Overview of the Nature, Extent, Health Risks, and Treatment of Arsenic-affected Drinking Water in Bangladesh
Seth H. Frisbie, Better Life Laboratories, Inc., East Calais, VT
Donald M. Maynard, The Johnson Company, Inc.,  Montpelier, VT
Erika J. Mitchell, Better Life Laboratories, Inc.,  East Calais, VT
Richard Ortega, Université de Bordeaux, Gradignan, France
Bibudhendra Sarkar, University of Toronto, Ontario Canada

Effect of Tungsten on Leaching of Lead from Contaminated Soils
Washington Braida, Stevens Institute of Technology
Christos Christodoulatos, Stevens Institute of Technology
Dimitris Dermatas, Stevens Institute of Technology
Michael Los, TACOM-ARDEC, US Army Heavy Metals Office
Steven L. Larson, US Army Corps of Engineers

Sorption, Desorption and Leaching Transport of Heavy Metals in Soils Common to New England
Alton Day Stone, Alton Engineer
James C. O'Shaughnessy, Worcester Polytechnic Institute

Passive Diffusion Sampling for Metals
John Tunks, Parsons, Denver, CO
John Hicks, Parsons, Denver, CO
Raphael Vazquez, AFCEE/ERT, Brooks City-Base, TX

Innovative Continuous On-Line Monitoring of Mercury and Arsenic
Hakan Gürleyük, Carl Hensman and Phil Kilner, Frontier Geosciences, Seattle, W
William T. Dietze, Ph.D., TraceDetect, Seattle, WA

Stabilization of Metals in Soils by Xanthan and Chitosan, With or Without Cross-Linking
Omid Etemadi, University of Southern California
Ioana G. Petrisor, University of Southern California
Victor Chen, University of Southern California
Teh Fu Yen, University of Southern California

Environmental Legacy of Arsenical Herbicide Application to Lakes and Ponds in Massachusetts 
Valerie Monastra, Department of Urban and Environmental Policy and Planning,
John Durant, Department of Civil and Environmental Engineering
Sheldon Krimsky, Department of Urban and Environmental Policy and Planning

Overview of the Nature, Extent, Health Risks, and Treatment of Arsenic-affected Drinking Water in Bangladesh

Seth H. Frisbie, Better Life Laboratories, Inc., 293 George Rd., East Calais, VT 05650, Tel: 802-456-7054, Fax: 802-456-7054, Email: shf3@cornell.edu
Donald M. Maynard, The Johnson Company, Inc., 100 State St., Montpelier, VT 05602, Tel: 802-229-4600, Fax: 802-229-5876, Email DMM@jcomail.com
Erika J. Mitchell, Better Life Laboratories, Inc., 293 George Rd., East Calais, VT 05650, Tel 802-456-7054, Fax: 802-456-7054, Email em63@cornell.edu
Richard Ortega, Laboratoire de Chimie Nucléaire Analytique et Bioenvironnementale, CNRS UMR 5084, Université de Bordeaux 1, 33175 Gradignan, France, Tel: (33) 557 12 09 07, Fax: (33) 557 12 09 00, Email ortega@cenbg.in2p3.fr
Bibudhendra Sarkar, Department of Structural Biology and Biochemistry, The Hospital for Sick Children and Department of Biochemistry, University of Toronto, Toronto, Ontario M5G 1X8, Canada, Tel: 416-813-5921, Fax: 416-813-5379, Email bsarkar@sickkids.on.ca

This is an overview of our 6 years of research on arsenic-affected drinking (tubewell) water in Bangladesh.  Our team produced the first national-scale maps of arsenic, chloride, phosphate, nitrate, sulfide, sulfate, total iron, ferrous iron, and dissolved oxygen in Bangladesh’s groundwater.  The map of arsenic concentration suggests over 50,000,000 Bangladeshis are drinking water with unsafe levels of this carcinogen.  These maps, oxidation-reduction potentials, pH measurements, and bench-scale testing suggest the major sources of arsenic in Bangladesh’s groundwater may be the dissolution of non-pyrite minerals in a reducing environment, and the anion exchange of sorbed arsenate or sorbed arsenite.  Our important discovery that tubewells often contain an analytical interference to the 1,10-phenanthroline methods for measuring iron suggested that non-arsenic toxins are widely distributed in Bangladesh’s drinking water.  Furthermore, the finding of severe melanosis, keratosis, skin cancer and other symptoms of chronic arsenic poisoning, especially among children, indicated that other metals are magnifying the toxic effects of arsenic.  Unfortunately, our subsequent research confirmed that Bangladeshis are commonly exposed to non-arsenic toxins in their drinking water.  Tens of millions of Bangladeshis are drinking water with unsafe levels of manganese, lead, nickel, or chromium.  This research also suggests that groundwater with unsafe levels of arsenic, manganese, lead, nickel and chromium may extend beyond Bangladesh’s border into the 4 adjacent and densely populated states in India.  In addition to the health risks from individual toxins, possible multimetal synergistic and inhibitory effects are discussed.  Antimony was detected in 98% of the samples from this study and magnifies the toxic effects of arsenic.  In contrast, selenium and zinc were below our detection limits in large parts of Bangladesh and prevent the toxic effects of arsenic.  Finally, several options for supplying safe drinking water in Bangladesh are evaluated.

