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The Occurrence and Sources of Perchlorate in Massachusetts

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The Occurrence and Sources of Perchlorate in Massachusetts Massachusetts Department of Environmental Protection DRAFT REPORT TThhee OOccccuurrrreennccee aanndd SSoouurrcceess ooff PPeerrcchhlloorraattee iinn MMaassssaacchhuusseettttss August 2005 Updated April 2006 Massachusetts Department of Environmental Protection 1 Winter Street Boston, MA 02108 http://www.mass.gov/dep/ This page intentionally blank *** DRAFT REPORT *** Executive Summary In recent years, the Massachusetts Department of Environmental Protection (MassDEP) has undertaken a series of initiatives and studies to ascertain the extent to which the perchlorate ion is present in the groundwater and surface waters of the state. While many questions remain, based upon the totality of information obtained to date, the agency has made a number of preliminary findings and conclusions: Occurrence The perchlorate ion is not pervasive in surface water or groundwater in Massachusetts, having been found in only 9 of 600 tested public water supply systems at or above an analytical Reporting Limit of 1 µg/L (ppb). Detections have in most cases been related to known or suspected uses or releases of perchlorate-containing materials. Sources The most prevalent sources of perchlorate contamination in environmental media in Massachusetts were found to be blasting agents, military munitions, fireworks, and, to a lesser extent, hypochlorite (bleach) solutions. Additionally, at one location, a perchloric acid user was identified as a significant source of perchlorate contamination to a river system. Impacts The order-of-magnitude impacts associated with observed sources to date include: • Blasting agents - hundreds to thousands of µg/L (ppb) in groundwater and small streams • Military Munitions - hundreds of µg/L (ppb) in groundwater • Fireworks - single digit to double digit µg/L (ppb) in groundwater • Industrial Perchloric Acid Use - hundreds of µg/L (ppb) in effluent from municipal sewage treatment plant; single to double digit µg/L (ppb) in receiving river systems Based upon a limited sampling effort, hypochlorite solutions used at water and wastewater treatment plants were found to contain between 260 and 6750 µg/L (ppb) of perchlorate, with concentrations of perchlorate increasing with time of product storage. This could result in detectable levels of perchlorate (0.2 – 0.4 µg/L) in chlorinated drinking water distribution systems. Perchlorate was also found in household bleach, from 89 µg/L (ppb) to 8000 µg/L (ppb), with concentrations increasing with time of product storage. While the on-site discharge of household bleach via washing machine use could result in low-level impacts to groundwater, discharges of perchlorate to conventional (anaerobic) septic tanks were found to be treated to less than 1 µg/L (ppb). Analytical The use of a modified EPA Method 314.0 was shown to reliably detect and quantify 1 µg/L (ppb) or greater concentrations of the perchlorate ion in drinking water matrices common in Massachusetts (i.e., less than 500 µS/cm specific conductance). This page intentionally blank TABLE OF CONTENTS 1.0 INTRODUCTION ……………………………………………………………………………………………………………………………. 1 2.0 BACKGROUND ………………………………………………………………………………………………………………………………….1 2.1 Production and Uses of Perchlorates ………………………………………………………………………. 1 2.2 Fate and Transport of the Perchlorate Ion …………………………………………………………..2 2.3 Initial Detections of Perchlorate in Massachusetts ………………………………………….. 3 3.0 OCCURRENCE OF PERCHLORATE IN MASSACHUSETTS …………………………..……………………………….. 3 4.0 SOURCES OF PERCHLORATE IN MASSACHUSETTS ……………………………………………………………………. 7 4.1 Explosives and Blasting Agents ……………………………………………………………………………….. 7 4.1.1 Potential Environmental Release Mechanisms and Pathways ……………… 9 4.1.2 Blasting near Public Water Supply Systems …………………………………………. 10 4.1.2.1 Millbury ……………………………………………………………………………………………. 10 4.1.2.2 Westford ………………………………………………………………………………………… 12 4.1.2.2 Boxborough …………………………………………………………………………………….. 14 4.1.3 Discussion ………………………………………………………………………………………………………. 16 4.1.4 Nitrate …………………………………………………………………………………………………………… 16 4.2 Fireworks ……………………………………………………………………………………………………………………… 19 4.2.1 Potential Environmental Release Mechanisms and Pathways ………………. 20 4.2.2 Modeling of Potential Impacts from Fireworks Displays …………………….. 21 4.2.3 Fireworks Displays near Public Water Supplies in Massachusetts …… 21 4.2.3.1 Chesterfield ……………………………………………………………………………………. 23 4.2.3.2Westport …………………………………………………………………………………………. 24 4.2.3.3Williamstown …………………………………………………………………………………… 26 4.2.4 Bourne Fireworks Display ………..……………………………………………………………….. 27 4.3.5 Easthampton Fireworks Display ……………………………………………………………….. 