Gary M. Klecka

Natural attenuation of chlorinated ethene compounds: model development and field-scale application at the Dover site

Abstract A multi-dimensional and multi-species reactive transport model was developed to aid in the analysis of natural attenuation design at chlorinated solvent sites. The model can simulate several simultaneously occurring attenuation processes including aerobic and anaerobic biological degradation processes. The developed model was applied to analyze field-scale transport and biodegradation processes occurring at the Area-6 site in Dover Air Force Base, Delaware. The model was calibrated to field data collected at this site. The calibrated model reproduced the general groundwater flow patterns, and also, it successfully recreated the observed distribution of tetrachloroethene (PCE), trichloroethene (TCE), dichloroethylene (DCE), vinyl chloride (VC) and chloride plumes. Field-scale decay rates of these contaminant plumes were also estimated. The decay rates are within the range of values that were previously estimated based on lab-scale microcosm and field-scale transect analyses. Model simulation results indicated that the anaerobic degradation rate of TCE, source loading rate, and groundwater transport rate are the important model parameters. Sensitivity analysis of the model indicated that the shape and extent of the predicted TCE plume is most sensitive to transmissivity values. The total mass of the predicted TCE plume is most sensitive to TCE anaerobic degradation rates. The numerical model developed in this study is a useful engineering tool for integrating field-scale natural attenuation data within a rational modeling framework. The model results can be used for quantifying the relative importance of various simultaneously occurring natural attenuation processes.

Bisphenol A concentrations in receiving waters near US manufacturing and processing facilities

Bisphenol A (BPA) (CAS 80-05-7) was analyzed in receiving waters upstream and downstream of US manufacturers (1996 and 1997) and processors (1997) during seasonal low flow periods. BPA was not detected (< 1 microgram/l) in any surface water sample in 1996 or at six of seven sites in 1997. Concentrations near the seventh site ranged from 2 to 8 micrograms/l; however, its receiving stream had no measurable flow and concentrations represent undiluted effluent. All surface water concentrations from this and other studies were less than the freshwater predicted no effect concentration (PNEC) of 64 micrograms/l, suggesting that BPA discharges from manufacturing and processing facilities to surface water do not pose an environmental concern.

Reductive dechlorination of chlorinated methanes and ethanes by reduced iron (II) porphyrins

The reaction of a reduced iron (II) porphyrin with a series of chlorinated methanes and ethanes was examined under neutral conditions in buffered aqueous solutions containing an excess of the reducing agent. Carbon tetrachloride, chloroform and 1,1,1-trichloroethane were reduced to lower chlorinated homologs, while methylene chloride, 1,1,2-trichloroethane and 1,1-dichloroethane did not appear to be degraded in this system.

A Weight of Evidence Analysis of the Chronic Ecotoxicity of Nonylphenol Ethoxylates, Nonylphenol Ether Carboxylates, and Nonylphenol

ABSTRACT Nonylphenol ethoxylates (NPE) are widely used surfactant compounds with many domestic and industrial applications. Due to the nature of their use in down-the-drain applications, spent NPE are discharged to septic systems or to wastewater treatment plants. Biodegradation of parent material during treatment is often incomplete, leading to release of NPE and their degradation intermediates into the environment. Considerable aquatic toxicity research has occurred on NPE and particularly on nonylphenol (NP). Available data were subjected to a quality review and all studies of acceptable quality were used in a weight of evidence hazard assessment. Data for NP were further analyzed using a Species Sensitivities Distribution (SSD) approach. About 90 chronic values are available (ChVs, geometric mean of the no-observed effect concentration and lowest-observed effect concentration for each endpoint reported), which may be reduced to average ChVs for each tested species. Higher mole NPE (NPE ≥ 9) had ChVs ranging from 900 to 14,100 μg/L, ChVs for the low mole nonylphenol ether carboxylate (NPEC1) ranged from 3200 to 12,000 μg/L, ChVs for lower mole NPE (NPE1,2) ranged from 11 to 500 μg/L, and ChVs for NP ranged from 5 to 3500 μg/L. Using the SSD analysis for NP with higher quality study results, the 10th percentile chronic effect value is 5.7 μg/L, which supports the draft USEPA criteria on NP of 5.9 μg/L.

