Savage and Austin sites, and limited information about water-producing zones in the Faribault borehole, with transmissivity values ranging from about 100 to about 1000 ft2/day, and with hydraulic-head variations of about 2.4 feet within the open borehole interval. The model results indicate four water-producing zones in the Rochester borehole, with transmissivity values ranging from about 10 to almost 500ft2/day, and with head variations of about 2.0 feet in the open borehole interval.
Integration of lithologic logs, geophysical logs, and hydraulic tests is critical in characterizing heterogeneous aquifers. Typically only a limited number of aquifer tests can be performed, and these need to be designed to provide hydraulic properties for the principle aquifers in the system. This study describes the integration of logs and aquifer tests in the development of a hydrostratigraphic model for the surficial aquifer system in and around Big Cypress National Preserve in eastern Collier County, Florida. Borehole flowmeter tests provide qualitative permeability profiles in most of 26 boreholes drilled in the study area. Flow logs indicate the depth of transmissive units, which are correlated across the study area. Comparison to published studies in adjacent areas indicates that the main limestone aquifer of the Tamiami Formation in the study area corresponds with the gray limestone aquifer in western Dade County and the water table and lower Tamiami Aquifer in western Collier County. Four strategically located, multiwell aquifer tests are used to quantify the qualitative permeability profiles provided by the flowmeter log analysis. The hydrostratigraphic model based on these results defines the main aquifer in the central part of the study area as unconfined to semiconfined with a transmissivity as high as 30,000 m2/day. The aquifer decreases in transmissivity to less than 10,000 m2/day in some parts of western Collier County, and becomes confined to the east and northeast of the study area, where transmissivity decreases to below 5000 m2/day.
A heat-pulse flowmeter was used in six drainage wells in Kuwait City for flow profiling under both ambient and pumping conditions. The data collected were used in: (a) estimating the cross-flow among the screened intervals under ambient conditions; (b) estimating the relative transmissivity adjacent to the individual screen zones; and (c) determination of the hydraulic heads at the far boundaries of the large-scale aquifer zones. These inferences were cross-checked against known hydrogeology of the aquifer-aquitard system in the study area, and the calibration results of numerical flow modeling. The major conclusions derived from the flow measurements were: (a) the presence of natural downward cross-flow under ambient condition supported the hypothesis that the upper part of the Kuwait Group aquifer in the study area was divided into a series of permeable units (aquifers), separated by confining or semi-confining beds (aquitards); (b) the head differences between the different screened zones, derived through modeling of the flowmeter data of the wells, provided additional confirmation for the division of the upper part of the Kuwait Group aquifer into compartments in the study area; (c) flowmeter data indicated that the second and third aquifers were contributing most of the water to the well bores, compared with the uppermost (first) and the lowermost (fourth) aquifers; and (d) inflow to the wells during pumping was associated with discrete sub-intervals in the screened zones, controlled by local aquifer heterogeneity, and possibly clogging of screens and gravel pack
Dry Creek is a small stream that drains about 8.74 square miles of rugged mountainous terrain upstream from Tabor Dam in the Mission Range near St. Ignatius, Montana. Because of uncertainty in plausible peak discharges and concerns regarding the ability of the Tabor Dam spillway to safely convey these discharges, the flood hydrology for Dry Creek was evaluated on the basis of three hydrologic and geologic methods. The first method involved determining an envelope line relating flood discharge to drainage area on the basis of regional historical data and calculating a 500-year flood for Dry Creek using a regression equation. The second method involved paleoflood methods to estimate the maximum plausible discharge for 35 sites in the study area. The third method involved rainfall-runoff modeling for the Dry Creek basin in conjunction with regional precipitation information to determine plausible peak discharges. All of these methods resulted in estimates of plausible peak discharges that are substantially less than those predicted by the more generally applied probable maximum flood technique.
A solute breakthrough curve measured during a two-well tracer test was successfully predicted in 1986 using specialized contaminant transport models. Water was injected into a confined, unconsolidated sand aquifer and pumped out 125 feet (38.3 m) away at the same steady rate. The injected water was spiked with bromide for over three days; the outflow concentration was monitored for a month. Based on previous tests, the horizontal hydraulic conductivity of the thick aquifer varied by a factor of seven among 12 layers. Assuming stratified flow with small dispersivities, two research groups accurately predicted breakthrough with three-dimensional (12-layer) models using curvilinear elements following the arc-shaped flowlines in this test. Can contaminant transport models commonly used in industry, that use rectangular blocks, also reproduce this breakthrough curve? The two-well test was simulated with four MODFLOW-based models, MT3D (FD and HMOC options), MODFLOWT, MOC3D, and MODFLOW-SURFACT. Using the same 12 layers and small dispersivity used in the successful 1986 simulations, these models fit almost as accurately as the models using curvilinear blocks. Subtle variations in the curves illustrate differences among the codes. Sensitivities of the results to number and size of grid blocks, number of layers, boundary conditions, and values of dispersivity and porosity are briefly presented. The fit between calculated and measured breakthrough curves degenerated as the number of layers and/or grid blocks decreased, reflecting a loss of model predictive power as the level of characterization lessened. Therefore, the breakthrough curve for most field sites can be predicted only qualitatively due to limited characterization of the hydrogeology and contaminant source strength.
Perkins, K.S. and Nimmo, J.R., 2000, Measurement of hydraulic properties of the B-C interbed and their influence on contaminant transport in the unsaturated zone at the Idaho National Engineering and Environmental Laboratory: U.S. Geological Survey Water-Resources Investigations Report 00-4073.
The intensely layered character of the 200-m thick unsaturated zone near the Radioactive Waste Management Complex (RWMC) Subsurface Disposal Area (SDA) at the Idaho National Engineering and Environmental Laboratory (INEEL) critically affects both vertical and horizontal water fluxes. Because of the potential for radionuclide migration from the SDA to the Snake River Plain Aquifer, it is important to investigate the role of the unsaturated zone in contaminant transport processes. The unsaturated zone consists of thick layers of fractured basalts interbedded with thinner layers of sediment. These interbeds and basalts were deposited approximately 50,000 to 450,000 years ago during the late Pleistocene. As a part of a drilling program to develop a standard methodology for subsurface characterization and risk assessment at INEEL, hydraulic properties of the 34-m deep sedimentary interbed (known as the B-C interbed (Anderson and Lewis, 1989)) have been measured at one location in the vicinity of the SDA, including particle size distributions, water retention functions, saturated and unsaturated hydraulic conductivity, and related properties. In porous media, water flux is usually modeled in terms of Darcy's law for steady flow and Richards' equation for transient flow. Both of these formulations require knowledge of the unsaturated hydraulic conductivity (K) of the media, a property that is difficult to measure and highly sensitive to variations in water content. The transient case additionally requires knowledge of the water retention relation, which similarly varies to a high degree within the medium. The interbeds may play several critical roles in long-range transport processes: (a) retardation of downward-moving water as it encounters layer boundaries, (b) generation of perched water, (c) homogenization of preferential flow that has been focused by basalt fractures, and (d) the formation of long-range, highly conductive horizontal flow paths for contaminants. Within these sedimentary layers, there may be little or no impediment to lateral flow. Drastic differences in hydraulic properties between the basalt and interbeds, and within the interbeds themselves, are likely to promote such flow.
