BOREAS TGB-07 Dry Deposition Herbicide and Organochlorine Flux Data Summary: The BOREAS TGB-07 team measured the concentration and flux of several agricultural pesticides in air, rainwater, and dry deposition samples in order to determine the associated yearly deposition rates. This data set contains information on the dry deposition flux of seven herbicides [2,4- dichlorophenoxyacidic_acid (2,4-D), bromoxynil, dicamb, 2-methyl-4- chlorophenoxyacetic acid (MCPA), triallate, trifluralin, and diclop-methyl] known to appear in the atmosphere of the Canadian prairies. Also, the concentration of three herbicides (atrazine, alaclor and metolachlor), two groups of insecticides (lindane and breakdown products and dichlro-diphenyl- trichloroethane (DDT) and breakdown products), and several polychlorinated biphenyls commonly used in the central United States were measured. All of these chemicals are reported, in the literature, to be transported in the atmosphere. Many have been reported to occur in boreal and arctic food chains. The sampling was carried out from June 16 to August 13, 1993 and May 4 to July 20, 1994 at the BOREAS site in the Prince Albert National Park (Waskesiu). The data are stored in tabular ASCII files. Table of Contents * 1 Data Set Overview * 2 Investigator(s) * 3 Theory of Measurements * 4 Equipment * 5 Data Acquisition Methods * 6 Observations * 7 Data Description * 8 Data Organization * 9 Data Manipulations * 10 Errors * 11 Notes * 12 Application of the Data Set * 13 Future Modifications and Plans * 14 Software * 15 Data Access * 16 Output Products and Availability * 17 References * 18 Glossary of Terms * 19 List of Acronyms * 20 Document Information 1. Data Set Overview 1.1 Data Set Identification BOREAS TGB-07 Dry Deposition Herbicide and Organochlorine Flux Data 1.2 Data Set Introduction This data set contains herbicide and organochlorine quantities in dry deposition collected from Waskesiu. 1.3 Objective/Purpose The objective of this study was to measure the dry deposition of herbicides and organochlorines in the boreal forest at Waskesiu. 1.4 Summary of Parameters and Variables This data set contains herbicide and organochlorine quantities in dry deposition data collected Waskesiu. 1.5 Discussion The deposition into the boreal forest of seven herbicides [2,4- dichlorophenoxyacidic acid (2,4-D), bromoxynil, dicamba, 2-methyl-4- chlorophenoxyacetic acid (MCPA), triallate, trifluralin, and diclop-methyl] known to appear in the atmosphere of the Canadian prairies, three herbicides (atrazine, alachlor and metolachlor) commonly used in the central United States, two groups of insecticides (lindane and breakdown products and dichlro-diphenyl- trichloroethane (DDT) and breakdown products)plus several polychlorinated biphenyls was measured. All of these chemicals are reported, in the literature, to be transported in the atmosphere. Many have been reported to occur in boreal and arctic food chains. The sampling was carried out at the BOREAS site in the Prince Albert National Park (Waskesiu). 1.6 Related Data Sets BOREAS TGB-07 Ambient Air Herbicide and Organochlorine Concentration Data BOREAS TGB-07 Rainwater Herbicide and Organochlorine Concentration Data BOREAS TGB-09 Above-Canopy NMHC at SSA-OBS, SSA-OJP, and SSA-OA Sites BOREAS TGB-10 Volatile Organic Carbon Data over the SSA BOREAS TGB-10 Oxidant Concentration Data over the SSA BOREAS TGB-10 Oxidant Flux Data over the SSA. 2. Investigator(s) 2.1 Investigator(s) Name and Title Don Waite Environment Canada Allan Cessna Agriculture and Agri-Foods Canada Narine Gurprasad Environment Canada 2.2 Title of Investigation 2.3 Contact Information Contact 1 --------- Dr. Don Waite Environment Canada Regina, Saskatchewan Canada (306) 780-6438 (306) 780-7614 (fax) Don.Waite@EC.GC.CA Contact 2 --------- Sara K. Conrad Raytheon STX Corporation NASA/GSFC Greenbelt, MD (301)286-2624 Sara.Golightly@gsfc.nasa.gov 3. Theory of Measurements The dry/wet deposition sampler employs an XAD-2 resin column to extract dry deposits from a continuously flowing sheet of water and also