Edward T. Urbansky

Perchlorate Chemistry: Implications for Analysis and Remediation

Since the discovery of perchlorate in the ground and surface waters of several western states, there has been increasing interest in the health effects resulting from chronic exposure to low (parts per billion [ppb]) levels. With this concern has come a need to investigate technologies that might be used to remediate contaminated sites or to treat contaminated water to make it safe for drinking. Possible technologies include physical separation (precipitation, anion exchange, reverse osmosis, and electrodialysis), chemical and electrochemical reduction, and biological or biochemical reduction. A fairly unique combination of chemical and physical properties of perchlorate poses challenges to its analysis and reduction in the environment or in drinking water. The implications of these properties are discussed in terms of remediative or treatment strategies. Recent developments are also covered.

Perchlorate as an environmental contaminant.

Perchlorate anion (ClO4−) has been found in drinking water supplies throughout the southwestern United States. It is primarily associated with releases of ammonium perchlorate by defense contractors, military operations, and aerospace programs. Ammonium perchlorate is used as a solid oxidant in missile and rocket propulsion systems. Traces of perchlorate are found in Chile saltpeter, but the use of such fertilizer has not been associated with large scale contamination. Although it is a strong oxidant, perchlorate anion is very persistent in the environment due to the high activation energy associated with its reduction. At high enough concentrations, perchlorate can affect thyroid gland functions, where it is mistakenly taken up in place of iodide. A safe daily exposure has not yet been set, but is expected to be released in 2002. Perchlorate is measured in environmental samples primarily by ion chromatography. It can be removed by anion exchange or membrane filtration. It is destroyed by some biological and chemical processes. The environmental occurrence, toxicity, analytical chemistry, and remediative approaches are discussed.

Perchlorate levels in samples of sodium nitrate fertilizer derived from Chilean caliche

Paleogeochemical deposits in northern Chile are a rich source of naturally occurring sodium nitrate (Chile saltpeter). These ores are mined to isolate NaNO3 (16-0-0) for use as fertilizer. Coincidentally, these very same deposits are a natural source of perchlorate anion (ClO4-). At sufficiently high concentrations, perchlorate interferes with iodide uptake in the thyroid gland and has been used medicinally for this purpose. In 1997, perchlorate contamination was discovered in a number of US water supplies, including Lake Mead and the Colorado River. Subsequently, the Environmental Protection Agency added this species to the Contaminant Candidate List for drinking water and will begin assessing occurrence via the Unregulated Contaminants Monitoring Rule in 2001. Effective risk assessment requires characterizing possible sources, including fertilizer. Samples were analyzed by ion chromatography and confirmed by complexation electrospray ionization mass spectrometry. Within a lot, distribution of perchlorate is nearly homogeneous, presumably due to the manufacturing process. Two different lots we analyzed differed by 15%, containing an average of either 1.5 or 1.8 mg g-1. Inadequate sample size can lead to incorrect estimations; 100-g samples gave sufficiently consistent and reproducible results. At present, information on natural attenuation, plant uptake, use/application, and dilution is too limited to evaluate the significance of these findings, and further research is needed in these areas.

Perchlorate uptake by salt cedar (Tamarix ramosissima) in the Las Vegas Wash riparian ecosystem.

Perchlorate ion (ClO4-) has been identified in samples of dormant salt cedar (Tamarix ramosissima) growing in the Las Vegas Wash. Perchlorate is an oxidant, but its reduction is kinetically hindered. Concern over thyroid effects caused the Environmental Protection Agency (EPA) to add perchlorate to the drinking water Contaminant Candidate List (CCL). Beginning in 2001, utilities will look for perchlorate under the Unregulated Contaminants Monitoring Rule (UCMR). In wood samples acquired from the same plant growing in a contaminated stream, perchlorate concentrations were found as follows: 5-6 microg g(-1) in dry twigs extending above the water and 300 microg g(-1) in stalks immersed in the stream. Perchlorate was leached from samples of wood, and the resulting solutions were analyzed by ion chromatography after clean-up. The identification was confirmed by electrospray ionization mass spectrometry after complexation of perchlorate with decyltrimethylammonium cation. Because salt cedar is regarded as an invasive species, there are large scale programs aimed at eliminating it. However, this work suggests that salt cedar might play a role in the ecological distribution of perchlorate as an environmental contaminant. Consequently, a thorough investigation of the fate and transport of perchlorate in tamarisks is required to assess the effects that eradication might have on perchlorate-tainted riparian ecosystems, such as the Las Vegas Wash. This is especially important since water from the wash enters Lake Mead and the Colorado River and has the potential to affect the potable water source of tens of millions of people as well as irrigation water used on a variety of crops, including much of the lettuce produced in the USA.