Daily-to-weekly discharge during the snowmelt season is highly correlated among river basins in the upper elevations of the central and southern Sierra Nevada (Carson, Walker, Tuolumne, Merced, San Joaquin, Kings, and Kern Rivers). In many cases, the upper Sierra Nevada watershed operates in a single mode (with varying catchment amplitudes). In some years, with appropriate lags, this mode extends to distant mountains. A reason for this coherence is the broad scale nature of synoptic features in atmospheric circulation, which provide anomalous insolation and temperature forcings that span a large region, sometimes the entire western U.S. These correlations may fall off dramatically, however, in dry years when the snowpack is spatially patchy.
Major-element oxides and trace elements in the Phosphoria Formation at the Hot Springs Mine, Idaho were determined by a series of techniques. In this report, we examine the distribution of trace elements between the different solid components—aluminosilicates, apatite, organic matter, opal, calcite, and dolomite—that largely make up the rocks. High concentrations of several trace elements throughout the deposit, for example, As, Cd, Se, Tl, and U, at this and previously examined sites have raised concern about their introduction into the environment via weathering and the degree to which mining and the disposal of mined waste rock from this deposit might be accelerating that process. The question addressed here is how might the partitioning of trace elements between these solid host components influence the introduction of trace elements into ground water, surface water, and eventually biota, via weathering? In the case of Se, it is partitioned into components that are quite labile under the oxidizing conditions of subaerial weathering. As a result, it is widely distributed through out the environment. Its concentration exceeds the level of concern for protection of wildlife at virtually every trophic level.
The chemical and isotopic composition of water discharging from 44 springs and 32 wells in Shenandoah National Park (SNP) and vicinity were measured. The data include field measurements of water temperature, specific conductance, concentrations of dissolved oxygen (O2), and pH, and laboratory measurements of major-, minor-, and trace-element chemistry, concentrations of dissolved gases (nitrogen (N2), argon (Ar), helium (He), neon (Ne), oxygen (O2), and carbon dioxide (CO2)), tritium (3H) of water, concentrations of dissolved trace atmospheric gases, including chloroflurocarbons (CFC-11, CFC-12, and CFC-113), and sulfur hexaflouride (SF6), the stable 3He/4He isotope ratio (d3He) of dissolved He, stable 2H/1H and 18O/16O isotope ratios (d2H and d18O) of water, the stable 34S/32S isotope ratio (d34S) of dissolved sulfate, the stable 15N/14N isotope ratio (d15N) of dissolved nitrate, and the activity of radioactive sulfur-35 (35S) of dissolved sulfate. Water from selected springs and wells was sampled in April 1996, August-September 1997, and August-September 1999. Additional data on the atmospheric mixing ratios of CFC-11, CFC-12, CFC-113 and SF6 in air from the Big Meadows Air Monitoring Station, SNP are given approximately weekly for the period September 1995 through March 2000. Five springs (Lewis Spring, Furnace Spring, Byrd?s Nest 3, Browntown Valley Overlook Spring, and Hudson Spring) were sampled monthly between March 1999 and September 1999. Measurements were also made of 3H, d18O, and d2H of water from 30 streams near the base of the east and west flanks of the Blue Ridge Mountains that encompass Shenandoah National Park, Virginia, in April 1996 and September 1997.
Calcite grew continuously for 500,000 years on the submerged walls of an open fault plane (Devils Hole) in southern Nevada, U.S.A. at rates of 0.3 to 1.3 mm/ka, but ceased growing approximately 60,000 years ago, even though the fault plane remained open and was continuously submerged. The maximum initial in-situ growth rate on pre-weighed crystals of Iceland spar placed in Devils Hole (calcite saturation index, SI, is 0.16 to 0.21 at 33.7 °C) for growth periods of 0.75 to 4.5 years was 0.22 mm/ka. Calcite growth on seed crystals slowed or ceased following initial contact with Devils Hole groundwater. Growth rates measured in synthetic Ca-HCO3 solutions at 34 °C, CO2 partial pressures of 0.101, 0.0156 (similar to Devils Hole groundwater) and 0.00102 atm, and SI values of 0.2 to 1.9 were nearly independent of PCO, decreased with decreasing saturation state, and extrapolated through the historical Devils Hole rate. The results show that calcite growth rate is highly sensitive to saturation state near equilibrium. A calcite crystal retrieved from Devils Hole, and used without further treatment of its surface, grew in synthetic Devils Hole groundwater when the saturation index was raised nearly 10-fold that of Devils Hole water, but the rate was only 1/4 that of fresh laboratory crystals that had not contacted Devils Hole water. Apparently, inhibiting processes that halted calcite growth in Devils Hole 60,000 years ago continue today.
Stable isotope data ( 2H and 18O) were used in conjunction with chlorofluorocarbon (CFC) and tritium/helium-3 ( 3H/3He) data to determine the fraction and age of irrigation water in ground water mixtures from farmed parts of the Eastern Snake River Plain (ESRP) Aquifer in south-central Idaho. Two groups of waters were recognized: (1) regional background water, unaffected by irrigation and fertilizer application, and (2) mixtures of irrigation water from the Snake River with regional background water. New data are presented comparing CFC and 3H/3He dating of water recharged through deep fractured basalt, and dating of young fractions in ground water mixtures. The 3H/3He ages of irrigation water in most mixtures ranged from about zero to eight years. The CFC ages of irrigation water in mixtures ranged from values near those based on 3H/3He dating to values biased older than the 3H/3He ages by as much as eight to 10 years. Unsaturated zone air had CFC-12 and CFC-113 concentrations that were 60% to 95%, and 50% to 90%, respectively, of modern air concentrations and were consistently contaminated with CFC-11. Irrigation water diverted from the Snake River was contaminated with CFC-11 but near solubility equilibrium with CFC-12 and CFC-113. The dating indicates ground water velocities of 5 to 8 m/d for water along the top of the ESRP Aquifer near the southwestern boundary of the Idaho National Engineering and Environmental Laboratory (INEEL). Many of the regional background waters contain excess terrigenic helium with a 3H/3He isotope ratio of 7 X 10-6 to 11 x 10-6 (R/Ra approximately equal to 5 to 8) and could not be dated. Ratios of CFC data indicate that some rangeland water may contain as much as 5% to 30% young water (ages of less than or equal to two to 11.5 years) mixed with old regional background water. The relatively low residence times of ground water in irrigated parts of the ESRP Aquifer and the dilution with low-NO3- irrigation water from the Snake River lower the potential for NO3- contamination in agricultural areas.
Gram quantities of aquatic humic substances (AHS) were extracted from the Wakarusa River-Clinton Lake Reservoir system, near Lawrence, KS, to support nuclear magnetic resonance (NMR) experimental studies, report concentrations of dissolved organic carbon (DOC) and AHS, define sources of the AHS, and determine if the AHS yield sufficient quantities of haloacetic acids (HAA5) and trihalomethanes (THM4) that exceed U.S. Environmental Protection Agency (EPA) Maximum Contaminant Levels (MCL) in drinking water. AHS from the Wakarusa River and Clinton Lake originated from riparian forest vegetation, reflected respective effects of soil organic matter and aquatic algal/bacterial sources, and bore evidence of biological degradation and photodegradation. AHS from the Wakarusa River showed the effect of terrestrial sources, whereas Clinton Lake humic acid also reflected aquatic algal/bacterial sources. Greater amounts of carbon attributable to tannin-derived chemical structures may correspond with higher HAA5 and THM4 yields for Clinton Lake fulvic acid. Prior to appreciable leaf-fall from deciduous trees, the combined (humic and fulvic acid) THM4 formation potentials for the Wakarusa River approached the proposed EPA THM4 Stage I MCL of 80 mg/L, and the combined THM4 formation potential for Clinton Lake slightly exceeded the proposed THM4 Stage II MCL of 40 mg/L. Finally, AHS from Clinton Lake could account for most (>70%) of the THM4 concentrations in finished water from the Clinton Lake Water Treatment Plant based on September 23, 1996, THM4 results.