collects separate rain samples. The sampler consists of a 1 x 0.5 m, stainless steel (316 grade) tray, with 5 cm high sides, onto which water is sprayed from a header pipe located at one end. The water runs down the tray, collecting any particles which fall onto it. In addition, aerosols and vapour phase chemicals which contact the water surface may be absorbed. As the water moves through the apparatus, it passes from the tray down into reservoir within the body of the sampler. Water from this reservoir is pumped, through a composite column (glass wool/XAD-2 resin) which retains the particulates and dissolved organic chemicals, and then returns back to the header pipe where it recirculates across the collecting surface. At the end of the sampling period the glass wool/XAD-2 resin column is extracted with acetone and the extract analyzed for target chemicals. 4. Equipment: 4.1 Sensor/Instrument Description 4.1.1 Collection Environment The data were collected under all environmental conditions. 4.1.2 Source/Platform Ground. 4.1.3 Source/Platform Mission Objectives None given. 4.1.4 Key Variables The key variable is herbicide or organochlorine quantity in dry deposits per day. 4.1.5 Principles of Operation As the water moves through the apparatus it passes, from the tray, down into a 32 L reservoir within the body of the sampler. Water from this reservoir is pumped, through a composite column (glass wool/XAD-2 resin) which retains the particulates and dissolved organic chemicals, and then returns back to the header pipe where it recirculates across the collecting surface. The tray slopes (5%) from about 105 to 100 cm above the ground surface. A constant speed, stainless steel centrifugal pump is used to circulate the water. The flow rate to the header is adjustable by means of a ball valve located between the pump and resin column. Water flow is from 3.5 to 4 L min-1 which produces enough water to cover the entire tray surface without causing splash at the header. This flow rate results in the circulation or turnover of the water contained in the reservoir every 8 - 9 minutes. This turnover rate, combined with the design whereby water is returned to the top and drawn off from the bottom of the reservoir, reduces the potential for particle trapping within the reservoir. All parts of the sampler in contact with the water flow are constructed of either 316 grade stainless steel or Teflon. The deionized water used is acidified to pH 1.8, using sulphuric, acid to facilitate the adsorption of acidic pesticides by the XAD-2 resin. Because such a large volume (~30 L) of deionized water circulates through the XAD-2 resin, it is imperative that the water be free of even very small concentrations of the compounds to be monitored. This is achieved by circulating, for 30 min at the beginning of each sampling period, the acidified deionized water through the sampler and through an XAD-2 clean-up cartridge (described below) identical to the one used to collect the samples. A sample of the process water is taken for analysis just prior to replacing the clean-up column. This process water sample is extracted and analysed to verify that no residual contamination is still present. If detectable background contamination is found in the process water, the sample can be rejected or corrections can be made. The structure and reproducible packing of the XAD-2 resin column are critical to the operating efficiency of the sampler. The column consists of a 5 cm inside diameter, stainless steel pipe fitted at one end with a coupling. From two to several layers of glass marbles are placed into the bottom or inlet of the column to diffuse the flow of water entering the column. By varying the volume of glass marbles, the volume of resin can be changed. Our columns contained 2 layers of marbles and 250 mL of resin, the maximum volume available in the length of pipe used. Resting on the marbles is a perforated disc of 50 mm thick Teflon followed by a plug of approximately 2 g of Pyrex brand borosilicate glass wool. The glass wool retains the 250 mL of XAD-2 