Critical Review of Environmental Forensic Techniques: Part I

A multitude of forensic techniques are available for age dating and source identification, including aerial photography interpretation, corrosion models, the commercial availability of a compound, chemical associations with discrete type processes, chemical profiling, degradation models and contaminant transport models. These techniques, however, are rarely challenged or discussed in the literature relative to the scrutiny encountered in environmental litigation. When introduced as scientific evidence, the governing assumptions and quality of the data are critically evaluated and frequently successfully challenged. The purpose of this paper is to review five types of forensic techniques and discuss their merits so that a user can decide which technique, or combination of techniques, is most appropriate for developing the technical portion of a case.     

Levels and isomer profiles of Dechlorane Plus in the surface soils from e-waste recycling areas and industrial areas in South China

Dechlorane Plus (DP) is a highly chlorinated flame retardant. Levels of DP were measured in surface soils from e-waste recycling areas and industrial areas in South China. Higher DP levels were found in e-waste recycling areas (undetectable-47.4 ng/g) than those in industrial areas (0.0336-4.65 ng/g) in South China. The highest DP concentration (3327 ng/g) was found at the e-waste recycling site in Qingyuan, while DP levels fell dramatically with increasing distance away from the recycling site, suggesting that the e-waste recycling activities are an important source of DP emissions. The mean ratios of anti-DP to total DP (f_anti) for different sampling areas ranged from 0.58 to 0.76 and showed no significant difference from the ratio for the technical DP products (t-test, p > 0.05). Further intensive studies are needed to investigate the process of DP degradation and its degradation products.     

Batch reactor kinetic studies on the reductive dechlorination of chlorinated ethylenes by tetrakis-(4-sulfonatophenyl)porphyrin cobalt

Tetrakis-(4-sulfonatophenyl)porphyrin cobalt was identified as a highly-active reductive dechlorination catalyst for chlorinated ethylenes. Through batch reactor kinetic studies, degradation of chlorinated ethylenes proceeded in a step-wise fashion with the sequential replacement of Cl by H. For perchloroethylene (PCE) and trichloroethylene (TCE), the dechlorination products were quantified and the C₂ mass was accounted for. Degradation of the chlorinated ethylenes was found to be first-order in substrate. Dechlorination trials with increasing catalyst concentration showed a linearly increasing pseudo first-order rate constant which yielded rate laws for PCE and TCE degradation that are first-order in catalyst. The dechlorination activity of this catalyst was compared to that of another water-soluble cobalt porphyrin under the same reaction conditions and found to be comparable for PCE and TCE.     

Quantification of biotransformation of chlorinated hydrocarbons in a biostimulation study: added value via stable carbon isotope analysis

Stable carbon isotope analysis of chlorinated aliphatic compounds was performed at an in situ biostimulation pilot test area (PTA) at a site where 1,2-dichloroethane (1,2-DCA) and trichloroethene (TCE) were present in groundwater. Chlorinated products of TCE reductive dechlorination (cis-dichloroethene (cDCE) and vinyl chloride (VC)) were present at concentrations of 17.5 to 126.4 micromol/L. Ethene, a potential degradation product of both 1,2-DCA dihaloelimination and TCE reductive dechlorination was also present in the PTA. Emulsified soybean oil and lactate were added as electron donors to stimulate anaerobic dechlorination in the PTA. Stable carbon isotope analysis provided evidence that dechlorination was occurring in the PTA during biostimulation, and a means of monitoring changes in dechlorination efficiency over the 183 day monitoring period. Stable carbon isotope analysis was also used to determine if ethene production in the PTA was due to dechlorination of TCE, 1,2-DCA, or both. Fractionation factors (alpha) were determined in the laboratory during anaerobic biotransformation of 1,2-DCA via a dihaloelimination reaction in four separate enrichment cultures. These alpha values (as well as the previously published ranges of alpha for the dechlorination of TCE, cDCE and 1,2-DCA) were used, along with isotopic values measured during the pilot test, to derive quantitative estimates of biotransformation during the pilot test. Dechlorination was found to account for 10.7 to 35.9%, 21.9 to 74.9%, and 54.4 to 67.8% of 1,2-DCA, TCE and cDCE concentration loss respectively in the PTA. Stable carbon isotope analysis indicates that dechlorination of 1,2-DCA, TCE and cDCE were all significant processes during the pilot test, while ethene production during the pilot test was dominated by 1,2-DCA dihaloelimination. This study demonstrates how stable carbon isotope analysis can provide more conservative estimates of the extent of biotransformation than do conventional protocols. In addition, in a complex mixed plume such as this, compound specific isotope analysis is shown to be one of the few methods available for clarifying dominant biotransformation pathways where breakdown products are non-exclusive (i.e. ethene).     

Characterizing natural degradation of tetrachloroethene (PCE) using a multidisciplinary approach

A site in mid-western Sweden contaminated with chlorinated solvents originating from a previous dry cleaning facility, was investigated using conventional groundwater analysis combined with compound-specific isotope data of carbon, microbial DNA analysis, and geoelectrical tomography techniques. We show the value of this multidisciplinary approach, as the different results supported each interpretation, and show where natural degradation occurs at the site. The zone where natural degradation occurred was identified in the transition between two geological units, where the change in hydraulic conductivity may have facilitated biofilm formation and microbial activity. This observation was confirmed by all methods and the examination of the impact of geological conditions on the biotransformation process was facilitated by the unique combination of the applied methods. There is thus significant benefit from deploying an extended array of methods for these investigations, with the potential to reduce costs involved in remediation of contaminated sediment and groundwater.Electronic supplementary materialThe online version of this article (10.1007/s13280-020-01418-5) contains supplementary material, which is available to authorized users.     