Effect of Tungsten on Leaching of Lead from Contaminated Soils

Washington Braida, Center for Environmental Engineering, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, NJ 07030, Tel: 201-216-5681, Fax: 201-216-8303 , Email: wbraida@stevens-tech.edu
Christos Christodoulatos, Center for Environmental Engineering, Stevens Institute of Technology, Castle Point on Hudson, Hoboken, NJ 07030, Tel: 201-216-5675, Fax: 201-216-8303 , Email: christod@stevens-tech.edu
Dimitris Dermatas, Stevens Institute of Technology, Civil, Environmental, and Ocean Engineering Department, Castle Point on Hudson, Hoboken, NJ 07030, Tel: 201-216-8926, Fax: 201-216-5352, Email: ddermata@stevens-tech.edu
Michael Los, TACOM-ARDEC, US Army Heavy Metals Office, Picatinny Arsenal, Picatinny, NJ 07806 Tel: 973-724-7038, Fax: 973-724-2034, Email: mlos@pica.army.mil
Steven L. Larson, US Army Corps of Engineers, Engineer Research and Development Center, Environmental Laboratory, 3909 Halls Ferry Rd, Vicksburg, MS, 39180, Tel: 601-634-3431, Fax: 601- 634-2742, Email: larsons@wes.army.mil

The dissolution behavior of tungsten metal and tungsten heavy alloys is not well understood.  This research focuses on the effects of firing tungsten-based ammunition on soil contaminated with legacy lead.  In this study, soil columns containing lead-contaminated soil from Fort Irwin range 5 (pH 8.2, initial lead concentration 5000 mg/kg) were leached with DI water for a period ranging between 78 and 85 days.  One column was used as a control and three other columns were amended with 1 gram of either tungsten oxide (WO₃, 20 mm particle size), ammunition grade tungsten powder (5 mm particle size), or a 90W:7Ni:3Fe mixture of metallic powder (5 mm particle size).  After 100 pore volumes were passed through the columns, no significant differences were found among the amounts of lead leached from the control columns and the tungsten-amended columns (values were systematically higher for the non-amended column, ranged from non detectable to 0.200 mg/L and were always smaller than the lowest calibration standard).  pH of the columns’ effluents ranged between 6.5 and 7.7 which significantly reduced lead leaching.  However, in the conditions tested large amounts of tungsten leached from the columns containing tungsten amended soils (leachate concentration ranged between 1 and 15mg/L).  Tungsten leached appeared to be in the form of dissolved tungsten (particle size smaller than 0.2 mm) and colloidal tungsten particles (particle sizes between 0.2 mm and 20mm).  The dissolved concentration/total concentration ratio ranged from 0.68 for W metallic powder to 1 for WO₃.  This study provides useful information for the management of firing range soils contaminated with a mixture of heavy metals. 

Sorption, Desorption and Leaching Transport of Heavy Metals in Soils Common to New England

Alton Day Stone, PE, LSP, Alton Engineering, 10 Rugg Road, Sterling, MA 01564, Tel: 978-422-8014, Fax: 978-422-8014, Email: adaystone@aol.com
James C. O'Shaughnessy, Ph.D., PE, Civil Engineering Department, Worcester Polytechnic Institute, 100 Institute Road, Worcester, MA 01609, Tel: 508-831-5309, Fax: 508-831-5808, Email: jco@wpi.edu

Heavy metals are recognized as human health and environmental contaminants of concern.  Non-industrial human exposures typically involve metals dissolved in water, sorbed in the soil, or contained in foods. Leaching of heavy metals to groundwater supplies is of particular concern.  Heavy metals bioaccumulate in biota, and bioconcentrate in animals at higher trophic levels in the food chain.  Animal exposures typically include ingestion of water, plant material and contact with soil. Risk characterization is a formal part of the process for remediation of properties contaminated with hazardous materials. The risk posed by heavy metals in the environment is a function of toxicity, physical parameters, and the mobility of the metal in the soil.  To date, there is limited quantitative data regarding the sorption, leaching, and transport of metals in the vadose zone.  This paper presents the results of bench scale experiments to evaluate these phenomena.  Sixteen study soil columns were prepared using soils common to New England.  Soils contained varying amounts of plastic and non-plastic fines, and included outwash sands, clay and till deposits.  Physical parameters of each column were determined, including - cation exchange capacity, particle size parameters and plasticity.  Each column was filled with one liter of solution containing known concentrations of cadmium, chromium, copper, nickel and zinc.  After a four-day contact period, columns were gravity drained for two days, and the volume of effluent solution and associated metals concentrations determined.  Columns were then leached by application of 20 tap water rinses of approximately one pore volume each, and the concentration of each metal in the rinse lixiviant determined.  Data was used to investigate the capacity of soils to sorb metals, whether soil physical parameters are predictive of sorption, the ability of tap water to leach the metals, and the kinetics of the leaching process. 

