Perchlorate in fish from a contaminated site in east-central Texas

Perchlorate, a known thyroid endocrine disruptor, contaminates surface waters near military instillations where solid fuel rocket motors are manufactured or assembled. To assess potential perchlorate exposure to fish and the human population which may feed on them, fish were collected around the Naval Weapons Industrial Reserve Plant in McLennan County, TX, and analyzed for the presence of the perchlorate anion. The sampling sites included Lake Waco and Belton Lake, and several streams and rivers within their watersheds. The general tendency was that perchlorate was only found in a few species sampled, and perchlorate was not detected in every individual within these species. When detected in the fish, perchlorate tissue concentrations were greater than that in the water. This may be due to highly variable perchlorate concentrations in the water coupled with individual-level variation in elimination from the body, or to routes of exposure other than water.     

Influence of soil type and extraction conditions on perchlorate analysis by ion chromatography

Perchlorate is a stable anion that has been introduced into the environment through activities related to its production and use as a solid rocket propellant. Perchlorate is thought to transport through soils without being adsorbed; thus, for determination of perchlorate in soil, samples are typically extracted with water prior to analysis. The completeness of extraction depends on perchlorate existing as a free ion within the soil matrix. In this study, perchlorate extraction efficiency was evaluated with five soil types under two different oxygen states. For each soil, 30% (w/w) slurries were prepared and equilibrated under either oxic or anoxic conditions prior to spiking with a stock solution of sodium perchlorate, and the slurries were then maintained for 1-week or 1-month. At the end of the exposure, slurries were centrifuged and separated into aqueous and soil phases. After phase separation, the soil was washed first with deionized water and then with 50mM NaOH, producing second and third aqueous phases, respectively. Perchlorate concentrations in the three aqueous phases were determined using ion chromatography. The results obtained from this study suggest that matrix interference and signal suppression due to high conductivity have greater effects upon observed perchlorate concentrations by ion chromatography than does perchlorate interaction with soil. Thus, a single water extraction is sufficient for quantitative determination of perchlorate in soil.     

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: Problems,Detection, and Solutions

The perchlorate anion (ClO 4 m ) is produced when the solid salts of ammonium, potassium, and sodium perchlorate, and perchloric acid dissolve in water. Ammonium perchlorate, used in solid rocket engine fuels, has a limited shelf life and must periodically be replaced. Before 1997, perchlorate could not be readily detected in groundwater at concentrations below 100 µg/L, until the California Department of Health Services developed an acceptable analytical method that lowered the detection limit to 4 µg/L. Subsequently, groundwater containing perchlorate were soon encountered in several western states, and contamination became apparent in Colorado River water. Most perchlorate salts have high water solubilities; concentrated solutions have densities greater than water. Once dissolved, perchlorate is extremely mobile, requiring decades to degrade. Health effects from ingesting low dosage perchlorate-contaminated water are not well known: it interferes with the body's iodine intake, causing an inhibition of human thyroid production. Contaminated surface and groundwater treatment may require bio- and/or phytoremediation technologies. Perchlorate in groundwater is relatively unretarded; it probably travels by advection. Therefore, it may be used as a tracer for hydrocarbon and metal contaminants that are significantly more retarded. Possible forensic techniques include chlorine isotopes for defining multiple or commingled perchlorate plumes.     

Aluminum-based drinking-water treatment residuals: a novel sorbent for perchlorate removal

Perchlorate contamination of aquifers and drinking-water supplies has led to stringent regulations in several states to reduce perchlorate concentrations in water at acceptable levels for human consumption. Several perchlorate treatment technologies exist, but there is significant cost associated with their use, and the majority of them are unable to degrade perchlorate to innocuous chloride. We propose the use of a novel sorbent for perchlorate, i.e. an aluminum-based drinking-water treatment residual (Al-WTR), which is a by-product of the drinking-water treatment process. Perchlorate sorption isotherms (23+/-1 degrees C) showed that the greatest amount (65%) of perchlorate removed by the Al-WTR was observed with the lowest initial perchlorate load (10 mg L(-1)) after only 2 h of contact time. Increasing the contact time to 24 h, perchlorate removal increased from 65 to 76%. A significant correlation was observed between the amounts of perchlorate removed with evolved chloride in solution, suggesting degradation of perchlorate to chloride.     

