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Determination of trace level perchlorate in drinking water and ground water by ion chromatography.

Ammonium perchlorate, a key ingredient in solid rocket propellants, has recently been found in ground and surface waters in the USA in a number of states, including California, Nevada, Utah, and West Virginia. Perchlorate poses a health risk and preliminary data from the US Environmental Protection Agency reports that exposure to less than 4-18 micrograms/l provides adequate human health protection. An ion chromatographic method was developed for the determination of low microgram/l levels of perchlorate in drinking and ground waters based on a Dionex IonPac AS11 column, a 100 mM hydroxide eluent, large loop (1000 microliters) injection, and suppressed conductivity detection. The method is free of interferences from common anions, linear in the range of 2.5-100 micrograms/l, and quantitative recoveries were obtained for low microgram/l levels of perchlorate in spiked drinking and ground water samples. The method detection limit of 0.3 microgram/l permits quantification of perchlorate below the levels which ensure adequate health protection. A new polarizable anion analysis column, the IonPac AS16, and its potential applicability for this analysis is also discussed.

Anions↗

Analysis of 500-ng/l levels of bromate in drinking water by direct-injection suppressed ion chromatography coupled with a single, pneumatically delivered post-column reagent.

In July 1997, the US Environmental Protection Agency (EPA) began sampling and analyzing drinking water matrices from US municipalities serving populations greater than 100,000 for low-level bromate (> 0.20 microgram/l) in support of the Information Collection Rule (ICR) using the selective anion concentration (SAC) method. In September 1997, EPA published Method 300.1 which lowered the Method 300.0 bromate method detection limit (MDL) from 20.0 to 1.4 micrograms/l. This paper describes the research conducted at the EPA's Technical Support Center laboratory investigating a single post-column reagent, o-dianisidine (ODA), which has been successfully coupled to EPA Method 300.1 to extend the MDL for bromate. Initial studies indicate that this method offers a MDL which approaches the EPA's SAC method with the added benefit of increased specificity, shortened analysis time and reduced sample preparation. The method provides excellent ruggedness and acceptable precision and accuracy with a bromate MDL in reagent water of 0.1 microgram/l, and a method reporting limit of 0.50 microgram/l.

Borates↗

Determination of explosives in soil and ground water by liquid chromatography-amperometric detection.

Electrochemical reduction of trinitrotoluene (TNT) and several nitroaromatics has been exploited toward the development of an amperometric detector for liquid chromatography (LC). Up to a ten-fold increase in sensitivity was accomplished for the explosives using amperometric detection instead of conventional UV measurement. A working glassy carbon electrode (poised at -0.80 V vs. Ag/AgCl) offered a detection limit of 9, 44 and 550 nM for trinitrobenzene, TNT and 1,4-dinitrobenzene, respectively. Separation of eleven TNT-related compounds in a mixture was achieved within 15 min using a C18 column and a mobile phase consisting of acetonitrile-50 mM phosphate buffer pH 5 (1:2, v/v) and 18 mM sodium dodecylsulfate. The LC-amperometric detection system was applicable for analyzing soil extracts and ground water and the results obtained agreed well with that of the US Environmental Protection Agency recommended procedure. Extension to analysis of HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) and RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) was accomplished with a silver working electrode instead of a glassy carbon electrode installed in a thin channel cell.

Carbon↗

Quantitative determination of polycyclic aromatic hydrocarbons, polychlorinated biphenyls and organochlorine pesticides in sewage sludges using supercritical fluid extraction and mass spectrometric detection.

Supercritical CO2 extraction (SFE) proved to be a valuable, fast, quantitative and partly selective extraction technique for determining polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and chlorinated pesticides (OCPs) in sewage sludges of different catchment areas based on a comparison study with certified reference materials (CRMs) and on recovery data. Most PCB extracts could be measured directly after SFE whereas for PAHs a short clean-up improved the final separation by high-resolution capillary gas chromatography. Due to the amount of coextracted compounds and the low levels of OCPs, extracts obtained by SFE had to be submitted to a multistep clean-up for final measurement. Average concentrations of 6.9 mg/kg dry mass (dm) for the sum of the 16 Environmental Protection Agency PAHs, 0.1 mg/kg dm for the sum of the seven PCB congeners and 0.002-0.072 mg/kg dm for the OCPs were found in the sewage sludges. Compared to studies performed earlier in our laboratory PAHs are still present in similar concentrations whereas PCB levels have decreased significantly. OCPs could be detected in only low amounts. A correlation between sludge type and degree of contamination could only be found for PAHs.