resin (Caledon Laboratories Ltd., Georgetown, ON) which is packed into the column as a slurry in deionized water. The resin is capped with approximately 12 g of glass wool that is compressed with the upper sieve plate (50 mm Teflon) which also functions as a washer. The upper sieve plate/washer is held in place by a short section of pipe attached to the lower section with 3 stainless steel bolts. The upper section of pipe permits the water to leave the resin with a free and unrestricted flow, reducing the possibility of channelled flow within the resin. Tests of water flow in the column, conducted using dyes, showed uniform contact with the resin. The upper or outlet section of column connects directly with a tube leading to the header pipe. 4.1.6 Sensor/Instrument Measurement Geometry 1 - Dust Collector; a newly designed sampler employing an XAD-2 resin column to extract dry deposits from a continuously flowing sheet of water and collecting separate rain samples; 2 - PUF Sampler; a high volume air sampler collecting ambient concentrations of material on a sampling unit consisting of a glass fibre filter followed by a polyurethane foam (PUF) plug and XAD-2 resin cartridge. 4.1.7 Manufacturer of Sensor/Instrument None given. 4.2 Calibration 4.2.1 Specifications None given. 4.2.1.1 Tolerance None given 4.2.2 Frequency of Calibration None given. 4.2.3 Other Calibration Information The water flow through the sampler was from 3.5 to 4.0 l min-1. 5. Data Acquisition Methods The herbicide analyses were carried out at the Agriculture and Agri-Food Canada Research Station at Regina, Saskatchewan, whereas insecticide and organochlorine analysis was carried out by the Environment Canada laboratory in Edmonton, Alberta. All residues were quantified and confirmed using a Hewlett-Packard gas chromatograph equipped with a mass selective detector (GC-MSD). Elution of XAD-2 Resin Columns used in the Dust Collector The wet XAD-2 resin columns were vacuum aspirated for 30 minutes to remove as much residual water as possible. Air entering the columns was passed through a PUF plug to remove organic contaminants. The columns were then extracted by back flushing with 1000 mL of acetone at a rate of 10 mL min-1. This extracted both the organic compounds of interest and any remaining residual water from the resin. The acetone extract was concentrated to ~ 100 mL using a rotary evaporator (water bath at 30oC) and then transferred to a 250 mL evaporating flask and further concentrated as an aqueous phase to ~ 50 mL. This aqueous phase was then made up to volume (100 mL) with water and divided into 50 mL aliquots. One aliquot was acidified to pH 2 with dilute H2SO4 solution, extracted with dichloromethane and the extract methylated with diazomethane and subjected to Florisil column clean-up prior to GC-MSD analysis for extracted herbicides (Cessna et al., 1985). The second aqueous aliquot was extracted with dichloromethane, subjected to Florisil column clean-up and analysed for insecticides and organochlorines by GC-MSD. Extraction of PUF/XAD-2 Sampling Units On alternate weeks the PUF/XAD-2 sampling units were extracted for herbicide or for insecticide and organochlorine content. For herbicide analysis, the sampling unit was soxhlet extracted for 8 h with acetone (Grover et al., 1994). The acetone extract was concentrated to ~ 0.5 mL using a rotary evaporator (water bath 30o C) and then methylated with ethereal diazomethane. The methylated extract was subjected to Florisil column cleanup prior to analysis by GC-MSD. For insecticide and organochlorine analysis, the PUF sampling unit was soxhlet extracted for 12 h with dichloromethane. The extract was concentrated using a rotary evaporator and then subjected to Florisil column cleanup prior to analysis by GC-MSD. Residue Analysis and Confirmation The Hewlett-Packard GC-MSD system and operating conditions used for herbicide residue analysis have been described previously (Cessna et al., 1997). A similar GC/MSD system was used for inseecticide and organochlorine analysis, however the column employed