Comparison of biotic and abiotic treatment approaches for co-mingled perchlorate, nitrate, and nitramine explosives in groundwater

Biological and abiotic approaches for treating co-mingled perchlorate, nitrate, and nitramine explosives in groundwater were compared in microcosm and column studies. In microcosms, microscale zero-valent iron (mZVI), nanoscale zero-valent iron (nZVI), and nickel catalyzed the reduction of RDX and HMX from initial concentrations of 9 and 1 mg/L, respectively, to below detection (0.02 mg/L), within 2 h. The mZVI and nZVI also degraded nitrate (3 mg/L) to below 0.4 mg/L, but none of the metal catalysts were observed to appreciably reduce perchlorate ( approximately 5 mg/L) in microcosms. Perchlorate losses were observed after approximately 2 months in columns of aquifer solids treated with mZVI, but this decline appears to be the result of biodegradation rather than abiotic reduction. An emulsified vegetable oil substrate was observed to effectively promote the biological reduction of nitrate, RDX and perchlorate in microcosms, and all four target contaminants in the flow-through columns. Nitrate and perchlorate were biodegraded most rapidly, followed by RDX and then HMX, although the rates of biological reduction for the nitramine explosives were appreciably slower than observed for mZVI or nickel. A model was developed to compare contaminant degradation mechanisms and rates between the biotic and abiotic treatments.     

Perchlorate: Problems,Detection, and Solutions

The perchlorate anion (ClO₄^–) is produced when the solid salts of ammonium, potassium, and sodium perchlorate, and perchloric acid dissolve in water. Ammonium perchlorate, used in solid rocket engine fuels, has a limited shelf life and must periodically be replaced. Before 1997, perchlorate could not be readily detected in groundwater at concentrations below 100 μg/L, until the California Department of Health Services developed an acceptable analytical method that lowered the detection limit to 4 μg/L. Subsequently, groundwater containing perchlorate were soon encountered in several western states, and contamination became apparent in Colorado River water. Most perchlorate salts have high water solubilities; concentrated solutions have densities greater than water. Once dissolved, perchlorate is extremely mobile, requiring decades to degrade. Health effects from ingesting low dosage perchlorate-contaminated water are not well known: it interferes with the body's iodine intake, causing an inhibition of human thyroid production. Contaminated surface and groundwater treatment may require bio- and/or phytoremediation technologies. Perchlorate in groundwater is relatively unretarded; it probably travels by advection. Therefore, it may be used as a tracer for hydrocarbon and metal contaminants that are significantly more retarded. Possible forensic techniques include chlorine isotopes for defining multiple or commingled perchlorate plumes.     

Photocatalytic Treatment of RDX Wastewater with Nano-Sized Titanium Dioxide (5 pp)

Background, Aim and Scope The polynitramines, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), are important military explosives and regulated toxic hazardous compounds. Production, testing and use of the compounds has resulted in numerous acres of contaminated soils and groundwater near many munitions facilities. Economical and efficient methods for treatment of wastewater and cleanup of soils or groundwater containing RDX and HMX are needed. This study focuses on the photocatalytic treatment of RDX wastewater with nano-sized titanium dioxide (nano-TiO2) under simulated sunlight, whose intensity and wavelength are similar to that of the real sunlight in Xi'an at noon. The objective is to determine the potential for RDX destruction with nano-TiO2 in aqueous solution. Materials and Methods: An activated carbon fiber (ACF) cloth-loaded with nano-TiO2 was put into the RDX containing solution, and the concentration of RDX was measured (by HPLC–UV) at regular time intervals under simulated sunlight. Results: The RDX degradation percentage of the photocatalytic process is higher than that of Fenton oxidation before 80 min, equivalent after 80 min, and it reaches 95% or above after 120 min. The nano-TiO2 catalyst can be used repeatedly. Discussion: The photocatalytic degradation kinetics of RDX under simulated sunlight can be described by a first-order reaction kinetics equation. The possible degradation mechanism of RDX was presented and the degradation performance was compared with that of biological method. Conclusions: It was demonstrated that the degradation of RDX wastewater is very effective with nano-TiO2 as the photocatalytic catalyst under simulated sunlight. The efficiency of the nano-TiO2 catalyst for RDX degradation under simulated sunlight is nearly identical to that of Fenton oxidation. Recommendations and Perspectives: To date, a number of catalysts show poor absorption and utilization of sunlight, and still need ultraviolet light irradiation during wastewater degradation. The nano-TiO2 used in the described experiments features very good degradation of RDX under simulated sunlight, and the manufacturing costs are rather low (around 10 Euro/m2). Moreover, the degradation efficiency is higher compared to that of the biological method. This method exhibits great potential for practical applications owing to its easiness and low cost. If it can be applied extensively, the efficiency of wastewater treatment will be enhanced greatly.     