Chromatography↗

Automated in-tube solid-phase microextraction-high-performance liquid chromatography for carbamate pesticide analysis.

In-tube solid-phase microextraction (SPME) is an automated version of SPME that can be easily coupled to a conventional HPLC autosampler for on-line sample preparation, separation and quantitation. It has been termed "in-tube" SPME because the extraction phase is coated inside a section of fused-silica tubing rather than coated on the surface of a fused-silica rod as in the conventional syringe-like SPME device. The new in-tube SPME technique has been demonstrated as a very efficient extraction method for the analysis of polar and thermally labile analytes. The in-tube SPME-HPLC method used with the FAMOS autosampler from LC Packings was developed for detecting polar carbamate pesticides in clean water samples. The main parameters relating to the extraction and desorption processes of in-tube SPME (selection of coatings, aspirate/dispense steps, selection of the desorption solvents, and the efficiency of desorption solvent, etc.) were investigated. The method was evaluated according to the reproducibility, linear range and limit of detection. This method is simple, effective, reproducible and sensitive. The relative standard deviation for all the carbamates investigated was between 1.7 and 5.3%. The method showed good linearity between 5 and 10000 microg/l with correlation coefficients between 0.9824 and 0.9995. For the carbamates studied, the limits of detection observed are lower than or similar to that of US Environmental Protection Agency or National Pesticide Survey methods. Detection of carbaryl present in clean water samples at 1 microg/l is possible.

Carbamates↗

Characterization of chlorinated compounds using a dual chlorine-selective pulsed discharge emission detector-helium-pulsed discharge photoionization detector system.

The Cl-selective pulsed discharge emission detector (Cl-PDED) response is dependent only upon the Cl content, irrespective of the molecular structures of the compounds. This provides a simple, fast quantitative method of analysis for chlorinated compounds. The response of the helium-pulsed discharge photoionization detector (He-PDPID) is a function of the molecular structure and the number of photoionizable electrons using the He2 band at 13.5-17.5 eV. The ratio of the responses of the two detectors is independent of concentration and can be used to characterize the Cl-containing compounds along with the retention time, or the ratio can be used as evidence for coelution. The dual Cl-PDED-He-PDPID detector system is a useful tool for peak identification. The effect of coeluting hydrocarbons on the Cl-PDED response was evaluated by spiking a gasoline sample with US Environmental Protection Agency mixture 502. All Cl-PDED responses were greater than 90% of the response in the absence of the hydrocarbons.

Chlorine↗

Determination of interfering triazine degradation products by gas chromatography-ion trap mass spectrometry.

Deethylatrazine (DEA), an atrazine degradation product, has been added to the US Environmental Protection Agency's Drinking Water Contaminant Candidate List (CCL). In its gas chromatographic analysis, DEA can coelute with deisopropylatrazine (DIA), another degradation product. The present work demonstrates that the coelution of DEA and DIA can induce a significant (up to approximately 50%) positive bias in the DEA determination, when using an ion-trap mass spectrometer as the detector. The DIA determination is unaffected by the coelution within experimental error. This may be explained in terms of gas-phase ion fragment populations. A correction factor to the observed DEA concentration may be developed based on the measured DIA concentration.

Atrazine↗

The impact of ferrous ion reduction of chlorite ion on drinking water process performance.