Perchlorate retention and mobility in soils

Adsorption and release of perchlorate in a variety of soils, minerals, and other media were studied when the solid media were exposed to low and high aqueous solutions of perchlorate salts. Low level ClO4- exposure was investigated by subjecting triplicate 5.0 g portions of a solid medium (38 different soils, minerals, or dusts) to 25 mL of an aqueous ammonium perchlorate (NH4ClO4) solution containing 670 ng mL(-1) (6.8 microM) perchlorate. This corresponds to a perchlorate-to-soil ratio of 3.4 microg g(-1) (34 nmol g(-1)). At this level of exposure, more than 90% of the perchlorate was recovered in the aqueous phase, as determined by ion chromatography. In some cases, more than 99% of the perchlorate remained in the aqueous phase. In some cases, the apparent loss of aqueous perchlorate was not clearly distinguishable from the variation due to experimental error. The forced perchlorate anion exchange capacities (PAECs) were studied by soaking triplicate 5.0 g portions of the solid media in 250 mL of 0.20 M sodium perchlorate (NaClO4) followed by repeated deionized water rinses (overnight soaks with mixing) until perchlorate concentrations fell below 20 ng mL(-1) in the rinse solutions. The dried residua were leached with 15.0 mL of 0.10 M sodium hydroxide. The leachates were analyzed by ion chromatography and the perchlorate concentrations thus found were subsequently used to calculate the PAECs. The measurable PAECs of the insoluble and settleable residua ranged from 4 to 150 nmol g(-1) (micromol kg(-1)), with most in the 20-50 nmol g(-1) range. In some soils or minerals, no sorption was detectable. The mineral bentonite was problematic, however. Overall, the findings support the widely accepted idea that perchlorate does not appreciably sorb to soils and that its mobility and fate are largely influenced by hydrologic and biologic factors. They also generally support the idea that intrasoil perchlorate content is depositional rather than sorptive. On the other hand, sorption (anion replacement) of perchlorate appears to occur in some soils. Therefore, the measurement of perchlorate in soils requires accounting for ion exchange phenomena; leaching with water alone may give inaccurate results. If perchlorate anion exchange is confirmed to be negligible, then leaching procedures may be simplified accordingly.

Analysis of hydroponic fertilizer matrixes for perchlorate: comparison of analytical techniques.

Seven retail hydroponic nitrate fertilizer products, two liquid and five solid, were comparatively analyzed for the perchlorate anion (ClO4-) by ion chromatography (IC) with suppressed conductivity detection, complexation electrospray ionization mass spectrometry (cESI-MS), normal Raman spectroscopy, and infrared spectroscopy using an attenuated total reflectance crystal (ATR-FTIR) coated with a thin film of an organometallic ion-exchange compound. Three of the five solid products were found by all techniques to contain perchlorate at the level of approximately 100-350 mg kg(-1). The remaining products did not contain perchlorate above the detection level of any of the techniques. Comparative analysis using several analytical techniques that depend on different properties of perchlorate allow for a high degree of certainty in both the qualitative and quantitative determinations. This proved particularly useful for these samples, due to the complexity of the matrix. Analyses of this type, including multiple spectroscopic confirmations, may also be useful for other complicated matrixes (e.g., biological samples) or in forensic/regulatory frameworks where data are likely to be challenged. While the source of perchlorate in these hydroponic products is not known, the perchlorate-to-nitrate concentration ratio (w/w) in the aqueous extracts is generally consistent with the historical weight percent of water soluble components in caliche, a nitrate-bearing ore found predominantly in Chile. This ore, which is the only well-established natural source of perchlorate, is mined and used, albeit minimally, as a nitrogen source in some fertilizer products.

Total organic carbon analyzers as tools formeasuring carbonaceous matter in natural waters

For some utilities, new US drinking water regulations may require the removal of disinfection byproduct (DBP) precursor material as a means of minimizing DBP formation. The Environmental Protection Agencys Stage 1 DBP Rule relies on total organic carbon (TOC) concentrations as a measure of the effectiveness of treatment techniques for removing organic material that could act as DBP precursors. Accordingly, precise and accurate methods are needed for the determination of TOC and dissolved organic carbon (DOC) concentrations in raw and finished potable water supplies. This review describes the current analytical technologies and summarizes the key factors affecting measurement quality. It provides a look into the fundamental principles and workings of TOC analyzers. Current peroxydisulfuric acid wet ashing methods and combustion methods are discussed. Issues affecting quality control, such as non-zero blanks and preservation, are covered. Some of the difficulties in analyzing water for TOC and DOC that were identified up to 20 years ago still remain problematic today. Limitations in technology, reagent purity, operator skill and knowledge of natural organic matter (NOM) can preclude the level of precision and accuracy desirable for compliance monitoring.

