Pilot‐scale evaluation using bioaugmentation to enhance PCE dissolution at dover AFB national test site

An Interstate Technology and Regulatory Council (ITRC) forum was recently held that focused on six case studies in which bioremediation of dense nonaqueous‐phase liquids (DNAPLs) was performed; the objective was to demonstrate that there is credible evidence for bioremediation as a viable environmental remediation technology. The first two case studies from the forum have been previously published; this third case study involves a pilot‐scale demonstration that investigated the effects of biological activity on enhancing dissolution of an emplaced tetrachloroethene (PCE) DNAPL source. It used a controlled‐release test cell with PCE as the primary DNAPL in a porous media groundwater system. Both laboratory tests and a field‐scale pilot test demonstrated that bioaugmentation can stimulate complete dechlorination to a nontoxic end product and that the mass flux from a source zone increases when biological dehalorespiration activity is enhanced through nutrient (electron donor) addition and bioaugmentation. All project goals were met. Important achievements include demonstrating the ability to degrade a PCE DNAPL source to ethene and obtaining significant information on the impacts to the microbial populations and corresponding isotope enrichments during biodegradation of a source area. © 2007 Wiley Periodicals, Inc.     

Ultra trace simultaneous determination of 50 polycyclic aromatic hydrocarbons in biota using pMRM GC-MS/MS

Abstract

A saponification extraction method with gas chromatography pseudo-MRM (pMRM) mass spectrometry detection was developed for the determination of 50 total polycyclic aromatic hydrocarbons (TPAH50, a combination of parent and alkylated homologues) in biota. The method was aimed at monitoring and identification of potential TPAH contaminants in bitumen impacted environments. Alkylated PAHs were determined by multi-level, quantitative calibration using parent PAHs. The developed and thoroughly validated method required only one injection for TPAH50 analysis which represents significant saving of time and expensive authentic alkylated standards. The current method was tested with certified reference mussel tissue NIST 1974c and performed well. In a comparison study, the method reached a limit of quantitation (LOQ) for the TPAH50 between 0.1 and 0.2?ng g^?1, while the QuEChERs enhanced matrix removal – lipid (EMR) kit produced by Agilent showed an LOQ of 5–10?ng g^?1. The current method relied on response factors (RF) for the quantitation of alkylated PAHs determined against parent PAHs. These RFs were shown to be stable and consistent over the course of 1 year, during which over 200 routine environmental biota monitoring samples were analyzed. The environmental biota monitoring samples analyzed include muscle, carcass and liver, with an average total PAH50 concentration of 13, 90 and 135?ng g^?1, respectively. Results show significant differences in the distributions of 1 ringed, 2 ringed, 3 ringed, 4 ringed, and 5+ ringed TPAHs between the types of biota samples.     

Bioaccumulation of the pharmaceutical 17α-ethinylestradiol in shorthead redhorse suckers (Moxostoma macrolepidotum) from the St. Clair River, Canada

17α-ethynylestradiol (EE2), a synthetic estrogen prescribed as a contraceptive, was measured in Shorthead Redhorse Suckers (ShRHSs) (Moxostoma macrolepidotum) collected near a wastewater treatment plant (WWTP) in the St. Clair River (Ontario, Canada). We detected EE2 in 50% of the fish samples caught near the WWTP (Stag Island), which averaged 1.6 ± 0.6 ng/g (wet weight) in males and 1.43 ± 0.96 ng/g in females. No EE2 was detected in the samples from the reference site (Port Lambton) which was 26 km further downstream of the Stag Island site. Only males from Stag Island had VTG induction, suggesting the Corunna WWTP effluent as a likely source of environmental estrogen. EE2 concentrations were correlated with total body lipid content (R² = 0.512, p < 0.01, n = 10). Lipid normalized EE2 concentrations were correlated with δ¹⁵N (R² = 0.436, p < 0.05, n = 10), suggesting higher EE2 exposures in carnivores. Our data support the hypothesis of EE2 bioaccumulation in wild fish.     