The use of chlorine dioxide (ClO2) as a primary disinfectant and pre-oxidant in drinking water treatment is being explored as an alternative to chlorine for reducing disinfection by-product formation and to assure compliance with United States Environmental Protection Agency's Stage 1 Disinfection/ Disinfection By-Products Rule. However, the ClO2 by-product chlorite ion (ClO2-) is also regulated by the same regulation. Ferrous iron (Fe(II)) has been shown to effectively reduce chlorite ion to chloride ion (Cl-) and this study was conducted to evaluate the impact on overall treatment process performance due to the ferric hydroxide solids that form from the reaction. Ferrous iron application was explored at three different points in a pilot-scale water treatment system: pre-rapid mix. pre-settling and pre-filter. Chlorite ion concentrations were effectively reduced from 2mg/L to less than 0.3mg/L using an Fe(II) dose of approximately 6mg/L for all trials. Fe(II) addition at the rapid mix caused no adverse effects and, in fact, allowed for reduction of the alum dose due to the newly formed ferric hydroxide acting as a supplemental coagulant. An increase of 241 and 247% of total suspended solids influent to the filter process was observed when Fe(II) was applied at the pre-settling and pre-filter locations. Pilot-scale filter runs during these trials were less than 2 h and never obtained true steady state conditions. Jar testing was performed to better understand the nature of the ferric hydroxide solids that are formed when Fe(II) was oxidized to Fe(III) and to explore the effectiveness of Fe(II) addition at intermediate stages in the flocculation process.

Chlorides↗

Derivation of acute ecological risk criteria for chlorite in freshwater ecosystems.

Chlorine dioxide has been proposed as an alternative to chlorine because it is a powerful disinfection agent that does not react with ammonia or chlorinated organics to form chloramines or trihalomethanes. The major reduction product formed when chlorine dioxide is added to water is the chlorite ion. Chlorite has been shown to be less toxic than free or combined chlorine. However, previous studies with eight freshwater families produced a US Environmental Protection Agency (USEPA) acute water quality criteria (WQC) lower than the WQC for chlorine. In the current study, an additional 12 families were added to the toxicological database to determine ecological risk criteria (ERC) using both the standard USEPA WQC methodology and the USEPA Office of Pesticide Programs (OPP) probabilistic approach. Chlorite LC50 values for the 20 family database ranged from 0.27 mg/L for the Daphnidae to 208.76 mg/L for the Salmonidae. The Daphnidae were by far the most sensitive family tested, with an LC50 44 times lower than the next most sensitive family tested, the Hyalellidae (LC50=1.19 mg/L) and 214 times lower than the most sensitive fish family tested, the Ictaluridae (LC50=5.79 mg/L). The Criteria Maximum Concentration calculated using the USEPA WQC methodology was 0.025 mg/L while the 95% ERC calculated using the USEPA OPP probabilistic methodology was 0.135 mg/L. The USEPA OPP probabilistic approach yields a criterion more consistent with the overall species sensitivity distribution and is not overly skewed by the low Daphnidae LC50 as is the USEPA WQC approach.

Animals↗

Synthetic fuel for imitation of municipal solid waste in experimental studies of waste incineration.

Synthetic fuel is prepared to imitate municipal solid waste (MSW) in experimental studies of incineration processes. The fuel is composed based on the Environmental Protection Agency reports on the materials contained in MSW. Uniform synthetic fuel pellets are prepared using available and inexpensive components including newsprint, hardwood mulch, low density polyethylene, iron, animal feed, sand, and water to imitate paperbound, wood, yard trimming, plastic, metal, food wastes, and other materials in MSW. The synthetic fuel preparation procedure enables one to reproduce and modify the fuel for a wide range of experiments in which the mechanisms of waste incineration are addressed. The fuel is characterized using standard ASTM tests and it is shown that its parameters, such as combustion enthalpy, density, as well as moisture, ash and fixed carbon contents are adequate for the representation of municipal solid waste. In addition, chlorine, nitrogen, and sulfur contents of the fuel are shown to be similar to those of MSW. Experiments are conducted in which the synthetic fuel is used for operation of a pilot-scale incinerator research facility. Steady-state temperature operation regimes are achieved and reproduced in these experiments. Thermodynamic equilibrium flame conditions are computed using an isentropic one-dimensional equilibrium code for a wide range of fuel/air ratios. The molecular species used to represent the fuel composition included cellulose, water, iron, polyethylene, methanamine, and silica. The predicted concentrations of carbon monoxide, nitric oxides, and oxygen in the combustion products are compared with the respective experimental concentrations in the pilot-scale incinerator exhaust.