Seasonal variation and factors influencing perchlorate in water,snow, soil and corns in Northeastern China

Seasonal variation and influencing factors of perchlorate in snow, surface soil, rain, surface water, groundwater and corn were studied. Seven hundreds and seventy samples were collected in different periods in Harbin and its vicinity, China. Perchlorate concentrations were analyzed by ion chromatography–electrospray mass spectrometry. Results indicate that fireworks and firecrackers display from the Spring Festival to the Lantern Festival (February 2, 2011–February 17, 2011) can result in the occurrence of perchlorate in surface soil and snow. Perchlorate distribution is affected by wind direction in winter. Melting snow which contained perchlorate can dissolve perchlorate in surface soil, and then perchlorate can percolate into groundwater so that perchlorate concentrations in groundwater increased in spring. Perchlorate concentrations in groundwater and surface water decrease after rainy season in summer. Groundwater samples collected in the floodplain areas of the Songhua River and the Ashi River contained higher perchlorate concentrations than that far away with the rivers. The corns have the ability to accumulate perchlorate.     

Perchlorate in water, soil, vegetation, and rodents collected from the Las Vegas Wash, Nevada, USA

Water, soil, vegetation, and rodents were collected from three areas along the Las Vegas Wash, a watershed heavily contaminated with perchlorate. Perchlorate was detected at elevated concentrations in water, soil, and vegetation, but was not frequently detected in rodent liver or kidney tissues. Broadleaf weeds contained the highest concentrations of perchlorate among all plant types examined. Perchlorate in rodent tissues and vegetation was correlated with perchlorate concentrations in soil as expected, however rodent residues were not highly correlated with plant perchlorate concentrations. This indicates that soil may be a greater source, or a more constant source of perchlorate exposure in rodents than vegetation.     

Degradation of explosives-related compounds using nickel catalysts

We report the ability of nickel-based catalysts to degrade explosives compounds in aqueous solution. Several nickel catalysts completely degraded the explosives, although rates varied. Nearly all of the organic explosive compounds tested, including 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), and octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), were rapidly degraded to below detection limits by a powdered nickel on an alumina-silicate support (Aldrich nickel catalyst). Perchlorate degradation was minimal (<25%). Degradation of TNT by Aldrich nickel catalyst resulted in apparent first-order kinetics. Significant gaseous 14C was released and collected in an alkaline solution (most likely carbon dioxide) from [14C]RDX and [14C]HMX, indicating heterocyclic ring cleavage. Significant gaseous 14C was not produced from [14C]TNT, but spectrophotometric evidence indicated loss of aromaticity. Degradation occurred in low ionic strength solutions, groundwater, and from pH 3 to pH 9. Degradation of TNT, RDX, and HMX was maintained in flow-through columns of Aldrich nickel catalyst mixed with sand down to a hydraulic retention time of 4h. These data indicate that nickel-based catalysts may be an effective means for remediation of energetics-contaminated groundwater.     

中国高氯酸盐污染现状及去除技术研究进展

高氯酸盐是广泛存在于水体环境中的具有高稳定性、高扩散性和持久性的内分泌干扰物,其毒理机制、环境污染、迁移转化和处理技术已成为目前环保领域的研究热点.简要介绍了高氯酸盐的特性、来源及对人体的危害,对比了国内外不同地区高氯酸盐的污染状况,综述了中国已开展的高氯酸盐处理技术,为高氯酸盐环境污染问题的研究提供参考.     