Calcium carbonate crystallization is an important process in numerous terrestrial and aquatic ecosystems. Moreover, calcium carbonate scale formation on heat transfer surfaces is an important industrial problem. Humic substances, which are ubiquitous in natural waters, often reduce or inhibit calcite crystal growth, and may, therefore, have application in scale prevention. This study quantifies and interprets calcite crystal growth rate reduction due to humic substance fractions isolated from surface water. We conducted calcite growth experiments at constant pH (8.5), temperature (250C), supersaturation (S = 4.5), PCO2 (10-3.5 atm), and ionic strength (0.1 KNO3) with various concentrations of natural organic isolates. Plant-derived aquatic hydrophobic acids from the Everglades were effective growth inhibitors. Organic acid molecular weight correlated with growth inhibition as did aromaticity, aliphatic content and heteroatom content; however, carboxyl content did not. Growth inhibition over a range of organic inhibitor concentrations for Everglades' samples is consistent with a Langmuir adsorption mechanism blocking growth sites on the calcite surface.
Robbins, E.I., Rodgers, T.M., Alpers, C.N., and Nordstrom, D.K., 2000, Ecogeochemistry of the subsurface food web at pH 0-2.5 in Iron Mountain, California, USA: Hydrobiologia, v. 433, p. 15-23.
Pyrite oxidation in the underground mining environment of Iron Mountain, California, has created the most acidic pH values ever reported in aquatic systems. Sulfate values as high as 120000 mg/L and iron as high as 27600 mg/L have been measured in the mine water, which also carries abundant other dissolved metals including Al, Zn, Cu, Cd, Mn, Sb and Pb. Extreme acidity and high metal concentrations apparently do not preclude the presence of an underground acidophilic food web, which has developed with bacterial biomass at the base and heliozoans as top predators. Slimes, oil-like films, flexible and inflexible stalactites, sediments, water and precipitates were found to have distinctive communities. A variety of filamentous and non-filamentous bacteria grew in slimes in water having pH values <1.0. Fungal hyphae colonize stalactites dripping pH 1.0 water; they may help to form these drip structures. Motile hypotrichous ciliates and bdelloid rotifers are particularly abundant in slimes having a pH of 1.5. Holdfasts of the iron bacterium Leptothrix discophora attach to biofilms covering pools of standing water having a pH of 2.5 in the mine. The mine is not a closed environment - people, forced air flow and massive flushing during high intensity rainfall provide intermittent contact between the surface and underground habitats, so the mine ecosystem probably is not a restricted one.
Lake Belle Taine (480 ha) in north central Minnesota receives on average 76,000 m3d-1 of water from Little Sand Creek but has no outlet. Water seeps out of the lake, flows through glacial outwash, and discharges into three nearby lake lakes with stages 13-14 m lower than Belle Taine. Seepage-meter data indicate water is seeping out of Belle Taine at velocities up to 263 cm d-1. Hydraulic-head measurements made in the lake bed indicate the sediments are unsaturated beneath a portion of the lake edge, and a wedge of unsaturated sediments extends beneath the lake bed as much as 20 m from the shoreline. At the shoreline the water table is as much as 6.7 m below the lake surface. Modeling results of a similar hypothetical setting indicate that the horizontal extent of an unsaturated zone beneath a lake depends on (1) the permeability contrast between the outwash and the lake bed, (2) anisotropy, (3) lake bed slope, and (4) thickness of the lower-permeability lake bed sediments. Although rarely documented, unsaturated sediments beneath a lake may not be extremely uncommon. Similar, much smaller unsaturated-zone areas also have been observed beneath two other lakes in Minnesota.
Determining the discharge of ground water to Shingobee Lake (66 ha), north-central Minnesota, is complicated by the presence of numerous springs situated adjacent to the lake and in the shallow portion of the lakebed. Springs first had to be located before these areas of more rapid discharge could be quantified. Two methods that rely on the distribution of aquatic plants are useful for locating springs. One method identifies areas of the near-shore lakebed where floating-leaf and emergent aquatic vegetation are absent. The second method uses the distribution of marsh marigold (Caltha palustris L.) to locate springs that discharge on land near the shoreline of the lake. Marsh marigold produces large (2 to 4 cm diameter) yellow flowers that provide a ready marker for locating ground water springs. Twice as many springs (38) were identified using this method as were identified using the lack of near-shore vegetation. A portable weir was used to measure discharge from onshore springs, and seepage meters were used to measure discharge from near-shore springs. Of the total 56.7 L/s that enters the lake from ground water, approximately 30% comes from onshore and near-shore springs.
The fate of halogenated disinfection byproducts (DBPs) in treatment wetlands and the changes in the DBP formation potential as wastewater treatment plant (WWTP)-derived water moves through the wetlands were investigated. Wetland inlet and outlet samples were analyzed for total organic halide (TOX), trihalomethanes (THM), haloacetic acids (HAA), dissolved organic carbon (DOC), and UV absorbance. Removal of DBPs by the wetland ranged from 13 to 55% for TOX, from 78 to 97% for THM, and from 67 to 96% for HAA. The 24-h and 7-day nonpurgeable total organic halide (NPTOX), THM, and HAA formation potential yields were determined at the inlet and outlet of these wetlands. The effect of wetlands on the production of DBP precursors and their DBP-formation potential yield from wastewater was dramatic. The wetlands increased DBP yield up to a factor of almost 30. Specific changes in the DOC precursors were identified using 13C NMR spectroscopy.
Rybicki, N.B., Reel, J.T., Ruhl, H.A., Gammon, P.T., Carter V., and Lee, J.K., 2000, Sawgrass density, biomass, and leaf area index: A flume study in support of research on wind sheltering effects in the Florida Everglades, U.S. Geological Survey Open-File Report 00-172.
A 9.9-ha combined habitat and wastewater treatment demonstration wetland was constructed and planted in the summer of 1994, at Eastern Municipal Water District's (EMWD) Hemet/San Jacinto Regional Water Reclamation Facility (RWRF) in southern California. From January 1996 through September 1997, the marsh-pond-marsh wetland system was operated to polish an average of 3785 m3d-1 (1 x 106 gal/day) of secondary-treated effluent from the RWRF. Nitrogen removal was a major objective of this wetland treatment. Weekly inflow/outflow water quality monitoring of the wetland was supplemented with biannual, 45-station synoptic surveys within the system to determine internal distribution patterns of the nitrogen species (total ammonia, nitrite, nitrate, and organic nitrogen), total organic carbon (TOC), and ultraviolet absorbance at 254 nm (UV254). Synoptic surveys were carried out during May 22 and September 17, 1996, and May 6 and September 25, 1997 and the results were mapped using the ARC/INFO processing package and inverse distance weighted mathematical techniques. Distribution patterns of the various nitrogen species, TOC, and UV254 within the wetland indicate that the nitrogen dynamics of the system are influenced both by variations in treatment plant loading, and, increasingly, by the degree of coverage and maturity of the emergent vegetation.
