Montgomery Watson Applied Research Department

Technology Transfer Note

Water

No. 13, September 1997

TREATMENT ALTERNATIVES FOR PERCHLORATE

SUMMARY: Perchlorate (ClO4-) is used in solid rocket fuel, fireworks, and various pyrotechniques. Unfortunately, several groundwaters in California were contaminated by trace levels of perchlorate. Due to concern about its possible health effects, the California Department of Health Services (CalDHS) has adopted a provisional action level of 18 micrograms per liter for perchlorate in drinking water. At the present time, Cal DHS does not identify any effective treatment, recommending that when a utility finds a well which has perchlorate above this level it should remove the well from service. This has resulted in the closure of several groundwater wells in the state. Perchlorate is measured using a special Ion Chromatography (IC) method. Currently, a handful of laboratories across the country (including Montgomery Watson Laboratories) are certified for perchlorate analysis. There are currently four possible treatment processes for perchlorate that merit discussion. They are 1) anaerobic biodegradation, 2) Reverse Osmosis (RO) filtration, 3) GAC reduction, and 4) Ion-Exchange (IX). It is too early to cast a final judgement on any of these processes. This memo will attempt to provide a useful perspective on each. If you have any questions about the contents of this document, please call Dr. Samer Adham at (626) 568-6751, or contact him at samer.adham@us.mw.com. Perchlorate (ClO4-) has been detected in various California groundwaters at levels as high as 1,000 g/L, and most recently in Colorado River water at 7 to 9 g/L. The problem was first discovered during a Superfund monitoring program in northern California in February 1997. Since then, perchlorate has been detected in 69 out of 232 wells monitored. Of those wells, 24 had perchlorate levels above the state provisional action level. This Technology Transfer Note is a white paper on treatment alternatives for removing perchlorate from groundwater. The information included in this document was obtained largely from published literature as well as bench-scale testing conducted by Montgomery Watson during the summer of 1997. What is Perchlorate? Perchlorate is the electrochemical oxidation product of chlorate (ClO3-) according to the following half-reaction: ClO3- + H2O ClO4- + 2H + + 2e-; Eo = -1.23 V While perchlorate is a very strong oxidant (and highly explosive) in its solid state (e.g., ammonium perchlorate [NH4ClO4] is used as a solid rocket fuel), it is extremely stable when dissolved in water at concentrations as high as 1,000 mg/L. The sources of perchlorate contamination in various groundwaters has not been conclusively identified. However, contamination has been found in the vicinity of several former manufacturers and/or users of solid rocket fuel in northern and southern California. As an ion, perchlorate can be measured using a special, but straightforward, Ion-Chromatography (IC) method using a DIONEX IC column. Only a handful of commercial laboratories, including Montgomery Watson Laboratories, are certified for perchlorate analysis. The minimum reporting limit for the method is 4 g/L. Information on MONTGOMERY WATSON history, health effects and analytical protocols can be found on the CalDHS home page [www.dhs.cahwnet.gov/prevsrv/ddwem/index.htm]. Health Effects of Perchlorate Perchlorate, in very high doses, has been used in medicine in the treatment of Graves disease and therefore, there is an abundance of health effects information. When injested, perchlorate inhibits the ability of the thyroid gland to perform its normal function. Regulatory Requirements As a result of reviewing the 1992 and 1995 evaluations of perchlorate by USEPA, DHS Drinking Water Program considers the 18-ppb concentration of perchlorate in drinking water to be protective of public health. There is a possibility that the action level could be reduced in the future. If so, 4 g/L seems to be a likely minimum for two reasons: it is the minimum detection limit (MDL) of the analytical method and it is the lower range of CalDHS regulatory window, depending on the safety factor used. Treatment Alternatives Currently, there are four treatment alternatives for removing perchlorate from groundwater that are being actively considered. These include 1) anaerobic biodegradation, 2) Reverse-Osmosis (RO) filtration, 3) removal with GAC, and 4) Ion-Exchange (IX). The following paragraphs discuss the applicability of the four treatment alternatives for the removal of perchlorate from groundwater. Anaerobic Biodegradation In this process, microorganisms are used to biologically reduce perchlorate to other reduced forms such as chlorate or chloride. One bacterial species capable of this Page 1