Passive Diffusion Sampling for Metals

John Tunks, Parsons, 1700 Broadway, Ste. 900, Denver, CO 80290, Tel: 303-764-8740 , Fax: 303-831-8208
John Hicks, Parsons, 1700 Broadway, Ste. 900, Denver, CO. 80290, Tel: 303-764-1941, Fax: 303-831-8208
Raphael Vazquez, AFCEE/ERT, 3207 Sidney Brooks, Brooks City-Base, TX  78235-5344, Tel: 210-536-1431, Fax: 210-536-4330

Groundwater sample collection using passive diffusion samplers (PDSs) represents a relatively new technology that employs passive sampling methods for monitoring selected dissolved constituents in groundwater.  To date, the most common application of diffusion sampling has been for long-term monitoring of volatile organic compounds.  Results of a field-scale PDS demonstration for inorganics at Grissom Air Reserve Base, Indiana will be presented.  The primary objective of this PDS demonstration is to assess the effectiveness of the PDS method by comparing groundwater analytical results for metals obtained using the current (conventional) sampling method with results obtained using the PDS method.  The comparison of the conventional and diffusion sampling results will allow assessment of the appropriateness of implementing diffusion sampling for metals at each sampled well.  Details will include a general description of the work performed, a summary of how PDS and conventional results compared, and a comparative cost analysis of the two sampling approaches.

Innovative Continuous On-Line Monitoring of Mercury and Arsenic

Hakan Gürleyük, Ph.D., Research Scientist, Frontier Geosciences, 414 Pontius Ave. N, Seattle, WA 98109, Tel: 206-622 6960, Fax: 206- 622 6870, Email: HakanG@FrontierGeosciences.com
Carl Hensman, Ph.D., Research Scientist, Frontier Geosciences, 414 Pontius Ave. N, Seattle, WA 98109, Tel: 206-622 6960, Fax: 206-622 6870
Phil Kilner, Research Analyst, Frontier Geosciences, 414 Pontius Ave. N, Seattle, WA 98109, Tel: 206-622 6960, Fax: 206-622 6870
William T. Dietze, Ph.D., Chief Technical Officer, TraceDetect, 180 N. Canal St., Seattle, WA 98103, Tel: 206-523 2009, Fax: 206-523 2042

Most natural water systems and process and waste streams are monitored using periodic grab sampling and analysis. Spot monitoring like this results in a low-resolution understanding of a stream’s chemistry. With a limited number of data points, one high spike may pull the average concentration up exceeding discharge limits. To better understand and monitor temporal variability of mercury in complex matrices Frontier Geosciences has developed an innovative continuous mercury monitoring system. The system utilizes online sample preparation involving chemical, thermal, and UV digestion. Detection is achieved by cold vapour atomic florescence spectrometry (CV-AFS).  The analyzer is run using either EPA method 1631 or 245.7 to achieve a detection range of sub-ppt to 100 ppb levels. The system is capable of measuring mercury concentration at 5-minute intervals. This interval can be increased as needed by the operator. Modifications to the physical instrument, to the analyzer chemistry, and to the analytical method have been made, optimizing the system to run matrices ranging from drinking water to petroleum hydrocarbon, and organic rich process water from a natural gas plant. Due to the increased interest in arsenic, we have also built an on-line monitoring instrument for arsenic. This instrument incorporates a similar sample treatment system with a different chemistry suitable for As. Sub-ppb detection limits are achieved using Anodic Stripping Voltammetry with the patented NanoBand Electrodes in a novel flowcell. Continuous monitoring achieved using these systems increases data resolution enabling researchers and plant operators to better understand chemically complex and temporally variable systems. Geochemical trends that are not apparent under spot monitoring may come to light. Dischargers can better tailor treatment systems and insure proper operation in rapidly changing situations. The instrument can be built to collect samples from various parts of process for continuous mass balance determinations. The details of the method and results of a number of field studies will be presented.

