Containing Arsenic-Enriched Groundwater Tracing Lead Isotopic Compositions Of Common Arsenical Pesticides In A Coastal Maine Watershed Containing Arsenic-Enriched Ground Water

Proceedings of the Annual International Conference on Soils, Sediments, Water and Energy, Jan 2010

Arsenical pesticides and herbicides were extensively used on apple, blueberry, and potato crops in New England during the first half of the twentieth century. Lead arsenate was the most heavily used arsenical pesticide until it was officially banned. Lead arsenate, calcium arsenate, and sodium arsenate have similar Pb isotope compositions: 208Pb/207Pb = 2.3839-2.4722, and 206Pb/207Pb = 1.1035-1.2010. Other arsenical pesticides such as copper acetoarsenite (Paris green), methyl arsonic acid and methane arsonic acid, as well as arsanilic acid are widely variable in isotope composition. Although a complete understanding of the effects of historical use of arsenical pesticides is not available, initial studies indicate that arsenic and lead concentrations in stream sediments in New England are higher in agricultural areas that intensely used arsenical pesticides than in other areas. The Pb isotope compositions of pesticides partially overlap values of stream sediments from areas with the most extensive agricultural use. The lingering effects of arsenical pesticide use were tested in a detailed geochemical and isotopic study of soil profiles from a watershed containing arsenic-enriched ground water in coastal Maine. Acid-leach compositions of the soils represent lead adsorbed to mineral surfaces or held in soluble minerals (Fe- and Mn-hydroxides, carbonate, and some micaceous minerals), whereas residue compositions likely reflect bedrock compositions. The soil profiles contain labile Pb (acid-leach) showing a moderate range in 206Pb/207Pb (1.1870-1.2069), and 208Pb/207Pb (2.4519-2.4876). Isotope values vary as a function of depth: the lowest Pb isotope ratios (e.g., 208Pb/206Pb) representing labile lead are in the uppermost soil horizons. Lead contents decrease with depth in the soil profiles. Arsenic contents show no clear trend with depth. A multi-component mixing scheme that included lead from the local parent rock (Penobscot Formation), lead derived from combustion of fossil fuels, and possibly lead from other anthropogenic sources (e.g., pesticides), could account for Pb isotope variations in the soil profiles. In agricultural regions, our preliminary data show that the extensive use of arsenical pesticides and herbicides can be a significant anthropogenic source of arsenic and lead to stream sediments and soils.

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Containing Arsenic-Enriched Groundwater Tracing Lead Isotopic Compositions Of Common Arsenical Pesticides In A Coastal Maine Watershed Containing Arsenic-Enriched Ground Water