Montgomery Watson Applied Research Department

Technology Transfer NoteWater No. 13, July 1997

TREATMENT ALTERNATIVES FOR PERCHLORATE

transformation is Wolinla succinogenes HPA-1. Laboratory and field tests are currently being conducted at the University of Colorado at Boulder, and at Tyndall Air Force Base, Florida. Testing at Tyndall Air Force Base was mainly conducted for the removal of ammonium perchlorate from solid rocket fuel, and not from contaminated groundwater. The biological process removed ammonium perchlorate from 3,000 mg/L to less than 0.5 mg/L (500 g/L). It is not clear at this time whether this process can reduce perchlorate to levels lower than 18 g/L. The process could be considered as a surface treatment process in that water would be pumped to the surface and treated using a suspended growth or attached growth process. Another approach is to implement this treatment in-situ by injecting the selected bacterial culture into the aquifer and allowing it to biodegrade perchlorate underground. In both processes, perchlorate acts as the electron acceptor, and thus anaerobic conditions would be required. Depending on the redox potential required, sulfide generation may be a problem in some waters. Reverse Osmosis Membrane Filtration RO membrane filtration has long been used to remove ions from water supplies. It is commonly used for the treatment of groundwaters with high TDS levels. Considering the charge of perchlorate, it is anticipated that it should be removed by RO membranes, at least as well as nitrate. Considering that perchlorate is soluble at levels as high as 200,000 mg/L, no precipitation is anticipated on the concentrate side of the membrane. Work is currently being done by Montgomery Watson to determine the percent rejection of perchlorate with RO membranes. The drawbacks of RO membrane processes are their high energy requirements, as well as the production of a high TDS brine that may contain high levels of nitrate, sulfate, and perchlorate. The production rate of the brine stream can be as high as 15% of the total groundwater treated. Removal With GAC GAC is commonly used for the removal of organic contaminants from drinking water supplies. GAC has also been considered for the removal of highly-oxidized chemicals such as chlorine, bromate, and chlorite. However, in the case of these compounds, studies have shown that the removal mechanism is not via conventional adsorption, but rather through a chemical reduction reaction occuring on the surface of the carbon. It seems likely this is also true for perchlorate. If so, the removal of perchlorate with GAC is conceptually achieved by the occurrence of the following reduction reaction at the surface of the carbon: 2C + ClO4- Cl- + 2CO2 This reaction is similar to that for the removal of chlorine from water with GAC. Information on the removal of perchlorate with GAC is sketchy. Limited data obtained Page 2 from an existing GAC treatment system at the City of Riverside, California indicate that perchlorate is removed with GAC. However, other information suggests that GAC is a very inefficient process for the removal of perchlorate. Ion-Exchange Perhaps the most promising process for the removal of perchlorate from drinking water supplies is Ion-Exchange (IX). IX processes are commonly used for the treatment of waters with high nitrate levels. The performance of the IX process is highly impacted by the sulfate concentration in the water. Bench-scale batch studies conducted by Montgomery Watson suggest that the affinity of the IX resin for perchlorate is higher than that for nitrate. These results were confirmed by subsequent column tests. The main problem with the use of IX for perchlorate removal is the production of a high TDS brine stream during the regeneration process. Approximately 10 lbs of salt (about 10 gallons of a 10% solution for example) is required for each cubic foot of resin regenerated. In addition there is rinse water that must be disposed of. This brine stream may range from 1% to 5% of the volume of water treated, usually in the range of 1 to 2%. However, there are several design and operational options that may both reduce the volume of the brine stream, and remove most of the objectionable ions in it prior to final disposal. These options are currently being evaluated by Montgomery Watson.

This document was prepared by Dr. Issam Najm of Montgomery Watsons Applied Research Department in Pasadena, California, and is provided as a service to all Montgomery Watson employees and clients. The information provided in this document is based on data published in the literature and bench-scale testing conducted by Montgomery Watson. More detailed information on perchlorate occurrence and treatment is available. If you have any questions or you need additional information, please call Dr. Samer Adham at (626) 568-6751. He can also be contacted at samer.adham@us.mw.com.