Stream discharges and concentrations of dissolved and colloidal metals (Al, Ca, Cu, Fe, Mg, Mn, Pb, and Zn), SO4, and dissolved silica were measured to identify chemical transformations and determine mass transports through two mixing zones in the Animas River that receive the inflows from Cement and Mineral Creeks. The creeks were the dominant sources of Al, Cu, Fe, and Pb, whereas the upstream Animas River supplied about half of the Zn. With the exception of Fe, which was present in dissolved and colloidal forms, the metals were dissolved in the acidic, high-SO4 waters of Cement Creek (pH 3.8). Mixing of Cement Creek with the Animas River increased pH to near-neutral values and transformed Al and some additional Fe into colloids which also contained Cu and Pb. Aluminium and Fe colloids had already formed in the mildly acidic conditions in Mineral Creek (pH 6.6) upstream of the confluence with the Animas River. Colloidal Fe continued to form downstream of both mixing zones. The Fe- and Al-rich colloids were important for transport of Cu, Pb, and Zn, which appeared to have sorbed to them. Partitioning of Zn between dissolved and colloidal phases was dependent on pH and colloid concentration. Mass balances showed conservative transports for Ca, Mg, Mn, SO4, and dissolved silica through the two mixing zones and small losses (<10%) of colloidal Al, Fe and Zn from the water column.
Elemental selenium, Se(o), is a prevalent chemical form in sediments, but little is known about its bioavailability. We evaluated the bioavailability of two forms of Se(o) by generating radioscopic 75Se(o) through bacterial dissimilatory reduction of 75SeO32- by pure bacterial cultures (SES) and by an anaerobic sediment microbial consortium (SED). A third form was generated by reducing 75SeO32- with ascorbic acid (AA). Speciation determinations showed that AA and SES were > 90% Se(O), but SED showed a mixture of Se(o), seleoanions, and a residual fraction. Pulse-chase techniques were used to measure assimilation efficiencies (AE) of these particulate Se forms by the bivalve Potamocorbula amurensis. Mean AE values were 3 ± 2% for AA, 7 ± 1% for SES, and 28 ± 15% for SED, showing that the bioavailability of reduced, particle-associated Se is dependent upon its origin. To determine if oxidative microbial processes increased Se transfer, SES 75Se(o) was incubated with an aerobic sediment microbial consortium. After 113 d of incubation, 36% of SES Se(o) was oxidized to SeO32-. Assimilation of total particulate Se was unaffected however (mean AE = 5.5%). The mean AE from the diatom Phaedactylum tricornutum was 58 ± 8%, verifying the importance of Se associated with biogenic particles. Speciation and AE results from SED suggest that selenoanion reduction in wetlands and estuaries produces biologically available reduced selenium.
The potential to use ice cores from alpine glaciers in the midlatitudes to reconstruct paleoclimatic records has not been widely recognized. Although excellent paleoclimatic records exist for the polar regions, paleoclimatic ice core records are not common from midlatitude locations. An ice core removed from the Upper Fremont Glacier in Wyoming provides evidence for abrupt climate change during the mid-1800s. Volcanic events (Krakatau and Tambora) identified from electrical conductivity measurements (ECM) and isotopic and chemical data from the Upper Fremont Glacier were reexamined to confirm and refine previous chronological estimates of the ice core. At a depth of 152 m the refined age-depth profile shows good agreement (1736 ± 10 A.D.) with the 14C age date (1729 ± 95 A.D.). The d18O profile of the Upper Fremont Glacier (UFG) ice core indicates a change in climate known as the Little Ice Age (LIA). However, the sampling interval for d18O is sufficiently large (20 cm) such that it is difficult to pinpoint the LIA termination on the basis of d18O data alone. Other research has shown that changes in the d18O variance are generally coincident with changes in ECM variance. The ECM data set contains over 125,000 data points at a resolution of 1 data point per millimeter of ice core. A 999-point running average of the ECM data set and results from f tests indicates that the variance of the ECM data decreases significantly at about 108 m. At this depth, the age-depth profile predicts an age of 1845 A.D. Results indicate the termination of the LIA was abrupt with a major climatic shift to warmer temperatures around 1845 A.D. and continuing to present day. Prediction limits (error bars) calculated for the profile ages are plus or minus 10 years (90% confidence level). Thus a conservative estimate for the time taken to complete the LIA climatic shift to present-day climate is about 10 years, suggesting the LIA termination in alpine regions of central North America may have occurred on a relatively short (decadal) timescale.
Hydrologists often attempt to estimate formation properties from aquifer tests for which only the hydraulic responses in a pumped well are available. Borehole storage, turbulent head losses, and borehole skin, however, can mask the hydraulic behavior of the formation inferred from the water level in the pumped well. Also, in highly permeable formations or in formations at significant depth below land surface, where there is a long column of water in the well casing, oscillatory water levels may arise during the onset of pumping to further mask formation responses in the pumped well. Usually borehole phenomena are confined to the early stages of pumping or recovery, and late-time hydraulic data can be used to estimate formation properties. In many instances, however, early-time hydraulic data provide valuable information about the formation, especially if there are interferences in the late-time data. A mathematical model and its Laplace transform solution that account for inertial influences and turbulent head losses during pumping is developed for the coupled response between the pumped borehole and the formation. The formation is assumed to be homogeneous, isotropic, of infinite areal extent, and uniform thickness, with leakage from an overlying aquifer, and the screened or open interval of the pumped well is assumed to fully penetrate the pumped aquifer. Other mathematical models of aquifer flow can also be coupled with the equations describing turbulent head losses and the inertial effects on the water column in the pumped well. The mathematical model developed in this paper is sufficiently general to consider both underdamped conditions for which oscillations arise, and overdamped conditions for which there are no oscillations. Through numerical inversion of the Laplace transform solution, type curves from the mathematical model are developed to estimate formation properties through comparison with the measured hydraulic response in the pumped well. The mathematical model is applied to estimate formation properties from a singlewell test conducted near Waialua, Oahu, Hawaii. At this site, both the drawdown and recovery showed oscillatory water levels in the pumped well, and a step-drawdown test showed that approximately 86% of the drawdown is attributed to turbulent head losses. Analyses at this site using late-time drawdown data were confounded by the noise present in the measured water levels due primarily to nearby irrigation wells and ocean tides. By analyzing the early-time oscillatory recovery data at the Waialua site, upper and lower bounds were placed on the transmissivity, T, storage coefficient, S, and the leakance of the confining unit, K'/B'. The upper and lower bounds on T differ by a factor of 2. Upper and lower bounds on S and K'/B' are much larger, because drawdown stabilized relatively quickly after the onset of pumping.
Area-weighted thickness distributions of fundamental illite particles for samples of illite and illite-smectite from seven locations (including bentonites and hydrothermally altered pyroclastics) were measured by Pt-shadowing technique, by transmission electron microscopy. Most thickness distributions are described by lognormal distributions, which suggest a unique crystallization process. The shapes of lognormal distributions of fundamental illite particles can be calculated from the distribution mean because the shape parameters a and b 2 are interrelated:
b 2=0.107a-0.03.