Survey of bottled waters for perchlorate by electrospray ionization mass spectrometry (ESI-MS) and ion chromatography (IC)†

Perchlorate has been identified in ground and surface waters around the USA including some that serve as supplies for drinking water. Because perchlorate salts are used as solid oxidants in rockets and ordnance, water contamination may occur near military or aerospace installations or defense industry manufacturing facilities. This ion has been added to the Environmental Protection Agencys Contaminant Candidate List and the Unregulated Contaminant Monitoring Rule. Concern over perchlorate has prompted many residents in affected areas to switch to bottled water; however, bottled waters have not previously been examined for perchlorate contamination. Should the EPA promulgate a regulation for municipal water systems, US law requires the Food and Drug Administration to take action on bottled water. Methods will therefore be required to determine perchlorate concentrations not only in tap water, but also in bottled waters. Ion chromatography (IC) is the primary technique used for its analysis in drinking water, but it does not provide a unique identification. Confirmation by electrospray ionization mass spectrometry (ESI-MS) can serve in this capacity. The ESI-MS method can be applied to these products, but it requires an understanding of matrix effects, especially of high ionic strength that can suppress electrospray. When using methyl isobutyl ketone (MIBK) as the extraction solvent, the ESI-MS method can reach lower limits of detection of 6 ng ml −1 for some bottled waters. However, dilution required to negate ionic strength effects in mineral waters can raise this by a factor of 10 or more, depending on the sample. Decyltrimethylammonium cation (added as the bromide salt) is used to produce an ion pair that is extracted into MIBK. After extraction, the sum of the peak areas of the ions C10H21NMe3(Br)(ClO4)− (m/z = 380) and C10H21NMe3(ClO4)2− (m/z = 400) is used to quantitate perchlorate. Standard additions are used to account for most of the matrix effects. In this work, eight domestic brands and eight imported brands of bottled water were comparatively analyzed by the two techniques. For comparison, a finished potable water known to contain perchlorate was also tested. None of the bottled waters were found to contain any perchlorate within the lower limit of detection for the IC method. Recoveries on spiked samples subjected to the IC method were ≥98%. Published in 2000 for SCI by John Wiley & Sons, Ltd

Techniques and methods for the determination of haloacetic acids in potable water

Haloethanoic (haloacetic) acids (HAAs) are formed as disinfection byproducts (DBPs) during the chlorination of natural water to make it fit for consumption. Sundry analytical techniques have been applied in order to determine the concentrations of the HAAs in potable water supplies: gas chromatography (GC-MS, GC-ECD); capillary electrophoresis (CE); liquid chromatography (LC), including ion chromatography (IC); and electrospray ionization mass spectrometry (ESI-MS). Detection limits required to analyze potable water samples can be regularly achieved only by GC-ECD and ESI-MS. Without improvements in preconcentration or detector sensitivity, CE and LC will not find application to potable water supplies. The predominant GC-ECD methods use either diazomethane or acidified methanol to esterify (methylate) the carboxylic acid moiety. For HAA5 analytes, regulated under the EPAs Stage 1 DBP Rule, diazomethane is satisfactory. For HAA9 data gathered under the Information Collection Rule, acidified methanol outperforms diazomethane, which suffers from photo-promoted side reactions, especially for the brominated trihaloacetic acids. Although ESI-MS can meet sensitivity and selectivity requirements, limited instrumentation availability means this technique will not be widely used for the time being. However, ESI-MS can provide valuable confirmatory information when coupled with GC-ECD in a research setting.

Can fluoridation affect lead(II) in potable water? hexafluorosilicate and fluoride equilibria in aqueous solution

Recent reports have attempted to show that fluoridating potable water is linked to increased levels of lead(II) in the blood. We examine these claims in light of the established science and critically evaluate their significance. The completeness of hexafluoro‐silicate hydrolysis is of paramount importance in ensuring that total water quality is maintained. The possible impacts of such complexes as PbII—F—SiF5 or PbFx (2‐x) are discussed as are the contributions of fluoridation byproducts to total acid content. We calculate the fractional distribution of aqueous species based on known chemical equilibria and show the species concentrations for several different model tap waters. We discuss and quantitatively show the effects of other complexing anions, such as carbonate or hydroxide. Overall, we conclude that no credible evidence exists to show that water fluoridation has any quantitatable effects on the solubility, bioavailability, bio‐accumulation, or reactivity of lead(0) or lead(II) compounds. The governing factors are the concentrations of a number of other species, such as (bi)carbonate, hydroxide, or chloride, whose effects far exceed those of fluoride or fluorosilicates under drinking water conditions. Lastly, we consider some previous epidemiological studies of lead(II) exposure and how recent papers fare methodologically.