Chemicals of emerging concern in the Great Lakes Basin: an analysis of environmental exposures.

This review and statistical analysis was conducted to better understand the nature and significance of environmental exposures in the Great Lakes Basin and watershed to a variety of environmental contaminants. These contaminants of interest included current-use pesticides, pharmaceuticals, organic wastewater contaminants, alkylphenol ethoxylates, perfluorinated surfactants, flame retardants, and chlorinated paraffins. The available literature was critically reviewed and used to develop a database containing 19,611 residue values for 326 substances. In many papers, sampling locations were characterized as being downstream from municipal wastewater discharges, receiving waters for industrial facilities, areas susceptible to agricultural or urban contamination, or harbors and ports. To develop an initial assessment of their potential ecological significance, the contamination levels found were compared with currently available regulatory standards, guidelines, or criteria. This review was prepared for the IJC multi-board work group, and served as background material for an expert consultation, held in March, 2009, in which the significance of the contaminants found was discussed. Moreover, the consultation attempted to identify and assess opportunities for strengthening future actions that will protect the Great Lakes. Based on the findings and conclusions of the expert consultation, it is apparent that a wide variety of chemicals of emerging concern have been detected in environmental media (air, water, sediment, biota) from the Great Lakes Basin, although many are present at only trace levels. Although the presence of these contaminants raises concerns in the public and among the scientific community, the findings must be placed in context. Significant scientific interpretation is required to understand the extent to which these chemicals may pose a threat to the ecosystem and to human health. The ability to detect chemicals in environmental media greatly surpasses our ability to understand the implications of such findings. As advances in analytical technologies occur, it is probable that substances previously found to be non-detectable will be detected. However, their presence in environmental media should not be construed to mean that they are necessarily toxic or hazardous. Current-use pesticides are tightly regulated and extensive efforts have been made to analyze for their presence in surface waters from the Great Lakes Basin. The concentrations found in surface waters for many of the pesticides are below current regulatory criteria. However, the concentrations of certain pesticides exceeded current criteria in 6-32% of the samples analyzed. Detectable concentrations of pharmaceutical compounds were present in 34% of the surface water samples. Various prescription and non-prescription drugs were detected, most frequently at locations that were proximate to the point of discharge from wastewater treatment plants or agricultural operations. At present, there are no standards, guidelines, or criteria with which to compare these contaminant concentrations. Concentrations of alkylphenol ethoxylates and their metabolites have been well studied. All surface water nonylphenol concentrations were below US ambient water quality criteria. However, the concentrations reported for some locations exceeded Canadian guidelines for water or sediment. Only limited data were available for a wide variety of organic wastewater contaminants. Measured concentrations in Great Lakes waters were generally low. Where criteria exist for comparison, the concentrations found were generally below the associated regulatory standards. However, exceedences were noted for some classes of compounds, including phthalates and polycyclic aromatic hydrocarbons. The highest environmental concentrations were reported in biota for a number of persistent, bioaccumulative, and toxic compounds (e.g., polybrominated diphenyl ethers, perfluorinated surfactants). Various stewardship as well as government risk assessment and risk management programs have been implemented over the past years for many of these compounds. Because risk management strategies for some of these contaminants have been implemented only recently, their impact on environmental concentrations, to date, remains unclear. Current evidence suggests that the concentrations of some brominated flame retardants are trending downward, while the concentrations of others appear to be increasing. Regulatory criteria are not available for many of the chemicals of emerging concern that were detected in the Great Lakes Basin. When criteria do exist, it is important to recognize that they were developed based on the best available science at the time. As the science evolves, regulatory criteria must be reassessed in light of new findings (e.g., consideration of new endpoints and mechanisms of action). Further, there are significant scientific gaps in our ability to interpret environmental monitoring data, including the need for: (a) improving the understanding of the effects of mixtures, (b) information on use of, and the commercial life cycle of chemicals and products that contain them, (c) information on source contributions and exposure pathways, and (d) the need for thoughtful additional regulatory,environmental, and health criteria. Discharges from wastewater treatment plants were identified as an important source of contaminants to surface waters in the Great Lakes Basin. Combined sewer overflows and agricultural operations were also found to be important contributors to concentrations in surface waters. Concentrations of many of the chemicals were generally the highest in the vicinity of these sources, decline with increasing distance from sources, and were generally low or non-detectable in the open waters of the Great Lakes.