was a 30 m x 0.25 mm I.D. Rtx-5 column (0.25 ?m film thickness). For operation of the GC, helium was used as the carrier gas and the temperature program was: initially held at 80oC for 1 minute then ramped to 200oC at 15oC/min; held at 200oC for 5 minutes then increased at 8oC/min to 300oC and held for 10 minutes. A split/splitless injector was used in the splitless mode. Injection port and transfer line temperatures were 270oC and 280oC, respectively. Depending on the compound, from two to four ions were monitored on the MSD. The presence of each compound was considered to be confirmed if: all ions monitored were present; a peak appeared at the retention time (? 0.02 min) obtained for a standard solution of the pesticide in the reconstructed chromatiograms of all ions; and, the peak area ratio was within 30% of the ratio obtained using a standard solution of the pesticide. 6. Observations 6.1 Data Notes None. 6.2 Field Notes None. 7. Data Description 7.1 Spatial Characteristics 7.1.1 Spatial Coverage The North American Datum 1983 (NAD83) coordinates for the SSA measurement site are: Longitude Latitude ---------- --------- Waskesiu 106.0678 W 53.9178 N 7.1.2 Spatial Coverage Map None given. 7.1.3 Spatial Resolution The measurements were made at a single location in the SSA. 7.1.4 Projection Not applicable. 7.1.5 Grid Description Not applicable. 7.2 Temporal Characteristics 7.2.1 Temporal Coverage The data were collected from June 16 to August 13, 1993 and May 4 to July 20, 1994 7.2.2 Temporal Coverage Map All the data were collected at the same location. 7.2.3 Temporal Resolution The samplers operated 24 hours per day over each 7 day sampling period. 7.3 Data Characteristics Data characteristics are defined in the companion data definition file (tgb7ddho.def). 7.4 Sample Data Record Sample data format shown in the companion data definition file (tgb7ddho.def). 8. Data Organization 8.1 Data Granularity All of the Dry Deposition Herbicide and Organochlorine Flux Data are contained in one dataset. 8.2 Data Format(s) The data files contain numerical and character fields of varying length separated by commas. The character fields are enclosed with single apostrophe marks. There are no spaces between the fields. Sample data records are shown in the companion data definition file (tgb7ddho.def). 9. Data Manipulations 9.1 Formulae 9.1.1 Derivation Techniques and Algorithms None given. 9.2 Data Processing Sequence 9.2.1 Processing Steps None given. 9.2.2 Processing Changes None given. 9.3 Calculations 9.3.1 Special Corrections/Adjustments None given. 9.3.2 Calculated Variables None given. 9.4 Graphs and Plots None given. 10. Errors 10.1 Sources of Error Irreproducible packing of the XAD-2 resin column. 10.2 Quality Assessment Standard laboratory procedures involving blanks, spikes and replicates. 10.2.1 Data Validation by Source None given. 10.2.2 Confidence Level/Accuracy Judgment None given. 10.2.3 Measurement Error for Parameters None given. 10.2.4 Additional Quality Assessments None given. 10.2.5 Data Verification by Data Center The data were examined for general consistency and clarity. 11. Notes 11.1 Limitations of the Data None given. 11.2 Known Problems with the Data None given. 11.3 Usage Guidance None given. 11.4 Other Relevant Information None given. 12. Application of the Data Set The data can be used to quantify the Trace organic contaminants entering the site from atmospheric transport and identify chemicals which require further research. 13. Future Modifications and Plans None given. 14. Software 14.1 Software Description None given. 14.2 Software Access None given. 15. Data Access 15.1 Contact Information Ms. Beth Nelson BOREAS Data Manager NASA GSFC Greenbelt, MD (301) 286-4005 (301) 286-0239 (fax) Elizabeth.Nelson@gsfc.nasa.gov 15.2 Data Center Identification See 15.1. 