Air Pollutants↗

Occurrence and concentrations of polycyclic aromatic hydrocarbons in semipermeable membrane devices and clams in three urban streams of the Dallas-Fort Worth Metropolitan Area, Texas.

Semipermeable membrane devices (SPMDs) and Asiatic clams, Corbicula fluminea (MüLLER), were deployed at stream sites in the Dallas-Fort Worth Metropolitan Area to assess the presence of bioavailable, dissolved polycyclic aromatic hydrocarbons (PAHs). Twenty-four PAHs were detected in SPMDs, 20 of which occurred at all sites. Only three PAHs were detected in the co-deployed clams. Throughout all sites, non-alkylated PAHs were found at greater levels in SPMDs than alkylated forms. Nine of 16 Priority Pollutant PAHs were detected in SPMDs. Estimated concentrations of PAHs in water were generally two to three orders of magnitude less than standard minimum analytical reporting levels; however, for benz (a) anthracene, benzo (a) pyrene, and chrysene, estimated concentrations in water exceeded the U.S. Environmental Protection Agency's human health criteria for these carcinogens in water and aquatic organisms.

Animals↗

Estimate of methane emissions from the U.S. natural gas industry.

Global methane emissions from the fossil fuel industries have been poorly quantified and, in many cases, emissions are not well-known even at the country level. Historically, methane emissions from the U.S. gas industry have been based on sparse data, incorrect assumptions, or both. As a result, the estimate of the contribution these emissions make to the global methane inventory could be inaccurate. For this reason the assertion that global warming could be reduced by replacing coal and oil fuels with natural gas could not be defended. A recently completed, multi year study conducted by the U.S. Environmental Protection Agency's Office of Research and Development and the Gas Research Institute had the objective of determining methane emissions from the U.S. gas industry with an accuracy of +/-0.5% of production. The study concluded that, in the 1992 base year, methane emissions from the industry were 314 +/- 105 Bscf or 6.04 +/- 2.01 Tg (all conversions to international units are made at 15.56 degrees C and 101.325 kPa).

Air Pollutants, Occupational↗

Cancer risk assessment using blood dioxin levels and daily dietary TEQ intake in general populations of industrial and non-industrial countries.

We previously measured polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in U.S. foods and estimated the daily dioxin toxic equivalent (TEQ) intake to be from 0.3 to 3.0 pg 1-TEQ/kg body weight for adults. These values are similar to values reported in Canada, Germany, England, and the Netherlands. The U.S. Environmental Protection Agency (EPA) Dioxin Reassessment Draft Documents currently propose a cancer risk-specific dose estimate of 0.01 pg TEQ/kg body weight/day (U.S. EPA, 1994). This risk-specific dose estimate represents a lifetime (70 years) dose which results in a plausible upper bound cancer risk of 1 x 10(-6) (the probability of one additional cancer per one million exposed population over a lifetime). The proximate source of almost all dioxin intake in the general population is from food. Using our data for daily dietary dioxin exposure and the EPA's proposed risk specific dose, we estimate that over a lifetime a maximum of 30 to 300 excess cancers per million could result from the ingestion of dioxin containing food products. In the U.S. population of 260 million, a maximum range of 7,800 to 78,000 excess cancers over a lifetime (70 years) or 111 to 1,114 cases/year might be directly linked to dioxin exposure from food. Because these calculations are based on conservative approaches to setting an upper bound, "true" risk is not likely to exceed this value. At present, one-third of all Americans will develop cancer over a lifetime and one in four Americans are likely to die from cancer. For 1995, it was estimated that there would be 1,252,000 new cancer cases in the U.S. From this, we calculate that a maximum between 0.009% and 0.09% (111-1,114 cases/year) of all cancer cases in the U.S. might be directly linked to dioxin intake in food, assuming intakes have remained constant over a lifetime. Previous studies have suggested that as much as 70% of the total cancer risk in humans may be attributable to diet, primarily as a function of caloric and synthetic chemicals in the diet. (NAS, 1996) These figures do not take into account the ingestion of more contaminated food products, other sources of exposure, possible interactions of PCDDs and PCDFs with other chemicals, or increased incidence of cancer from the cancer promoting actions of dioxins. In addition, we reviewed average U.S. general population blood TEQ (ppt, lipid) levels, which reflect body burden, with levels of persons living in less industrialized countries. These data were used to compare the cancer risk of individuals living in the U.S., an industrial country, to those living in selected less industrialized countries. With the assumption that similar populations were being compared, it is estimated that in the non-industrial region of north Vietnam there is one-third the risk of dioxin-related cancer compared with the United States, while Cambodians have a dioxin-related cancer risk that is 14 fold less than the U.S. at this time.