The effects of tertiary treated municipal wastewater on fish communities of a small river tributary in Southern Ontario, Canada

Fish community changes associated with a tertiary treated municipal wastewater effluent outfall in the Speed River, Ontario, Canada, were evaluated at nine sites over two seasons (2008) using standardized electrofishing. Habitat evaluations were conducted to ensure that the riffle sites selected were physically similar. The fish community was dominated by several species of darters that differed in their response to the effluent outfall. There was a significant decrease in Greenside Darter (Etheostoma blennioides) but an increase in Rainbow Darter (E. caeruleum) abundance directly downstream of the outfall. Stable isotope signatures (δ¹³C and δ¹⁵N), which indicate shifts in energy utilization and flow, increased in Rainbow Darter downstream, but showed no change in Greenside Darter. Rainbow Darter may be exploiting a food source that is not as available at upstream sites giving them a competitive advantage over the Greenside Darter immediately downstream of the outfall.     

Mass culture of the rotifer Brachionus plicatilis and its evaluation as a food for larval anchovies

Growth rates of anchovy larvae, Engraulis mordax, reared for 19 days under constant environmental conditions on a diet of laboratory-cultured organisms, exceeded the growth rates of anchovies fed on a diet of wild plankton. The rotifer Brachionus plicatilis was found to be a nutritous food source when fed to the larvae in concentrations of 10 to 20/ml and in combination with the dinoflagellate Gymnodinium splendens (100/ml). Optimum conditions were determined for mass culture of the rotifer. A high food concentration was the most important parameter needed to assure a high yield of rotifers. Large volumes (464 I) of the unicellular flagellate Dunaliella sp. were cultured for feeding the rotifers. The rotifer culture technique described produces approximately 2.5×10⁶ organisms/day, providing a reliable food source for rearing studies. The lengths of B. plicatilis (without eggs) ranged between 99 and 281 , most rotifers being larger than 164 and less than 231 . Individuals weighed 0.16 g and contained 8×10^-4 cal.     

Quantifying chlorinated ethene degradation during reductive dechlorination at Kelly AFB using stable carbon isotopes

Stable isotope analysis of chlorinated ethene contaminants was carried out during a bioaugmentation pilot test at Kelly Air Force Base (AFB) in San Antonio Texas. In this pilot test, cis-1,2-dichloroethene (cDCE) was the primary volatile organic compound. A mixed microbial enrichment culture, KB-1, shown in laboratory experiments to reduce chlorinated ethenes to non-toxic ethene, was added to the pilot test area. Following bioaugmentation with KB-1, perchloroethene (PCE), trichloroethene (TCE) and cDCE concentrations declined, while vinyl chloride (VC) concentrations increased and subsequently decreased as ethene became the dominant transformation product. Shifts in carbon isotopic values up to 2.7 per thousand, 6.4 per thousand, 10.9 per thousand and 10.6 per thousand were observed for PCE, TCE, cDCE and VC, respectively, after bioaugmentation, consistent with the effects of biodegradation. While a rising trend of VC concentrations and the first appearance of ethene were indicative of biodegradation by 72 days post-bioaugmentation, the most compelling evidence of biodegradation was the substantial carbon isotope enrichment (2.0 per thousand to 5.0 per thousand) in ?13C(cDCE). Fractionation factors obtained in previous laboratory studies were used with isotope field measurements to estimate first-order cDCE degradation rate constants of 0.12 h(-1) and 0.17 h(-1) at 115 days post-bioaugmentation. These isotope-derived rate constants were clearly lower than, but within a factor of 2-4 of the previously published rate constant calculated in a parallel study at Kelly AFB using chlorinated ethene concentrations. Stable carbon isotopes can provide not only a sensitive means for early identification of the effects of biodegradation, but an additional means to quantify the rates of biodegradation in the field.     

Polybrominated diphenyl ethers and their methoxylated and hydroxylated analogs in Brown Bullhead (Ameiurus nebulosus) plasma from Lake Ontario