This growth process was simulated by the mathematical Law of Proportionate Effect that generates lognormal distributions. Simulations indicated that illite particles grow from 2-nm thick illite nuclei by surface-controlled growth, i.e., the rate of growth is restricted by how rapid crystallization proceeds given a near infinite supply of reactants, and not by the rate of supply of reactants to the crystal surface. Initially formed, 2-nm thick crystals may nucleate and grow within smectite interlayers from material produced by dissolution of single smectite 2:1 layers, thereby transforming the clay from randomly interstratified (Reichweite, R = 0) to ordered (R = 1) illite-smectite after the smectite single layers dissolve. In this initial period of illite nucleation and growth expandable layers range from 100 to 20%. After nucleation ceases, illite crystals may continue to grow by surface-controlled growth, and the expandable-layer content ranges from 20 to 0%. This latter period of illitization is characterized by three-dimensional growth. Other crystal-growth mechanisms, such as Ostwald ripening, supply-controlled growth, and the coalescence of smectite layers, do not produce the observed evolution of a and b 2 and the observed shapes of crystal thickness distributions.
A new method for concentrating nitrate from fresh waters for d15N and d18O analysis has been developed and field-tested for four years. The benefits of the method are: (1) elimination of the need to transport large volumes of water to the laboratory for processing; (2) elimination of the need for hazardous preservatives; and (3) the ability to concentrate nitrate from fresh waters. Nitrate is collected by, passing the water-sample through pre-filled, disposable, anion exchanging resin columns in the field. The columns are subsequently transported to the laboratory where the nitrate is extracted, converted to AgNO3 and analyzed for its isotope composition. Nitrate is eluted from the anion exchange columns with 15 ml of 3 M HCl. The nitrate-bearing acid eluant is neutralized with Ag2O, filtered to remove the AgCl precipitate, then freeze-dried to obtain solid AgNO3, which is then combusted to N2 in sealed quartz tubes for d15N analysis. For d18O analysis, aliquots of the neutralized eluant are processed further to remove non-nitrate oxygen-bearing anions and dissolved organic matter. Barium chloride is added to precipitate sulfate and phosphate; the solution is then filtered, passed through a cation exchange column to remove excess Ba2+, re-neutralized with Ag2O, filtered, agitated with activated carbon to remove dissolved organic matter and freeze-dried. The resulting AgNO3 is combusted with graphite in a closed tube to produce CO2, which is cryogenically purified and analyzed for its oxygen isotope composition. The 1 sigma analytical precisions for d15N and d18O are plus or minus 0.05 ppt and plus or minus 0.5 ppt, respectively, for solutions of KNO3 standard processed through the entire column procedure. High concentrations of anions in solution can interfere with nitrate adsorption on the anion exchange resins, which may result in isotope fractionation of nitrogen and oxygen (fractionation experiments were conducted for nitrogen only; however, fractionation for oxygen is expected). Chloride, sulfate, and potassium biphthalate, an organic acid proxy for dissolved organic material, added to KNO3 standard solutions caused no significant nitrogen fractionation for chloride concentrations below about 200 mg/l (5.6 meq/l) for 1000 ml samples, sulfate concentrations up to 2000 mg/l (41.7 meq/l) in 100 ml samples, and Potassium biphthalate for concentrations up to 200 mg/l carbon in 100 ml samples. Samples archived on the columns for up to two years show minimal nitrogen isotope fractionation.
Soler-Lopez, L.R., Webb, R.M.T., and Carrasquillo-Nieves, R.A., 2000, Sedimentation Survey of Lago La Plata, Puerto Rico, October 1998: U.S. Geological Survey Water Resources Investigations Report 00-4045.
Sediment accumulation has decreased the storage capacity of Lago La Plata from 40.21 million cubic meters in 1974 to 35.46 million cubic meters in 1998. In 24 years, the reservoir has lost about 12 percent of its original capacity, which represents an average annual capacity loss of about 0.5 percent. The trapping efficiency of the reservoir was estimated to be 85 percent in 1998. Based on the amount of accumulated sediment-contributing area, the sediment yield of the Lago La Plata Basin was estimated to be about 483 megagrams per square kilometer per year. At a current average capacity loss per year of 0.2 million cubic meters and assuming a constant trapping efficiency, the reservoir is expected to completely fill with sediments by the year 2175.
On September 21, 1998, Hurrican Georges made landfall on the island of Puerto Rico. A comparison of data collected in February and in October 1998 revealed the impact of the storm along the riverine branches of the reservoir bottom. Flooding that resulted from Hurricane Georges mobilized sediments deposited in upstream sections of Lago La Plata and transported them downstream to the deeper parts of the reservoir near the dam.
Soler-Lopez, L.R., Webb, R.M.T., and Carrasquillo-Nieves, R.A., 2000, Sedimentation Survey of Lago Guajataca, Puerto Rico, January 1999: U.S. Geological Survey Water Resources Investigations Report 00-4044.
Compared to other reservoirs in Puerto Rico, sediment accumulation in Lago Guajataca has been moderate since its construction in 1928. The storage capacity has been reduced from 48.46 million cubic meters in 1928 to 42.28 million cubic meters in 1999. This represents a storage loss of 6.18 million cubic meters or about 13 percent of the original capacity. The average long-term sedimentation rate was calculated to be 87,000 cubic meters per year or 0.2 percent of capacity loss per year. Using the capacity/inflow relation established by Brune in 1953, the trapping efficiency of the reservoir was estimated to be 97 and 96 percent for 1928 and 1999, respectively. Based on the average long-term trapping efficiency of the reservoir, the mean annual runoff, and the sediment contributing drainage area of the reservoir, the sediment yield of the Lago Guajataca basin was estimated to be about 1,188 megagrams per square kilometer per year. At the average long-term sedimentation rate, the remaining useful life of the reservoir, in terms of flood control and recreation, is about 486 years, which means the reservoir is expected to completely fill with sediments by the year 2485.
Alpine/subalpine ecosystems in Rocky Mountain National Park may be sensitive to atmospherically derived acidic deposition. Two- and three-component hydrograph separation analyses and correlation analyses were performed for six basins to provide insight into streamflow generation during snowmelt and to assess basin sensitivity to acidic deposition. Three-component hydrograph separation results for five basins showed that streamflow contained from 42 to 57% direct snowmelt runoff, 37 to 54% subsurface water, and 4 to 13% direct rain runoff for the May through October 1994 study period. Subsurface contributions were 89% of total flow for the sixth basin. The reliability of hydrograph separation model assumptions was explored. Subsurface flow was positively correlated with the amount of surficial material in a basin and was negatively correlated with basin slope. Basins with extensive surficial material and shallow slopes are less susceptible to ecosystem changes due to acidic deposition than basins with less surficial material and steeper slopes. This study was initiated to expand the intensive hydrologic research that has been conducted in Loch Vale basin to a more regional scale.
Taylor, Howard E., 2000, Inorganic substances, mass spectrometric in the analysis of, in R.A. Meyers, ed., Encyclopedia of Analytical Chemistry: Chichester, John Wiley & Sons, Ltd, p. 11761-11773.