28 4.2.6 Dartmouth Fireworks Study Area …………………………………………………………… 29 4.3 Hypochlorite/Bleach Products ………………………………………………………………………………… 32 4.3.1 Chemistry of Hypochlorite Products ………………………………………………………. 32 4.3.2 Perchlorate in Commercial Hypochlorite Products ……………………………….. 34 4.3.3 Perchlorate in Household Bleach ……………………………………………………………….. 36 4.3.4 Potential Impacts ………………………………………………………………………………………….. 37 4.4 Perchloric Acid …………………………………………………………………………………………………………….. 38 4.4.1 Chemistry of Perchloric Acid …………………………………………………………………… 39 4.4.2 Perchloric Acid Discharger in Northeastern Massachusetts …………… 39 5.0 ANCILLARY FINDINGS ……………………………………………………………………………………………………………… 41 5.1 Analytical Testing Procedures ……………………………………………………………………………….. 41 5.2 Perchlorate Treatment in Septic Tanks ……………………………………………………………….. 42 6.0 CONCLUSIONS ………………………………………………………………………………………………………………………………43 7.0 RECOMMENDATIONS …………………………………………………………………………………………………………………… 44 8.0 RESEARCH NEEDS ……………………………………………………………………………………………………………………….. 45 LIST OF REFERENCES ………………………………………………………………………………………………………………………………..47 HISTORY OF REVISIONS ………………………………………………………………………………………………………………………… 48 LIST OF TABLES Table 1 Some Uses for Perchlorate Salts and Perchloric Acid …………………….. 2 Table 2 Massachusetts Public Water Supplies Impacted by at least 1 µg/L of Perchlorate …………………………………………………………………. 6 Table 3 Use of Explosive Products at 3 Construction Sites …………………………… 11 Table 4 Public Water Supplies near Fireworks Displays …………………………………… 23 Table 5 Sampling of Commercial Hypochlorite Solutions ………………………………… 35 Table 6 Hypochlorite Study by Town of Tewksbury Water Treatment Plant . 35 Table 7 Perchlorate Content in 4 Household Bleach Products ………………………… 36 Table 8 Treatment of Perchlorate in a Septic Tank …………………………………………. 43 LIST OF FIGURES Figure 1 Public Water Supplies in Massachusetts ………………………………………………. 5 Figure 2 Impacted Public Water Supplies in Massachusetts ……………………………. 5 Figure 3 Millbury, MA Blasting Site ……………………………………………………………………… 12 Figure 4 Westford, MA Blasting Site …………………………………………………………………… 13 Figure 5 Boxborough, MA Blasting Site ……………………………………………………………….. 15 Figure 6 Nitrate Levels in Wells Impacted by Perchlorate from Suspected Blasting Sources …………………………………………………………………….. 17 Figure 7 Millbury, MA Perchlorate vs Nitrate ……………………………………………………. 18 Figure 8 Modeled Perchlorate Impacts to Groundwater from Fireworks Display …………………………………………………………………………….. 22 Figure 9 Chesterfield, MA Fireworks Site …………………………………………………………. 24 Figure 10 Westport, MA Fireworks Site …………………………………………………………………. 25 Figure 11 Williamstown, MA Fireworks Site …………………………………………………………. 26 Figure 12 Bourne, MA Fireworks Site …………………………………………………………………….. 27 Figure 13 Fireworks Study Area, University of Massachusetts at Dartmouth .. 31 Figure 14 Perchloric Acid Discharge, Concord and Merrimack Rivers, MA ……… 39 *** DRAFT REPORT *** 1.0 INTRODUCTION Perchlorate is of concern because of its toxicity. It interferes with iodide transport into the thyroid gland, decreasing the availability of iodide needed for the synthesis of thyroid hormones, and thus has the potential to affect metabolism and normal growth and development, which could result in brain damage. The impacts of disrupting thyroid hormone synthesis are greatest on pregnant women and their developing fetuses, infants, children, and individuals who have low levels of thyroid hormones. More information in this regard is available from MassDEP at http://www.mass.gov/dep/brp/dws/percinfo.htm Little is known about the prevalence of perchlorate in the environment, particularly at low concentrations. This is due in large part to the relatively recent introduction of mass- produced perchlorate-containing products to commercial and industrial marketplaces, combined with historical limitations in analytical testing technologies. In an effort to shed some light on this subject, MassDEP has over the last 12 months initiated a series of investigatory efforts and programs. The purpose of this report is to explain and document these activities, and provide and discuss data and preliminary findings. 2.0 BACKGROUND 2.1. Production and Uses of Perchlorate The unusual and desirable properties of Perchloric acid and perchlorate salts were first discovered in the early part of the 20th century. Both are powerful oxidizing agents that are also exceptionally stable and safe to use. (Schumacher, 1960) The large-scale production of perchlorate salts began in the 1940s for military purposes, and in the following decades, for use as a solid oxidant in rockets and missiles. The two most common salts are ammonium and potassium perchlorate. To this day, the defense industry and NASA remain the largest users of perchlorate in the United States. According to the Department of Defense, perchlorate is currently used in over 250 types of munitions. (http://www.dodperchlorateinfo.net/facts/uses­ benefits/) Given
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