Adult↗

Modeling assessment of transport and deposition patterns of anthropogenic mercury air emissions in the United States and Canada

In December 1997, the U.S. Environmental Protection Agency submitted its mercury study report to Congress, which included a modeling assessment of the long-range transport and deposition of mercury from various residential and industrial sources within the United States, based on numerical simulations of elemental mercury gas, divalent mercury gas and particulate mercury, using a special version of the Regional Lagrangian Model of Air Pollution (RELMAP). Observations of the deposition of total precipitated mercury at several locations within the U.S. were compared to the modeling results in order to evaluate the accuracy of the RELMAP simulations. However, the lack of Canadian mercury emissions data in the RELMAP modeling limited the usefulness of this model evaluation at locations near the Canadian border. An inventory of Canadian mercury emissions obtained from Environment Canada has now been added to the RELMAP mercury modeling, and the previous simulations and evaluation of modeled wet deposition have been repeated. The results indicate that emissions of mercury from Canada, as represented by the new inventory, do not significantly impact simulated wet deposition over the United States, nor the general results of the previous model evaluation. Analyses of the simulated transport and deposition patterns of mercury emissions from both the United States and Canada are presented, along with the simulated fraction of total mercury wet deposition, separately attributable to sources within each nation.

Journal Article↗

Infection transmission system models for microbial risk assessment.

Chemical risk assessments often focus on measuring exposure as if individuals were subject only to exogenous environmental sources of risk. For infectious diseases, exposure might not only depend on exogenous sources of microbes, but also on the infection status of other individuals in the population. For example, waterborne infections from agents such as Cryptosporidium parvum and Escherichia coli: O157:H7 might be transmitted from contaminated water to humans through drinking water; from interpersonal contact; or from infected individuals to the environment, and back to other susceptible individuals. These multiple pathways and the dependency of exposure on the prevalence of infection in a population suggest that epidemiological models are required to complement standard risk assessments in order to quantify the risk of infection. This paper presents new models of infection transmission systems that are being developed for the US Environmental Protection Agency as part of a project to quantify the risk of microbial infection. The models are designed to help inform water treatment system design decisions.

Animals↗

Bitumen fumes: review of work on the potential risk to workers and the present knowledge on its origin.

Bitumens fumes contain polycyclic aromatic compounds (PAC). There is a possibility of long-term health effects following chronic exposure by inhalation or skin contamination in asphalt road pavers and highway maintenance workers. Epidemiological and experimental studies on this topic are reviewed and the possible causes of cancer discussed with a primary focus on heterocyclic polyaromatic compounds. In 2001, the results of the IARC epidemiological study confirmed an excess of lung cancer despite a lower cancer mortality. In vitro genotoxicity and mechanistic studies demonstrated a mutagenic effect of bitumen fume condensates (BFC) and some data suggested that the polycyclic aromatic hydrocarbons (PAH) analysed were not the major genotoxic compounds in bitumen fume condensates. Other compounds such as nitrogen-, sulfur- and/or oxygen-containing PAH or their alkyl substituted analogues, mutagenic in the Ames mutation assay, may be involved in the genotoxic effect of BFC. After skin painting with BFC, DNA adducts were found in skin, lung and lymphocytes of all the treated animals. Differences in the adduct patterns were also observed, but a more polar adduct was common to the three tissues and not observed in those from rats treated with coal-tar fume condensates (CTFC). Rat inhalation experiments with bitumen fumes confirmed the presence of a DNA-adduct in the lungs with the same Rf as the previous polar adduct. This adduct therefore merits further investigation as a potential biomarker in lymphocyte DNA to follow exposed workers. All the analytical data and the mechanistic data are complementary and suggest the potential role of thiophenes in the genotoxicity of bitumen fumes. Some thiophenes have lower mutagenic activity than their isosteric PAH, whereas others are very potent carcinogens. Generally, the sulfur analogues of PAH (SPAH) in bitumen fumes have a higher concentration than the PAH of similar molecular weight, whereas the SPAH in coal-tar fumes have a much lower concentration than the corresponding PAH. This may explain why the more polar adducts have been detected only in animals exposed to bitumen fume. In a skin carcinogenicity study of condensed asphalt roofing fumes, it has been demonstrated that the most active fractions were those containing a variety of aromatic SPAH. In conclusion to this review, there is an interest in determining the chemical identity of the major DNA adducts induced by BFC. This would allow experimental studies on the carcinogenic potency of these compounds and their validation as potential biomarkers. These compounds could thus merit further analytical investigation in preference to the PAH included in the list of the US Environmental Protection Agency that are currently being analysed by the industry in field studies.