Mass spectrometry is an analytical technique used to measure the composition of a substance by isolating specific analyte components according to their individual atomic or molecular mass-to-charge ratios. Inorganic mass spectrometry is specifically used to determine the elemental and isotopic composition of the material being analyzed. The techniques are capable of the measurement of a range of concentrations from major components to ultratrace constituents. Several instrumental approaches are used to separate and measure the abundance of component ions formed from the sample. These techniques include electron ionization mass spectrometry (EIMS), inductively coupled plasma mass spectrometry (ICPMS), thermal ionization mass spectrometry (TIMS), and spark source mass spectrometry (SSMS). These techniques utilize a variety of mass spectrometers including ion trap, quadrupole, magnetic sector and time-of-flight mass analyzers, depending on the type of sample being analyzed and the desired quality of the results. Often sample introduction techniques can be utilized to enhance the capabilities for solving specific analytical chemistry problems.
The Colorado River in Marble and Grand Canyon displays evidence of annual supply limitation with respect to sand both prior to [Topping et al., this issue] and after the closure of Glen Canyon Dam in 1963. Systematic changes in bed elevation and systematic coupled changes in suspended-sand concentration and grain size result from this supply limitation. During floods, sand supply limitation either causes or modifies a lag between the time of maximum discharge and the time of either maximum or minimum (depending on reach geometry) bed elevation. If, at a cross section where the bed aggrades with increasing flow, the maximum bed elevation is observed to lead the peak or the receding limb of a flood, then this observed response of the bed is due to sand supply limitation. Sand supply limitation also leads to the systematic evolution of sand grain size (both on the bed and in suspension) in the Colorado River. Sand input during a tributary flood travels down the Colorado River as an elongating sediment wave, with the finest sizes (because of their lower settling velocities) traveling the fastest. As the fine front of a sediment wave arrives at a given location, the bed fines and suspended-sand concentrations increase in response to the enhanced upstream supply of finer sand. Then, as the front of the sediment wave passes that location, the bed is winnowed and suspended-sand concentrations decrease in response to depletion of the upstream supply of finer sand. The grain-size effects of depletion of the upstream sand supply are most obvious during periods of higher dam releases (e.g., the 1996 flood experiment and the 1997 test flow). Because of substantial changes in the grain-size distribution of the bed, stable relationships between the discharge of water and sand-transport rates (i.e., stable sand rating curves) are precluded. Sand budgets in a supply-limited river like the Colorado River can only be constructed through inclusion of the physical processes that couple changes in bed-sediment grain size to changes in sand-transport rates.
Topping, D.J., Rubin, D.M., and Vierra, L.E., Jr., 2000, Colorado River sediment transport: Part 1: Natural sediment supply limitation and the influence of Glen Canyon Dam: Water Resources Research, v. 36, p. 515-542.
Analyses of flow, sediment transport, bed-topographic, and sedimentologic data suggest that before the closure of Glen Canyon Dam in 1963, the Colorado River in Marble and Grand Canyons was annually supply-limited with respect to fine sediment (i.e., sand and finer material). Furthermore, these analyses suggest that the predam river in Glen Canyon was not supply-limited to the same degree and that the degree of annual supply limitation increased near the head of Marble Canyon. The predam Colorado River in Grand Canyon displays evidence of four effects of supply limitation: (1) seasonal hysteresis in sediment concentration, (2) seasonal hysteresis in sediment grain size coupled to the seasonal hysteresis in sediment concentration, (3) production of inversely graded flood deposits, and (4) development or modification of a lag between the time of a flood peak an the time of either maximum or minimum (depending on reach geometry) bed elevation. Analyses of sediment budgets provide additional support for the interpretation that the predam river was annually supply-limited with respect to fine sediment during all seasons. In the average predam year, sand would accumulate and be stored in Marble Canyon and upper Grand Canyon for 9 months of the year (from July through March) when flows were dominantly below 200-300 m3/s; this stored sand was then eroded during April through June when flows were typically higher. After closure of Glen Canyon Dam, because of the large magnitudes of the uncertainties in the sediment budget, no season of substantial sand accumulation is evident. Because most flows in the postdam river exceed 200-300 m3/s, substantial sand accumulation in the postdam river is unlikely.
The Bertaut-Warren-Averbach (BWA) technique and high-resolution transmission electron microscopy (HRTEM) were used to characterize the products of dry-ground pyrophyllite. Mean crystallite thickness and crystallite thickness distributions were measured for each sample using the BWA technique. Mean crystallite thickness decreases during the treatment with respect to grinding time and energy applied per unit mass. The BWA data were checked by HRTEM measurements and good fits were obtained for samples having small mean particle thicknesses. Samples with thicker particles could not be measured properly by HRTEM because the number of particles counted from images is statistically insufficient. The shape of the crystallite and the particle-size distribution were used to determine the mechanism of pyrophyllite particle degradation. Particles initially having a lognormal size distribution are first delaminated randomly, then some are delaminated preferentially, thereby producing polymodal thickness distributions. Finally all particles undergo delamination yielding a lognormal thickness distribution.
The effects of irrigation canals and the North Platte River on groundwater in western Nebraska, USA, were evaluated using chemical and isotopic data. The data indicated that groundwater in the associated alluvium generally is <20 years old with estimated recharge rates from about 10 to >100 cm year-1. Most groundwater is derived from surface water, as shown by H2O and U isotope analyses. Seasonal losses of canal water to the aquifer cause changes in groundwater quality. In the deepest parts of the alluvium, some water quality may reflect precipitation recharge, older river water, or cross-formational flow. The distribution and isotopic composition of NO3- are consistent with increased fertilizer use over time. Relatively high U concentrations in groundwater may be attributed to dissolution of volcanic ash or other minerals in underlying bedrock. The relatively high concentration of U in surface water at times is attributed to seepage from U-rich groundwater and flow of U-rich surface water from a tributary.
Component additivity (CA) and generalised composite (GC) approaches to deriving a suitable surface complexation model for description of U(VI) adsorption to natural mineral assemblages are pursued in this paper with good success. A single, ferrihydrite-like component is found to reasonably describe uranyl uptake to a number of kaolinitic iron-rich natural substrates at pH > 4 in the CA approach with previously published information on nature of surface complexes, acid-base properties of surface sites and electrostatic effects used in the model. The GC approach, in which little pre-knowledge about generic surface sites is assumed, gives even better fits and would appear to be a method of particular strength for application in areas such as performance assessment provided the model is developed in a careful, stepwise manner with simplicity and goodness of fit as the major criteria for acceptance.
Webb, R.H., Griffiths, P.G., Melis, T.S., and Hartley, D.R., 2000, Sediment delivery by ungaged tributaries of the Colorado River in Grand Canyon, Arizona: U.S. Geological Survey Water-Resources Investigations Report 00-4055.
Sediment input to the Colorado River in Grand Canyon, Arizona is a valuable resource required to sustain both terrestrial and aquatic ecosystems. A total of 768 ungaged tributaries deliver sediment to the river between Glen Canyon Dam and the Grand Walsh Cliffs (river miles- 15 to 276). The 32 tributaries between the dam and Lee?s Ferry produce only streamflow floods, whereas 736 tributaries in Grand Canyon produce streamflow floods and debris flows. We used three techniques to estimate annual streamflow sediment yield from ungaged tributaries to the Colorado River. For the Glen Canyon and Marble Canyon reaches (river miles -15 to 61.5), respectively, these techniques indicate that 0.065 x 106 and 0.610 x 106 Mg/yr (0.68 x 106 Mg/yr of total sediment) enters the river. This amount is 20 percent of the sediment yield of the Paria River, the only gaged tributary in this reach and a major sediment contributor to the Colorado River. The amount of sand delivered ranges from 0.10 x 106 to 0.51 x 106 Mg/yr, depending on the sand content of streamflow sediment. Sand delivered in Glen Canyon is notable coarser (D50 = 0.24 mm) than sand in other reaches (D50 = 0.15 mm). A relation is given for possible variation of this sediment delivery with climate.