Stabilization of Metals in Soils by Xanthan and Chitosan, With or Without Cross-Linking 

Omid Etemadi, Department of Civil and Environmental Engineering, University of Southern California, 3620 S. Vermont Ave., KAP 210 – MC 2531, Los Angeles, CA 90089-2531, Tel: 213-740-0594, Fax: 213-744-1426, Email:  oetemadi@usc.edu
Ioana G. Petrisor, Department of Civil and Environmental Engineering, University of Southern California, 3620 S. Vermont Ave., KAP 210 – MC 2531, Los Angeles, CA 90089-2531, Tel: 213-740-0594 , Fax: 213-744-1426, Email: petrisor@usc.edu
Victor Chen, Department of Civil and Environmental Engineering, University of Southern California, 3620 S. Vermont Ave., KAP 210 – MC 2531, Los Angeles, CA 90089-2531, Tel:  213-740-0593 , Fax: 213-744-1426, Email:  chemical160@hotmail.com
Teh Fu Yen, Department of Civil and Environmental Engineering, University of Southern California, 3620 S. Vermont Ave., KAP 210 – MC 2531, Los Angeles, CA 90089-2531, Tel:  213-740-0586, Fax: 213-744-1426, Email: tfyen@usc.edu

Environmental contamination with heavy metals and radionuclides is raising major environmental problems worldwide. Innovative technologies should be targeted for permanent enclosure and fixation of nuclear and other extreme hazardous metallic wastes in subsurface soils. Biopolymers may be potential tools for such innovative technologies, since they provide ample opportunity for chemical reaction with metals, soil particles, and other biopolymers. However, one problem remains to be solved, namely their biodegradability in soils. Starting from the additional ability of biopolymers to create cross-linking products resulting in interpenetrating networks, the current paper investigates the capacity of such networks to encapsulate metal contaminants in soil and keep them stable bound as compared with non-cross-linked biopolymers. Two biopolymers were investigated: xanthan and chitosan, as non-cross-linked and cross-linked, separately and in combination (as a cross-linked product). The experiments were performed in a laboratory drainage flow system, consisting of a column packed with soil, through which biopolymers solutions were run first, followed by Pb solution and leaching agents (water and 5% HCl). The changes in soil characteristics (permeability, shear strength) as well as the percentage of Pb retained in the column with subsequent leaching were analyzed. The results showed that both xanthan and chitosan with or without cross-linking, used separately or in combination, changed soil characteristics (decreased the permeability, increased the shear strength) acting as plugging agents and retained up to more than 90% of Pb in the soil column. However, more than 50% of the Pb retained could be leached by water or HCl in all experiments, except for the one with the cross-linked product of xanthan and chitosan. This product was able to retain most of the Pb from solution in a most stable form, and also displayed the strongest plugging effect. The cross-linked xanthan and chitosan product is therefore considered of interest for applications and will be further tested for its stability to biodegradation.

Environmental Legacy of Arsenical Herbicide Application to Lakes and Ponds in Massachusetts 

Valerie Monastra, Department of Urban and Environmental Policy and Planning, 97 Talbot Avenue, Medford, MA 02155, Tel: 617-627-3394, Fax:617-627-3377, Email Valerie.Monastra@tufts.edu
John Durant, Department of Civil and Environmental Engineering, Anderson Hall 200 College Ave., Medford, MA 02155, Tel: 617-627-5489, Fax:  617-627 3994
Sheldon Krimsky, Department of Urban and Environmental Policy and Planning, 97 Talbot Avenue, Medford, MA 02155, Tel: 617-627-3394, Fax: 617-627-3377

During the 1950's - 1960's many lakes and ponds in Massachusetts were treated with arsenical herbicides to control the growth of nuisance vegetation.  As a result of arsenical treatment the sediments of some waterbodies appear to contain very high levels of arsenic.  For example, Lake Quannapowitt contains between 95 - 225 mg/kg of As in shallow sediments dated to early 1960’s.  This is far above background level of 17 ppm of As (DEP, MA). Durant et al. (2003, in press) reported elevated As concentrations in the sediments of Spy Pond (Arlington, MA) which also has a record of arsenical pesticide applications.  They reported As concentrations up to 2600 ppm in the pond sediments dated 1962-1956 which have background concentrations between 10-40 ppm.  Many of the ponds treated with arsenic are used for recreational activities; thus, the potential of arsenic mobility in the ponds could pose a health risk and warrants the study of its distribution in the sediments and water column.  

In this study we investigated the ability of arsenic to be leached from the sediments into the water column as well as inorganic and organic complexes that may affect arsenic adsorption and mobility in various waterbodies.  In the fall of 2002, water and sediment samples from seven Massachusetts lakes and ponds that have a record of arsenic application.  Three of the sampled ponds were stratified and four were unstratified. The stratified ponds display reducing conditions below 3 meters depth.  Typical pH measurements were between 6.25 and 9.11.  It was found that Mn, Fe, Al, S and organic matter affected the behavior and distribution of As in the sediment and water samples.  Due to the relatively low dissolved oxygen levels and high pH of the pond waters sampled, there is a high potential for arsenic remobilization from sediments, particularly in the stratified lakes studied. 

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