Polybrominated diphenyl ethers (PBDEs), methoxylated PBDEs (MeO-PBDEs) and hydroxylated PBDEs (OH-PBDEs) were detected and quantified in Brown Bullhead (Ameiurus nebulosus) from Lake Ontario. Samples were collected in 2006 from three different locations near the city of Toronto: Frenchman’s Bay, Toronto Island, and Tommy Thompson Park. A total of 117 plasma samples were pooled into 19 samples, separating males and females by site of capture. Pooled samples were analyzed for 36 PBDEs, 20 MeO-PBDEs and 20 OH-PBDEs, but only six PBDEs, five MeO- and eight OH-compounds were confirmed against standards currently available. These peaks were quantified as “identified” peaks, while peaks matching ion ratios but not matching the retention time of the available standards were quantified as “unidentified” peaks. Both “identified” and “unidentified” concentrations were combined to obtain a total concentration. No significant variations were obtained for total PBDE concentrations, ranging from 3.33 to 9.02 ng g^?1 wet weight. However, OH- and MeO-PBDE totals ranged over 1 order of magnitude among the samples (not detected – 3.57 ng g^?1 wet weight for OH-PBDEs and not detected ?0.10 ng/g wet weight for MeO-PBDE). The results of this study suggested that these compounds are ubiquitous in biota. Source estimation of MeO- and OH-PBDEs in freshwater fish were discussed. Considering that up to date no freshwater sources for MeO- or OH-PBDEs have been reported, concentrations found should be mainly related to bioaccumulation from anthropogenic sources, although other sources could not be dismissed.     

Simulating Unstressed Crop Development and Growth Using the Unified Plant Growth Model (UPGM)

Since initial development of the EPIC model in 1989, the EPIC plant growth component has been incorporated into other erosion and crop management models (e.g., WEPS, WEPP, SWAT, ALMANAC, and GPFARM) and subsequently modified to meet research objectives of the model developers. This has resulted in different versions of the same base plant growth component. The objectives of this study are the following: (1) describe the standalone Unified Plant Growth Model (UPGM), initially derived from the WEPS plant growth model, to be used for merging enhancements from other EPIC-based plant growth models; and (2) describe and evaluate new phenology, seedling emergence, and canopy height sub-models derived from the Phenology Modular Modeling System (PhenologyMMS V1.2) and incorporated into UPGM. A 6-year (2005–2010) irrigated maize (Zea mays L.) study from northeast Colorado was used to calibrate and evaluate UPGM running both the original (i.e., based on WEPS) and new phenology, seedling emergence, and canopy height sub-models. Model statistics indicated the new sub-models usually resulted in better simulation results than the original sub-models. For example when comparing original and new sub-models, respectively, for predicting canopy height, the root mean square error (RMSE) was 53.7 and 40.7 cm, index of agreement (d) was 0.84 and 0.92, relative error (RE) was 26.0 and ?1.26 %, and normalized objective function (NOF) was 0.47 and 0.33. The new sub-models predict leaf number (old sub-models do not), with mean values for 4 years of 2.43 leaves (RMSE), 0.78 (d), 18.38 % (RE), and 0.27 (NOF). Simulating grain yield, final above ground biomass, and harvest index showed little difference when running the original or new sub-models. Both the new phenology and seedling emergence sub-models respond to varying water deficits, increasing the robustness of UPGM for more diverse environmental conditions. Future research will continue working to incorporate existing enhancements from other EPIC-based plant growth models to unify them into one model such as multispecies competition and N cycling.     

Variations in expression of carbon isotope fractionation of chlorinated ethenes during biologically enhanced PCE dissolution close to a source zone

The stable carbon isotope values of tetrachloroethene (PCE) and its degradation products were monitored during studies of biologically enhanced dissolution of PCE dense nonaqueous phase liquid (DNAPL) to determine the effect of PCE dissolution on observed isotope values. The degradation of PCE was monitored in a 2-dimensional model aquifer and in a pilot test cell (PTC) at Dover Air Force Base, both with emplaced PCE DNAPL sources. Within the plume down gradient from the source, the isotopic fractionation of dissolved PCE and its degradation products were consistent with those observed in biodegradation laboratory studies. However, close to the source zone significant shifts in the isotope values of dissolved PCE were not observed in either the model aquifer or PTC due to the constant input of newly dissolved, non fractionated PCE, and the small isotopic fractionation associated with PCE reductive dechlorination by the mixed microbial culture used. Therefore the identification of reductive dechlorination in the presence of PCE DNAPL was based upon the appearance of daughter products and the isotope values of those daughter products. An isotope model was developed to simulate isotope values of PCE during the dissolution and degradation of PCE adjacent to a DNAPL source zone. With the exception of very high degradation rate constants (>1/day) stable carbon isotope values of PCE estimated by the model remained within error of the isotope value of the PCE DNAPL, consistent with measured isotope values in the model aquifer and in the PTC.