Debris flows transport poorly-sorted sediment onto debris fans in the Colorado River. In the pre-dam era, debris fans were completely reworked during Colorado River floods, liberating all fine-grained sediment to the river; in the post-dam river on average only 25 percent of debris-fan volume is reworked, leading to storage of sand in the matrix of debris fans. We develop a sediment-yield model for debris flows that uses a logistic-regression model of debris-flow frequency in Grand Canyon, a regression model of debris-flow volumes, particle size distributions of intact debris-flow deposits, and debris-fan reworking. On average, debris flows deliver between 0.14 x 106 and 0.30 x 106 Mg/yr of sediment to debris fans throughout Grand Canyon. Together, streamflow and debris flow deliver nearly 2.8 x 106 Mg/yr of sediment to the Colorado River from ungaged tributaries. In the post-dam era of minimal debris-fan reworking, the combined sand delivery rate in Glen and Marble Canyons averages 0.32 x 106 Mg/yr, which is 20 percent of the sand delivery of the Paria River and double the 0.17 x 106 Mg/yr of sand estimated for this reach in the 1995 environmental impact statement for operation of Glen Canyon Dam.
Accessory calcite, present at concentrations between 300 and 3000 mg kg-1, occurs in fresh granitoid rocks sampled from the Merced watershed in Yosemite National Park, CA, USA; Loch Vale in Rocky Mountain National Park CO USA; the Panola watershed, GA USA; and the Rio Icacos, Puerto Rico. Calcite occurs as fillings in microfractures, as disseminated grains within the silicate matrix, and as replacement of calcic cores in plagioclase. Flow-through column experiments, using de-ionized water saturated with 0.05 atm. CO2, produced effluents from the fresh granitoid rocks that were dominated by Ca and bicarbonate and thermodynamically saturated with calcite. During reactions up to 1.7 yr, calcite dissolution progressively decreased and was superceded by steady state dissolution of silicates, principally biotite. Mass balance calculations indicate that most calcite had been removed during this time and accounted for 57-98% of the total Ca released from these rocks. Experimental effluents from surfically weathered granitoids from the same watersheds were consistently dominated by silicate dissolution. The lack of excess Ca and alkalinity indicated that calcite had been previously removed by natural weathering.
The extent of Ca enrichment in watershed discharge fluxes corresponds to the amounts of calcite exposed in granitoid rocks. High Ca/Na ratios relative to plagioclase stoichiometries indicate excess Ca in the Yosemite, Loch Vale, and other alpine watersheds in the Sierra Nevada and Rocky Mountains of the western United States. This Ca enrichment correlates with strong preferential weathering of calcite relative to plagioclase in exfoliated granitoids in glaciated terrains. In contrast, Ca/Na flux ratios are comparable to or less than the Ca/Na ratios for plagioclase in the subtropical Panola and tropical Rio Icacos watersheds, in which deeply weathered regoliths exhibit concurrent losses of calcite and much larger masses of plagioclase during transport-limited weathering. These results indicate that the weathering of accessory calcite may strongly influence Ca and alkalinity fluxes from silicate rocks during and following periods of glaciation and tectonism but is much less important for older stable geomorphic surfaces.
Daily rainfall and surface temperature series were simulated for the Animas River Basin, Colorado using dynamically and statistically downscaled output from the National Center for Environmental Prediction/ National Center for Atmospheric Research (NCEP/NCAR) re-analysis. A distributed hydrological model was then applied to the downscaled data. Relative to raw NCEP output, downscaled climate variables provided more realistic simulations of basin scale hydrology. However, the results highlight the sensitivity of modeled processes to the choice of downscaling technique, and point to the need for caution when interpreting future hydrological scenarios.
Geothermal convection in carbonate platforms could drive massive dolomitization by supplying mass transport of magnesium over long periods and at temperatures high enough to overcome kinetic limitations. Reactive-transport simulations based on Enewetak Atoll show dolomitization in a thin band at a permeability contrast near the base of the platform, which is consistent with field observations of dolomitized Eocene deposits. Dolomitization is predicted at approximately 6% per My at temperatures of 45-60 degrees C, and complete dolomitization could be accomplished in approximately 16 My. Calcium enrichment of pore fluids and upward transport of these fluids is established early, prior to 30 ky.
The vulnerability of wetlands to changes in climate depends on their position within hydrologic landscapes. Hydrologic landscapes are defined by the flow characteristics of ground water and surface water and by the interaction of atmospheric water, surface water, and ground water for any given locality or region. Six general hydrologic landscapes are defined; mountainous, plateau and high plain, broad basins of interior drainage, riverine, flat coastal, and hummocky glacial and dune. Assessment of these landscapes indicate that the vulnerability of all wetlands to climate change fall between two extremes: those dependent primarily on precipitation for their water supply are highly vulnerable, and those dependent primarily on discharge from regional ground water flow systems are the least vulnerable, because of the great buffering capacity of large ground water flow systems to climate change.
Principal component analysis was used to define patterns in water table hydrographs at four small, lake-watershed research sites in the United States. The analysis provided insights into (1) characteristics of ground water recharge in different parts of the watersheds; (2) the effect of seepage from lakes on water table fluctuations; and (3) the effect of differences in geologic properties on water table fluctuations. At two sites where all of the water table wells were completed in permeable deposits, glacial outwash in Minnesota and dune sand in Nebraska, the patterns of water table fluctuation primarily reflected timing and magnitude of recharge. The water table had more frequent and wider ranges in fluctuations where it was shallow compared with where it was deep. At two sites where the water table wells were completed in sand or till, a glaciated mountain valley in New Hampshire and stagnation moraine in North Dakota, the patterns of water table fluctuations were strongly related to the type of geologic unit in which the wells are completed. Furthermore, at the New Hampshire site, the patterns of water table fluctuations were clearly different for wells completed in sand downgradient of a lake compared with those completed in sandy terraces on a mountainside. The study indicates that principal component analysis would be particularly useful for summarizing large data sets for the purpose of selecting index wells for long-term monitoring, which would greatly reduce the cost of monitoring programs.
Wolock, D.M., and McCabe, G.J., 2000, Differences in topographic characteristics from 100- and 1000-meter resolution digital elevation model data: Hydrological Processes, v. 14, no. 6, p. 987-1002.