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: characterization of microbial community structure.

A polyphasic approach based on cultivation and direct recovery of 16S rRNA gene sequences was utilized for microbial characterization of an aquifer contaminated with chlorinated ethenes. This work was conducted in order to support the evaluation of natural attenuation of chlorinated ethenes in groundwater at Area 6 at Dover Air Force Base (Dover, DE). Results from these studies demonstrated the aquifer contained relatively low biomass (e.g. direct microscopic counts of < 10(7) bacteria/g of sediment) comprised of a physiologically diverse group of microorganisms including iron reducers, acetogens, sulfate reducers, denitrifiers, aerobic and anaerobic heterotrophs. Laboratory microcosms prepared with authentic sediment and groundwater provided direct microbiological evidence that the mineralization of vinyl chloride and cis-dichloroethene as well as each step in the complete reductive dechlorination of tetracloroethene to ethene can occur in the Area 6 aquifer. Enrichment cultures capable of the oxidative degradation of cis-1,2-dichloroethene (cis-DCE) and vinyl chloride (VC) were obtained from groundwater across the aquifer demonstrating the possible importance of direct, non-cometabolic oxidation of cis-DCE and VC in natural attenuation. Culture-independent analyses based upon recovery of 16S rRNA gene sequences revealed the presence of anaerobic organisms distributed primarily between two major bacterial divisions: the delta subdivision of the Proteobacteria and low-G + C gram positive. Recovery of sequences affiliated with phylogenetic groups containing known anaerobic-halorespiring organisms such as Desulfitobacterium, Dehalobacter, and certain groups of iron reducers provided qualitative support for a role of reductive dechlorination processes in the aquifer. This molecular data is suggestive of a functional linkage between the microbiology of the site and the apparent natural attenuation process. The presence and distribution of microorganisms were found to be consistent with a microbially driven attenuation of chlorinated ethenes within the aquifer and in accord with a conceptual model of aquifer geochemistry which suggest that both reductive and oxidative mechanisms are involved in heterogeneous, spatially distributed processes across the aquifer.

Biological transformations of 1,2-dichloroethane in subsurface soils and groundwater

Abstract The ability of naturally occurring microorganisms to biodegrade 1,2-dichloroethane was examined in soil/water microcosms prepared using aquifer material obtained from manufacturing sites in Louisiana and Texas with known histories of exposure to the compound, as well as in aquifer samples taken from a site in Oklahoma with no known history of 1,2-dichloroethane contamination. Biotransformation of 1,2-dichloroethane was noted under methanogenic or sulfate reducing conditions in all samples. Under anaerobic conditions, 1,2-dichloroethane was transformed to ethylene in a single step via reductive dihaloelimination. No other metabolites were detected in the reaction mixtures. Microbial adaptation appeared to be required for biotransformation of 1,2-dichloroethane. Lag periods ranging from 7 to 8 weeks preceded degradation in microcosms prepared with aquifer material from the Texas and Oklahoma sites. In contrast, no lag period was evident prior to biotransformation in microcosms prepared from the Louisiana manufacturing site, which is consistent with field evidence for natural biological attenuation in situ based on analysis of the groundwater chemistry. Aerobic biodegradation of 1,2-dichloroethane to carbon dioxide was also observed after 13 weeks in aquifer material from the Louisiana site, but was not evident in samples from the Texas or Oklahoma sites following 18 weeks of incubation. The ability of naturally occurring microorganisms to degrade 1,2-dichloroethane has bearing on assessments of the fate and lifetime of the compound in the environment, as well as having potential application in the remediation of contaminated groundwater.

Early life-stage and multigeneration toxicity study with bisphenol A and fathead minnows (Pimephales promelas).