Diamondback terrapins as indicator species of persistent organic pollutants: Using Barnegat Bay, New Jersey as a case study

The diamondback terrapin’s (Malaclemys terrapin) wide geographic distribution, long life span, occurrence in a variety of habitats within the saltmarsh ecosystem, predatory foraging behavior, and high site fidelity make it a useful indicator species for contaminant monitoring in estuarine ecosystems. In this study fat biopsies and plasma samples were collected from males and females from two sites within Barnegat Bay, New Jersey, as well as tissues from a gravid female and blue mussels (Mytilus edulis), which are terrapin prey. Samples were analyzed for persistent organic pollutants (POPs), including polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), chlorinated pesticides, and methyl-triclosan. Terrapins from the northern site, Spizzle Creek, closest to influences from industrial areas, had higher POP concentrations for both tissues than terrapins from the less impacted Forsythe National Wildlife Refuge. Sex differences were observed with males having higher contaminant concentrations in fat and females in plasma. PCB patterns in terrapin fat and plasma were comparable to other wildlife. An atypical PBDE pattern was observed, dominated by PBDEs 153 and 100 instead of PBDEs 47 and 99, which has been documented in only a few other turtle species. The typical PBDE patterns measured in mussels, terrapin prey, suggests that the terrapin may efficiently biotransform or eliminate PBDE 47 and possibly PBDE 99. Plasma contaminant concentrations significantly and positively correlated with those in fat. This study addresses several aspects of using the terrapin as an indicator species for POP monitoring: site and sex differences, tissue sampling choices, maternal transfer, and biomagnification.     

Organochlorine contaminants in coastal marine ecosystems of southern Alaska: inferences from spatial patterns in blue mussels (Mytilus trossulus)

We measured the concentrations and chemical structures of persistent organochlorines (OCs) in blue mussels (Mytilus trossulus) from 44 sites across southwest and southeast Alaska in an effort to determine both the sources of these compounds and the extent to which this region might be contaminated. High PCB concentrations were detected at Amchitka, Adak, and Unalaska Islands (83, 430, and 2800 μg kg⁻¹ dry weight, respectively) in the Aleutians with relatively low concentrations elsewhere (7.1-51 μg kg⁻¹ dry weight). Heavy PCB congener profiles (indicative of localized point sources) characterized the high concentration sites whereas distinctly lighter congener profiles (indicative of atmospheric transport) characterized the lower concentration sites. Elevated PCB concentrations at Adak were restricted to a small area along the island’s eastern shore, suggesting either limited dispersion or rapid dilution of these compounds. More uniform chlorinated pesticide concentrations among the collection sites suggests that these compounds are entering the Aleutian ecosystem from distant sources. Pesticide concentrations correlated significantly with seabird density across the islands we sampled, thus identifying biological transport as a delivery mechanism of these compounds to the Aleutian archipelago. Our findings do not implicate persistent organochlorines as a significant factor in the recent pinniped and sea otter population declines across southwest Alaska.     

The Development of a Prediction Model for the Kinetic Constant of Chlorinated Aliphatic Hydrocarbons

Kinetic constants are important design parameters to determine the degradation of a substrate in biological treatment systems. The objective of this study was to develop a regression model using a quantitative structure–activity relationship technique for the prediction of the first-order rate constants (k) of chlorinated aliphatic hydrocarbons (CAHs). The prediction model showed very good correlations between the measured and calculated rate constants of CAHs. It was likely that the higher-order connectivity indices were important factors for the prediction of the kinetic constants, implying more complicated connectivity indices contributed to the prediction of a biological property. This technique would provide a useful tool to establish the kinetics of other CAHs without costly or time-consuming tests.     

固相萃取-高效液相色谱法测定水中氯酚类化合物

采用固相萃取-高效液相色谱法测定水中7种氯酚类化合物,Waters OASIS WAX柱萃取效率最高,最佳萃取时间和洗脱时间分别为60和5 min。该法的线性范围为1.0~40 mg/L,检出限为0.015~0.5μg/L,精密度为0.558%~2.22%,回收率为83.2%~105%。该法适用于地表水及饮用水中氯酚类化合物的检测。     

A History of the Production and Use of Carbon Tetrachloride,Tetrachloroethylene, Trichloroethylene and 1,1,1-Trichloroethane in the United States: Part 2--Trichloroethylene and 1,1,1-Trichloroethane

Carbon tetrachloride (CTC), tetrachloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) were four of the most widely used cleaning and degreasing solvents in the United States. Part 2 of this article describes the history of TCE and TCA. TCE production in the United States began in the early 1920s. TCE was used as a replacement for petroleum distillates in the dry-cleaning industry, and became the solvent of choice for vapor degreasing in the 1930s. TCE's use as a degreaser decreased in the 1960s due to toxicity concerns and the increasing popularity of TCA. Significant TCA use began in the 1950s with the development of suitable stabilizer formulations. In the 1990s, TCA was phased out under the Montreal Protocol due to its role in stratospheric ozone depletion.