Characteristics of Composition B particles from blow-in-place detonations

We sampled residues from high-order and low-order blow-in-place detonations of mortars and projectiles filled with Composition B (Comp B), a TNT and RDX mixture. Our goals were to (1) characterize the types of explosive particles, (2) estimate the explosive 'footprint' for different munitions, and (3) estimate the mass of Comp B remaining after each detonation. The aerial deposition of Comp B particles helps estimate how large of an area is contaminated by a low-order detonation and how best to sample residue resulting from different rounds. We found that the high-order detonations deposited microgram to milligram quantities whereas the low-order detonations deposited gram quantities of Comp B. For the high-order detonations the concentration of Comp B in the residue decreased as a function of distance from the blast. The low-order tests scattered centimeter-sized chunks and millimeter-sized or smaller particles of Comp B. The chunks were randomly scattered whereas the number of millimeter-sized particles decreased with distance from the detonation. For both high- and low-order detonations we found that the smaller munitions deposited less Comp B than the larger munitions and deposited it closer to the detonation point.     

Reduction of perchlorate and nitrate by salt tolerant bacteria

Spent regenerant brine from ion-exchange technology for the removal of perchlorate and nitrate produces a high salt waste stream, which requires remediation before disposal. Bioremediation is an attractive treatment option. In this study, we enriched for salt tolerant bacteria from sediments from Cargill salt evaporation facility (California, USA), the Salton Sea (California, USA), and a high density hydrocarbon oxidizing bacterial cocktail. The bacterial cocktail enrichment culture reduced ClO4- from 500 to 260 mg 1 in 4 weeks. Salt tolerant bacterial isolates from the enrichment cultures and two denitrifying salt tolerant bacteria, Haloferax denitrificans and Parococcus halodenitricans, substantially reduced perchlorate. The highest rate of perchlorate removal was recorded with the isolate, Citrobacter sp.: 32% reduction in 1 week. This bacterium substantially reduced perchlorate in 0-5% NaCl solutions and maximally at 30 degrees C and at an initial pH 7.5. In simulated brines containing 7.5% total solids, the Citrobacter sp. significantly reduced both perchlorate and nitrate with 34.9 and 15.6% reduction, respectively, in 1 week. Coculture of a potent perchlorate reducing, non-salt tolerant (non-saline) bacterium, perclace and the Citrobacter sp. proved most effective for perchlorate removal in the brine (46.4% in 1 week). This study demonstrates that both anions can be reduced in treatment of brines from ion exchange systems.     

Determination of perchlorate in selected surface waters in the Great Lakes Basin by HPLC/MS/MS

Surface water samples were collected from 55 sites in the Great Lakes Basin and analyzed for the presence of perchlorate using HPLC/MS/MS with an isotopically enriched internal standard. Sites included areas impacted by heavy industry, urbanization, agriculture and atmospheric deposition. Perchlorate was detected at several of the sites at concentrations close to the method detection limit (0.2 microg/l). Despite these low concentrations, its presence was confirmed by sample concentration and determination of the isotopic ratio of perchlorate. The presence of perchlorate at two of the sites was related to a fireworks display which had occurred prior to sampling. The other detections of perchlorate were in rivers/creeks draining watersheds which had high density livestock and crop farming activity. We suspect the two are related. To our knowledge, these are the first reported concentrations of perchlorate in Canadian surface waters.     

Cool temperature performance of a wheat straw biofilter for treating dairy wastewater

A wheat straw biofilter was evaluated for attenuating pollutants in dairy (milkhouse and milking parlor) wastewater. During the 14-day study, the biofilter was operated in a sequential aerobic-anaerobic mode in a temperature range of 8-14 degrees C. While the biofilter was very effective (89% removal) in attenuating total suspended solids and moderately effective (76% removal) in attenuating oil and grease, its effectiveness in attenuating chemical oxygen demand was low (37% removal). The biofilter was ineffective in attenuating nitrate, while its effectiveness in attenuating ammonium (20% removal) and total Kjeldahl nitrogen (15% removal) was low. The biofilter was not effective in attenuating ortho-phosphate, total phosphorus, and fecal coliform. Though microbial degradation accounted for some pollutant removal, filtration seemed to be the primary mechanism. Lower temperature of operation and high oil and grease concentration (that reduced nutrient transfer to the biofilm) decreased microbial activity, reducing pollutant attenuation. Biofilter performance could be enhanced by using residual heat in the wastewater to raise the operating temperature of the biofilter and by removing oil and grease prior to applying the wastewater to the biofilter.     

Review on Fate,Toxicity, and Remediation of Perchlorate

Several issues regarding the adverse impacts of the chemical—perchlorate—have been identified recently. Perchlorate is a persistent chemical, and remains in water and soil, thereby accumulating in plants and animals. Fetuses suffer the most from perchlorate contamination. There are ongoing debates about the impacts, toxicity and health effects of perchlorate. Many studies have been conducted on its ecotoxicity and its effects, but standards do not exist for perchlorate. This study aims to review the sources, impacts, fate, transport and remediation of perchlorate.     