Proceedings of the Annual International Conference on Soils, Sediments, Water and Energy Volume 11 Article 6 January 2010 Containing Arsenic-Enriched Groundwater Tracing Lead Isotopic Compositions Of Common Arsenical Pesticides In A Coastal Maine Watershed Containing Arsenic-Enriched Ground Water Robert A. Ayuso U.S. Geological Survey Nora K. Foley U.S. Geological Survey Gilpin R. Robinson Jr. U.S. Geological Survey Anna S. Colvin U.S. Geological Survey Gail Lipfert University of Maine See next page for additional authors Follow this and additional works at: https://scholarworks.umass.edu/soilsproceedings Recommended Citation Ayuso, Robert A.; Foley, Nora K.; Robinson, Gilpin R. Jr.; Colvin, Anna S.; Lipfert, Gail; and Reeve, Andrew S. (2010) "Containing Arsenic-Enriched Groundwater Tracing Lead Isotopic Compositions Of Common Arsenical Pesticides In A Coastal Maine Watershed Containing Arsenic-Enriched Ground Water," Proceedings of the Annual International Conference on Soils, Sediments, Water and Energy: Vol. 11 , Article 6. Available at: https://scholarworks.umass.edu/soilsproceedings/vol11/iss1/6 This Conference Proceeding is brought to you for free and open access by ScholarWorks@UMass Amherst. It has been accepted for inclusion in Proceedings of the Annual International Conference on Soils, Sediments, Water and Energy by an authorized editor of ScholarWorks@UMass Amherst. For more information, please contact . Containing Arsenic-Enriched Groundwater Tracing Lead Isotopic Compositions Of Common Arsenical Pesticides In A Coastal Maine Watershed Containing Arsenic-Enriched Ground Water Authors Robert A. Ayuso, Nora K. Foley, Gilpin R. Robinson Jr., Anna S. Colvin, Gail Lipfert, and Andrew S. Reeve This conference proceeding is available in Proceedings of the Annual International Conference on Soils, Sediments, Water and Energy: https://scholarworks.umass.edu/soilsproceedings/vol11/iss1/6 Ayuso et al.: Containing Arsenic-Enriched Groundwater Tracing Lead Isotopic... PART II: HEAVY METALS Chapter 5 CONTAINING ARSENIC-ENRICHED GROUNDWATER TRACING LEAD ISOTOPIC COMPOSITIONS OF COMMON ARSENICAL PESTICIDES IN A COASTAL MAINE WATERSHED CONTAINING ARSENICENRICHED GROUND WATER Robert A. Ayuso1, Nora K. Foley1, Gilpin R. Robinson Jr.1, Anna S. Colvin1, Gail Lipfert2 and Andrew S. Reeve2 1 Mail Stop 954, National Center, U.S. Geological Survey, Reston VA, 20192; 2Department of Earth Sciences, University of Maine, Orono, ME 04469 Abstract: Arsenical pesticides and herbicides were extensively used on apple, blueberry, and potato crops in New England during the first half of the twentieth century. Lead arsenate was the most heavily used arsenical pesticide until it was officially banned. Lead arsenate, calcium arsenate, and sodium arsenate have similar Pb isotope compositions: 208Pb/207Pb = 2.3839-2.4722, and 206Pb/207Pb = 1.1035-1.2010. Other arsenical pesticides such as copper acetoarsenite (Paris green), methyl arsonic acid and methane arsonic acid, as well as arsanilic acid are widely variable in isotope composition. Although a complete understanding of the effects of historical use of arsenical pesticides is not available, initial studies indicate that arsenic and lead concentrations in stream sediments in New England are higher in agricultural areas that intensely used arsenical pesticides than in other areas. The Pb isotope compositions of pesticides partially overlap values of stream sediments from areas with the most extensive agricultural use. Produced by The Berkeley Electronic Press, 2006 Proceedings of the Annual International Conference on Soils, Sediments, Water and Energy, Vol. 11 [2006], Art. 6 68 Contaminated Soils- Heavy Metals The lingering effects of arsenical pesticide use were tested in a detailed geochemical and isotopic study of soil profiles from a watershed containing arsenic-enriched ground water in coastal Maine. Acid-leach compositions of the soils represent lead adsorbed to mineral surfaces or held in soluble minerals (Fe- and Mn-hydroxides, carbonate, and some micaceous minerals), whereas residue compositions likely reflect bedrock compositions. The soil profiles contain labile Pb (acid-leach) showing a moderate range in 206Pb/207Pb (1.1870-1.2069), and 208Pb/207Pb (2.4519-2.4876). Isotope values vary as a function of depth: the lowest Pb isotope ratios (e.g., 208Pb/206Pb) representing labile lead are in the uppermost soil horizons. Lead contents decrease with depth in the soil profiles. Arsenic contents show no clear trend with depth. A multi-component mixing scheme that included lead from the local parent rock (Penobscot Formation), lead derived from combustion of fossil fuels, and possibly lead from other anthropogenic sources (e.g., pesticides), could account for Pb isotope variations in the soil profiles. In agricultural regions, our preliminary data show that the extensive use of arsenical pesticides and herbicides can be a significant anthropogenic source of arsenic and lead to stream sediments and soils. Key words: 1. lead, arsenic, pesticides, New England, Maine, watershed, ground water, anthropogenic, soils, bedrock, Penobscot Formation, lead isotopes, sources, minerals INTRODUCTION Extensive application of arsenical pesticides and herbicides on apple, blueberry, and potato crops in New England during the first half of the twentieth century may have significantly contributed arsenic, lead, and other metals to the surface environment, and particularly to orchard soils (Veneman et al., 1983; Chormann, 1985; D’Angelo et al., 1996; Robinson and Ayuso, 2004). These metal-enriched soils can influence the composition of ground water. Lead arsenate, calcium arsenate, and sodium arsenate were the most important pesticides and herbicides, and among the three, lead arsenate was the most extensively applied pesticide (Peryea, 1998) in apple orchards. Copper acetoarsenite (Paris green) was also used throughout the region (Shepard, 1939; Veneman et al., 1983; Peryea, 1998). Before 1914 the U.S. imported most metallic arsenic from Germany (e.g., Smith, 1945). From 1914 to about 1930 the bulk of the arsenic production in the U.S. (marketed for commercial applications as As2O3, arsenic trioxide, or white arsenic) was derived as a metallurgical by-product of the smelting of copper, lead, and gold. Arsenic trioxide was used in the production of fertilizers, herbicides, and insecticides (Kirk-Othmer Encyclopedia of Chemical Technology, 1992; Ullman’s Encyclopedia, 1998), or if transformed to arsenic acid, used in the manufacture of https://scholarworks.umass.edu/soilsproceedings/vol11/iss1/6 Ayuso et al.: Containing Arsenic-Enriched Groundwater Tracing Lead Isotopic... TRACING PB ISOTOPIC COMPOSITIONS OF COMMON... 69 chromated copper arsenate, a preservative of wood products (Mineral Commodities Summary, 2004). A few companies accounted for the bulk of U.S. arsenic production in the first half of the twentieth century: Am (...truncated)


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Robert A. Ayuso, Nora K. Foley, Gilpin R. Robinson Jr., Anna S. Colvin, Gail Lipfert, Andrew S. Reeve. Containing Arsenic-Enriched Groundwater Tracing Lead Isotopic Compositions Of Common Arsenical Pesticides In A Coastal Maine Watershed Containing Arsenic-Enriched Ground Water, Proceedings of the Annual International Conference on Soils, Sediments, Water and Energy, 2010, pp. 6, Volume 11, Issue 1,