Regulatory guidelines for long term testing to assess the toxicity of xenobiotic compounds such as bisphenol A (BPA) with fish have focused on survival, growth, and development in early life stages. Early life stages are critical windows of exposure, but do not address later phases in the life cycle, such as reproduction, that are equally important for the continued survival of the organisms. Residual amounts of BPA are released to surface water. BPA has, therefore, been the subject of considerable toxicity testing with fish and other aquatic organisms. A long term multigeneration test with fish has been conducted to better interpret the environmental relevance of detectable levels of BPA. Fathead minnow (Pimephales promelas) were exposed for 444 days over the course of three generations that included F0 reproducing adults, F1 eggs grown to be reproducing adults, and F2 eggs. Endpoints included survival, growth, reproduction, and vitellogenin concentrations. Concentrations tested ranged from 1 to 1,280 μg/L. No observed effect concentrations (NOEC) of 640 μg/L and higher for growth parameters show few differences between age or generation. Reproductive NOEC in F0 and F1 breeding pairs were 640 and 160 μg/L, respectively. The lowest NOEC related to survival, growth and development or reproduction was 16 μg/L for F2 hatching success. This long term study covered both early life and adult reproduction stages that allowed examination of all critical windows of exposure. Overall, NOEC ranging from 16 to 1,280 μg/L were found, which are well above median and upper 95th percentile concentrations of BPA in fresh waters in North America and Europe (0.081 and 0.47 μg/L and 0.01 and 0.035 μg/L, respectively). The likelihood is low that measured concentrations of BPA in surface water would affect fish, even if exposed over more than one generation.

Relevance of drinking water as a source of human exposure to bisphenol A

A comprehensive search of studies describing bisphenol A (BPA) concentrations in drinking water and source waters (i.e., surface water and groundwater) was conducted to evaluate the relevance of drinking water as a source of human exposure and risk. Data from 65 papers were evaluated from North America (31), Europe (17), and Asia (17). The fraction of drinking water measurements reported as less than the detection limit is high; 95%, 48%, and 41%, for North America, Europe, and Asia, respectively. The maximum quantified (in excess of the detection limit) BPA concentrations from North America, Europe, and Asia are 0.099 μg/l, 0.014 μg/l, and 0.317 μg/l. The highest quantified median and 95th percentile concentrations of BPA in Asian drinking water are 0.026 μg/l and 0.19 μg/l, while high detection limits restricted the determination of representative median and 95th percentile concentrations in North America and Europe. BPA in drinking water represents a minor component of overall human exposure, and compared with the lowest available oral toxicity benchmark of 16 μg/kg-bw/day (includes an uncertainty factor of 300) gives margins of safety >1100. Human biomonitoring data indicate that ingestion of drinking water represents <2.8% of the total intake of BPA.

Simultaneous quantitation of testosterone, estradiol, ethinyl estradiol, and 11-ketotestosterone in fathead minnow fish plasma by liquid chromatography/positive atmospheric pressure photoionization tandem mass spectrometry

In the present work, for the first time, a rapid and sensitive liquid chromatography/positive atmospheric pressure photoionization tandem mass spectrometry (LC/APPI-MS/MS) method has been developed and validated for the simultaneous quantitation of testosterone, estradiol, ethinyl estradiol, and 11-ketotestosterone in fathead minnow fish plasma using no more than 10 microL of plasma. Compounds present in plasma were directly derivatized with dansyl chloride and 25 microL of the derivatized mixture was injected into the LC/APPI-MS/MS system. The gradient chromatographic elution was achieved on an Agilent Zorbax SB-C18 analytical column (2.1 mm x 50 mm, 1.8 microm particle size) with mobile phases consisting of acetonitrile, water and acetic acid. The flow rate was 0.5 to 0.7 mL/min and the total run time was 11.5 min. The lower limits of quantitation for testosterone, estradiol, ethinyl estradiol, and 11-ketotestosterone and were 1, 1, 1, and 2.5 ng/mL, respectively. Intra-batch precision was less than 19.4% and inter-batch precision was less than 11.7% for all four analytes. Accuracy was within 83.5-115.4% of nominal concentrations. This method is used for quantitation of sex steroid levels in fathead minnow tested in endocrine disruptor screening experiments.