Pilot-plant study of wastewater sludge decontamination using a ferrous sulfate bioleaching process.

The objective of this research was to investigate the performance of the ferrous sulfate bioleaching (FSBL) process in a pilot plant for decontamination and stabilization of wastewater sludge. Batch and continuous experiments, conducted with two 4-m3 bioreactors using indigenous iron-oxidizing bacteria (20% v/v of inoculum) with addition of 4.0 g ferrous sulfate heptahydrate per liter of sludge initially acidified to pH 4.0, were sufficient for effective heavy metal (cadmium, copper, manganese, zinc, and lead) removal yields. The average metal removal yields during the FSBL process were as follows: cadmium (69 to 75%), copper (68 to 70%), manganese (72 to 73%), zinc (65 to 66%), and lead (16%). The FSBL process was also found to be effective in removing both fecal and total coliforms (abatement > 5 to 6 log units). The nutrients content (nitrogen, phosphorus, and magnesium) were also preserved in decontaminated sludge.     

Toxicity of hexahydro-1,3,5-trinitro-1,3,5-triazine to larval zebrafish (Danio rerio)

Hexahydro-1,3,5-trinitro-1,3,5-triazine, a cyclonitramine commonly known as RDX, is used in the production of military munitions. Contamination of soil, sediment, and ground and surface waters with RDX has been reported in different places around the world. Acute and subacute toxicities of RDX have been relatively well documented in terrestrial vertebrates, but among aquatic vertebrates the information available is limited. The objective of this study was to characterize the acute toxicity of RDX to larval zebrafish. Mortality (LC50) and incidence of vertebral column deformities (EC50) were two of the end points measured in this study. The 96-h LC50 was estimated at 22.98 and 25.64 mgl(-1) in two different tests. The estimated no-observed-effective-concentration (NOEC) values of RDX on lethality were 13.27+/-0.05 and 15.32+/-0.30 mgl(-1); and the lowest-observed-effective-concentration (LOEC) values were 16.52+/-0.05 and 19.09+/-0.23 mgl(-1) in these two tests, respectively. The 96-h EC50 for vertebral deformities on survivors from one of the acute lethality tests was estimated at 20.84 mgl(-1), with NOEC and LOEC of 9.75+/-0.34 and 12.84+/-0.34 mgl(-1), respectively. Behavioral aberrations were also noted in this acute toxicity study, including the occurrence of whirling movement and lethargic behavior. The acute effects of RDX on survival, incidence of deformities, and behavior of larval zebrafish occurred at the high end of the most frequently reported concentrations of RDX in aquatic environments. The chronic effects of RDX in aquatic vertebrates need to be determined for an adequate assessment of the ecological risk of environmental RDX.     

Bioremediation of trace organic compounds found in precious metals refineries' wastewaters: a review of potential options

Platinum group metal (PGM) refining processes produce large quantities of wastewater, which is contaminated with the compounds that make up the solvents/extractants mixtures used in the process. These compounds often include solvesso, beta-hydroxyxime, amines, amides and methyl isobutyl ketone. A process to clean up PGM refinery wastewaters so that they could be re-used in the refining process would greatly contribute to continual water storage problems and to cost reduction for the industry. Based on the concept that organic compounds that are produced biologically can be destroyed biologically, the use of biological processes for the treatment of organic compounds in other types of waste stream has been favoured in recent years, owing to their low cost and environmental acceptability. This review examines the available biotechnologies and their effectiveness for treating compounds likely to be contained in precious metal extraction process wastewaters. The processes examined include: biofilters, fluidized bed reactors, trickle-bed bioreactors, bioscrubbers, two-phase partitioning bioreactors, membrane bioreactors and activated sludge. Although all processes examined showed adequate to excellent removal of organic compounds from various gaseous and fewer liquid waste streams, there was a variation in their effectiveness. Variations in performance of laboratory-scale biological processes are probably due to the inherent change in the microbial population composition due to selection pressure, environmental conditions and the time allowed for adaptation to the organic compounds. However, if these factors are disregarded, it can be established that activated sludge and membrane bioreactors are the most promising processes for use in the treatment of PGM refinery wastewaters.