15.3 Procedures for Obtaining Data Users may place requests by telephone, electronic mail, or FAX. 15.4 Data Center Status/Plans The TGB-07 dry deposition herbicide data are available from the EOSDIS ORNL DAAC (Earth Observing System Data and Information System) (Oak Ridge National Laboratory) (Distributed Active Archive Center). The BOREAS contact at ORNL is: ORNL DAAC User Services Oak Ridge National Laboratory (865) 241-3952 ornldaac@ornl.gov ornl@eos.nasa.gov 16. Output Products and Availability 16.1 Tape Products None 16.2 Film products None. 16.3 Other products Comma delimited ASCII files 17. References 17.1 Platform/Sensor/Instrument/Data Processing Documentation None given. 17.2 Journal Articles and Study Reports Cessna, A. J., Grover, R., Kerr, L. A. and Aldred, M.L. (1985) A multiresidue method for the analysis and verification of several herbicides in water. J. Agric. Food Chem. 33, 504-507. Cessna, A. J., Waite, D. T. and Constable, M. (1997) Concentrations of pentachlorophenol in atmospheric samples from three Canadian locations, 1994. Bull. Environ. Contamin. Toxicol. 58, 651-658. Grover, R., Smith, A. E. and Cessna, A. J. (1994) Fate of bromoxynil n- butyrate and iso-octanoate applied as a mixture to a wheat field. J. Environ. Qual. 23(6), 1304-1311. Sellers, P., F. Hall. 1994. Boreal Ecosystem-Atmosphere Study: Experiment Plan. Version 1994-3.0, NASA BOREAS Report (EXPLAN 94). Sellers, P., F. Hall, H. Margolis, B. Kelly, D. Baldocchi, G. den Hartog, J. Cihlar, M.G. Ryan, B. Goodison, P. Crill, K.J. Ranson, D. Lettenmaier, and D.E. Wickland. 1995. The boreal ecosystem-atmosphere study (BOREAS): an overview and early results from the 1994 field year. Bulletin of the American Meteorological Society. 76(9):1549-1577. Sellers, P., F. Hall, K.F. Huemmrich. 1996. Boreal Ecosystem-Atmosphere Study: 1994 Operations. NASA BOREAS Report (OPS DOC 94). Sellers, P., F. Hall. 1996. Boreal Ecosystem-Atmosphere Study: Experiment Plan. Version 1996-2.0, NASA BOREAS Report (EXPLAN 96). Sellers, P., F. Hall, K.F. Huemmrich. 1997. Boreal Ecosystem-Atmosphere Study: 1996 Operations. NASA BOREAS Report (OPS DOC 96). Sellers, P.J., F.G. Hall, R.D. Kelly, A. Black, D. Baldocchi, J. Berry, M. Ryan, K.J. Ranson, P.M. Crill, D.P. Lettenmaier, H. Margolis, J. Cihlar, J. Newcomer, D. Fitzjarrald, P.G. Jarvis, S.T. Gower, D. Halliwell, D. Williams, B. Goodison, D.E. Wickland, and F.E. Guertin. (1997). "BOREAS in 1997: Experiment Overview, Scientific Results and Future Directions", Journal of Geophysical Research (JGR), BOREAS Special Issue, 102(D24), Dec. 1997, pp. 28731-28770. Thompson, T. S., R. G. Treble, D. T. Waite and A. J. Cessna. 1997. Identification of pentachloronitrobenzene in ambient air extracts. Bull. Environ. Toxicol. Chem. 58:939-944. Waite, D. T., A. J. Cessna, N. P. Gurprasad and J. Banner. ___. Evaluation of a new sampler for collecting separate dry and wet atmospheric depositions of trace organic chemicals. Atmos. Environ. accepted Waite, D. T., N. P. Gurprasad, A. J. Cessna and D. V. Quiring. ____. Atmospheric pentachlorophenol concentrations in relation to air temperature at five Canadian locations. Chemosphere accepted. Waite, D. T., N. P. Gurprasad and M. B. Constable. 1996 Concentrations of pentachlorophenol and some related compounds in seasonally collected atmospheric samples from five Canadian locations. Organohalogen Compds. 28:482-489. 17.3 Archive/DBMS Usage Documentation None. 18. Glossary of Terms None given. 19. List of Acronyms BOREAS - BOReal Ecosystem-Atmosphere Study BORIS - BOREAS Information System DAAC - Distributed Active Archive Center EOS - Earth Observing System EOSDIS - EOS Data and Information System GSFC - Goddard Space Flight Center NASA - National Aeronautics and Space Administration NSA - Northern Study Area ORNL - Oak Ridge National Laboratory PANP - Prince Albert National Park SSA - Southern Study Area URL - Uniform Resource Locator (a World Wide Web address) 20. Document Information 20.1 Document Revision Date Written: 04-Dec-1997 Last updated: 14-Sep-1998 20.2 Document Review Date(s) BORIS Review: 27-Aug-1998 Science Review: 20.3 Document 20.4 Citation 20.5 Document Curator 20.6 Document URL Keywords organochlorines, herbicides, atmospheric transport, rain, dry deposition, ambient air TGB07_Dry_Herb_Conc.doc 09/14/98