Topographic characteristics computed from 100- and 1000-m resolution digital elevation model (DEM) data are compared for 50 locations representing varied terrain in the conterminous USA. The topographic characteristics are three parameters used extensively in hydrological research and modelling - slope (S), specific catchment area (As) and a wetness index computed as the logarithm of the specific catchment area divided by slope [ln(As/S)]. Slope values computed from 1000-m DEMs are smaller than those computed from 100-m DEMs; specific catchment area and the wetness index are larger for the 1000-m DEMs compared with the 100-m DEMs. Most of the differences between the 100- and 1000-m resolution DEMs can be attributed to terrain-discretization effects in the computation of the topographic characteristics and are not the result of smoothing or loss of terrain detail in the coarse data. In general, the terrain-discretization effects are greatest on flat terrain with long length-scale features, and the smoothing effects are greatest on steep terrain with short length-scale features. For the most part, the differences in the average values of the topographic characteristics computed from a 100- and 1000-m resolution DEMs are predictable; that is, biases in the mean values for the characteristics computed from a 1000-m DEM can be corrected with simple linear equations.
Yates, D.N., Warner, T.T., Leavesley, G.H., 2000, Prediction of a flash flood in complex terrain. Part II: A comparison of flood discharge simulations using rainfall input from radar, a dynamic model, and an automated algorithmic system: Journal of Applied Meteorology, v. 39, no. 6, p. 815-825.
Three techniques were employed for the estimation and prediction of precipitation from a thunderstorm that produced a flash flood in the Buffalo Creek watershed located in the mountainous Front Range near Denver, Colorado, on 12 July 1996. The techniques included 1) quantitative precipitation estimation using the National Weather Service's Weather Surveillance Radar-1988 Doppler and the National Center for Atmospheric Research's S-band, dual-polarization radars, 2) quantitative precipitation forecasting utilizing a dynamic model, and 3) quantitative precipitation forecasting using an automated algorithmic system for tracking thunderstorms. Rainfall data provided by these various techniques at short timescales (6 min) and at fine spatial resolutions (150 m to 2 km) served as input to a distributed-parameter hydrologic model for analysis of the flash flood. The quantitative precipitation estimates from the weather radar demonstrated their ability to aid in simulating a watershed's response to precipitation forcing from small-scale, convective weather in complex terrain. That is, with the radar-based quantitative precipitation estimates employed as input, the simulated peak discharge was similar to that estimated. The dynamic model showed the most promise in providing a significant forecast lead time for this flash-flood event. The algorithmic system did not show as much skill in comparison with the dynamic model in providing precipitation forcing to the hydrologic model. The discharge forecasts based on the dynamic-model and algorithmic-system inputs point to the need to improve the ability to forecast convective storms, especially if models such as these eventually are to be used in operational flood forecasting.
Cinder Pool is an acid-sulfate-chloride boiling spring in Norris Geyser Basin, Yellowstone National Park. The pool is unique in that its surface is partially covered with mm-size, black, hollow sulfur spherules, while a layer of molten sulfur resides at the bottom of the pool (18 m depth). The sulfur speciation in the pool was determined on four different days over a period of two years. Samples were taken to evaluate changes with depth and to evaluate the importance of the sulfur spherules on sulfur redox chemistry. All analyses were conducted on site using a combination of ion chromatography and colorimetric techniques. Dissolved sulfide (H2S), thiosulfate (S2O32-), polythionates (SxO62-), and sulfate were detected. The polythionate concentration was highly variable in time and space. The highest concentrations were found in surficial samples taken from among the sulfur spherules. With depth, the polythionate concentrations dropped off. The maximum observed polythionate concentration was 8 mu M. Thiosulfate was rather uniformly distributed throughout the pool and concentrations ranged from 35 to 45 mM. Total dissolved sulfide concentrations varied with time, concentrations ranged from 16 to 48 mM. Sulfate was relatively constant, with concentrations ranging from 1150 to 1300 mM. The sulfur speciation of Cinder Pool is unique in that the thiosulfate and polythionate concentrations are significantly higher than for any other acid-sulfate spring yet sampled in Yellowstone National Park. Complementary laboratory experiments show that thiosulfate is the intermediate sulfoxyanion formed from sulfur hydrolysis under conditions similar to those found in Cinder Pool and that polythionates are formed via the oxidation of thiosulfate by dissolved oxygen. This last reaction is catalyzed by pyrite that occurs as a minor constituent in the sulfur spherules floating on the pool's surface. Polythionate decomposition proceeds via two pathways: (1) a reaction with H2S, yielding thiosulfate and elemental sulfur; and (2) by disproportionation to sulfate and thiosulfate. This study demonstrates that the presence of a subaqueous molten sulfur pool and sulfur spherules in Cinder Pool is of importance in controlling the pathways of aqueous sulfur redox reactions. Some of the insights gained at Cinder Pool may be relevant to acid crater lakes where sulfur spherules are observed and variations in polythionate concentrations are used to monitor and predict volcanic activity.
Pore water and sediment Mo concentrations were measured in a suite of multicores collected at four sites along the northeastern flank of the Santa Barbara Basin to examine the connection between authigenic Mo formation and pore water sulfide concentration. Only at the deepest site (580 m), where pore water sulfide concentrations rise to >0.1 mM right below the sediment water interface, was there active authigenic Mo formation. At shallower sites (550, 430, and 340 m), where pore water sulfide concentrations were consistently <0.05 mM, Mo precipitation was not occurring at the time of sampling. A sulfide concentration of approximately 0.1 mM appears to be a threshold for the onset of Mo-Fe-S co-precipitation. A second threshold sulfide concentration of approximately 100 mM is required for Mo precipitation without Fe, possibly as Mo-S or as particle-bound Mo. Mass budgets for Mo were constructed by combining pore water and sediment results for Mo with analyses of sediment trap material from Santa Barbara Basin as well as sediment accumulation rates derived from 210Pb. The calculations show that most of the authigenic Mo in the sediment at the deepest site is supplied by diffusion from overlying bottom waters. There is, however, a non-lithogenic particulate Mo associated with sinking particles that contributes < or =15% to the total authigenic Mo accumulation. Analysis of sediment trap samples and supernant brine solutions indicates the presence of non-lithogenic particulate Mo, a large fraction of which is easily remobilized and, perhaps, associated with Mn-oxides. Our observations show that even with the very high flux of organic carbon reaching the sediment of Santa Barbara Basin, active formation of sedimentary authigenic Mo requires a bottom water oxygen concentration below 3 mM. However, small but measurable rates of authigenic Mo accumulation were observed at sites where bottom water oxygen ranged between 5 and 23 mM, indicating that the formation of authigenic Mo occurred in the recent past, but not at the time of sampling.
Sulfuspirillum barnesii is capable of anaerobic growth using ferric iron of arsenate as electron acceptors. Cell suspensions of S. barnesii were able to reduce arsenate to arsenite when the former oxyanion was dissolved in solution, or when it was adsorbed onto the surface of ferrihydrite, a common soil mineral, by a variety of mechanisms (e.g., coprecipitation, presorption). Reduction of Fe(III) in ferrihydrite to soluble Fe(III) also occurred, but dissolution of ferrihydrite was not required in order for adsorbed arsenate reduction to be achieved. This was illustrated by bacterial reduction of arsenate coprecipitated with aluminum hydroxide, a mineral that does not undergo reductive dissolution. The rate of arsenate reduction was influenced by the method in which arsenate became associated with the mineral phases and may have been strongly coupled with arsenate desorption rates. The extent of release of arsenite into solution was governed by adsorption of arsenite onto the ferrihydrite or alumina phases. The results of these experiments have interpretive significance to the mobilization of arsenic in large alluvial aquifers, such as those of the Ganges in India and Bangladesh, and in the hyporheic zones of contaminated streams.
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