Administration, Cutaneous↗

Fish tissue quality in the lower Mississippi River and health risks from fish consumption.

Between 1990 and 1994, samples of three shellfish species (i.e. blue crab, Callinectes sapidus;crayfish, Procambarus acutis; and river shrimp, Macrobrachium ohionii) and 16 fish species and were collected at six sites along the lower Mississippi River by the Louisiana Department of Environmental Quality, Office of Water Resources in coordination with the US Environmental Protection Agency. The fish species included: bigmouth buffalo (Ictiobus cyanellus); blue catfish (Ictalurus furcatus); carp (Cyprinus carpio); channel catfish (Ictalurus punctatus); cobia (Rachycentron canadum); flathead catfish (Pylodictis olivaris); freshwater drum (Aplodinotus grunniens); largemouth bass (Micropterus salmoides); long nose gar (Lepisosteus osseus); red drum (Sciaenops ocellatus); red snapper (Lutjanus campechanus); smallmouth buffalo (Ictiobus bubalus); spotted gar (Lepisosteus oculatus); striped bass (Morone saxatilis); white bass (Morone chrysops); and white crappie (Pomoxis annularis). Organic compound and heavy metal concentrations were measured in 161 composite fish tissue samples where each composite included three to 10 individual fish. Nineteen chemicals, found at measurable levels in sample tissues, were used in calculations of lifetime excess cancer and non-cancer risks due to fish consumption. We calculated: 574 chemical-specific cancer risks; 41 total cancer risks; and 697 margins of exposure based on a consumption rate of one 8-ounce meal per week (0.032 kg/day), a body weight of 70 kg and reported cancer potency factors and reference doses. We identified nine species of concern (blue catfish, carp, channel catfish, cobia, crayfish, flathead catfish, red drum, spotted gar and striped bass) based on total cancer risk greater than 10(-4) or margin of exposure greater than 1, and whether or not samples collected in subsequent years resulted in lower risks. The compounds primarily responsible for the elevated risks were aldrin, dieldrin, alpha-benzene hexachloride, gamma-benzene hexachloride, heptachlor epoxide, arsenic and mercury.

Animals↗

Levels and patterns of polycyclic aromatic hydrocarbons in incineration ashes.

Polycyclic aromatic hydrocarbons were analysed in weathered bottom ash from municipal solid waste incineration, fly ash from a mixed heating plant and an ash mixture from different kinds of biofuels. Although of different origin and age, all three ashes are evaluated in different small-scale fill applications. The ultimate goal is the usage of these ashes on a larger scale. The samples were Soxhlet extracted and analysed using GC/MS in the full scan mode. The sum of the 16 US EPA PAHs was found to vary from 140 microg/kg up to more than 77000 microg/kg. Total amounts of PAHs were similar in bottom ash and in fly ash. The concentration in the mixed biofuel ash was more than 10 times higher, and exceeded the generic guidelines for PAHs in soil set by the Swedish Environmental Protection Agency. The patterns of the individual PAHs normalised to the total concentration of PAHs were found to be very similar for all the three ashes. Naphthalene and phenanthrene were the dominating PAHs for all ash samples, but the mixed biofuel ash also contained high levels of fluoranthene and pyrene.

Journal Article↗