Reductive debromination of nonabrominated diphenyl ethers by sodium borohydride and identification of octabrominated diphenyl ether products

A method was developed to study reductive transformation of highly brominated diphenyl ethers (BDEs). The method development is a part of a broader project where it will be used to determine the susceptibility of environmental pollutants to reductive conditions, in an attempt to create a scheme for determination of chemical’s persistence. This paper focuses on identification of octabrominated diphenyl ether transformation products from reductive debromination of the three nonabrominated diphenyl congeners (nonaBDE), BDE-206, -207 and -208. Sodium borohydride was used to explore the reductive debromination of the nonaBDEs. The transformation products were collected at two time-points and identified products were quantified by GC-MS. The reduction of the nonaBDEs lead primarily to debrominated products, mainly octaBDEs. The three nonabrominated DEs gave isomer-related transformation product patterns. BDE-207 and BDE-208 showed a propensity for ortho-debromination in the initial reaction step, while no discrimination between initial debromination positions was seen for BDE-206. All three nonabrominated DEs displayed a preferred initial debromination on the fully brominated DE ring.     

Pollutants and the health of green sea turtles resident to an urbanized estuary in San Diego, CA

Rapid expansion of coastal anthropogenic development means that critical foraging and developmental habitats often occur near highly polluted and urbanized environments. Although coastal contamination is widespread, the impact this has on long-lived vertebrates like the green turtle (Chelonia mydas) is unclear because traditional experimental methods cannot be applied. We coupled minimally invasive sampling techniques with health assessments to quantify contaminant patterns in a population of green turtles resident to San Diego Bay, CA, a highly urbanized and contaminated estuary. Several chemicals were correlated with turtle size, suggesting possible differences in physiological processes or habitat utilization between life stages. With the exception of mercury, higher concentrations of carapace metals as well as 4,4′-dichlorodiphenyldichloroethylene (DDE) and γ chlordane in blood plasma relative to other sea turtle studies raises important questions about the chemical risks to turtles resident to San Diego Bay. Mercury concentrations exceeded immune function no-effects thresholds and increased carapace metal loads were correlated with higher levels of multiple health markers. These results indicate immunological and physiological effects studies are needed in this population. Our results give insight into the potential conservation risk contaminants pose to sea turtles inhabiting this contaminated coastal habitat, and highlight the need to better manage and mitigate contaminant exposure in San Diego Bay.     

Peroxidase-mediated removal of endocrine disrupting compound mixtures from water

Several classes of oxidative enzymes have shown promise for efficient removal of endocrine disrupting compounds (EDCs) that are resistant to conventional wastewater treatments. Although the kinetics of reactions between individual EDCs and selected oxidative enzymes are well documented in the literature, there has been little investigation of reactions with EDC mixtures. This makes it impossible to predict how enzyme-mediated treatment systems will perform since wastewater effluents generally contain multiple EDCs. This paper reports pseudo-first order rate constants for a model oxidative enzyme, horseradish peroxidase (HRP), during single-substrate (k₁) and mixed-substrate (k_1-MIX) reactions. Measured values are compared with literature values of three Michaelis-Menten parameters: half-saturation constant (K_M), enzyme turnover number (k_CAT), and the ratio k_CAT/K_M. Published reports had suggested that each of these could be correlated with HRP reactivity towards EDCs in mixtures, and empirical results from this study show that K_M can be used to predict the sequence of EDC removal reactions within a particular mixture. We also observed that k_1-MIX values were generally greater than k₁ values and that compounds exhibiting greatest estrogenic toxicities reacted most rapidly in a given mixture. Finally, because K_M may be tedious to measure for every EDC of interest, we have constructed a quantitative structure-activity relationship (QSAR) model to predict these values. This model predicts K_M quite accurately (R² = 89%) based on two molecular characteristics: molecular volume and hydration energy. Its accuracy makes this QSAR a useful tool for predicting which EDCs will be removed most efficiently during enzyme treatment of EDC mixtures.     

A Critique of Estimating Future Costs Using Most Likely Value

ASTM E2137 (Standard Guide for Estimating Monetary Costs and Liability for Environmental Matters, or E2137) is the guidance for developing estimates of future environmental costs. E2137 provides a hierarchy of cost estimation approaches, and expresses an explicit preference for the use of probabilistic cost analysis to develop expected values for environmental costs. Dr. Ram and his colleagues have published an article (Remediation Journal, Autumn 2013) which rejects the use of EV analysis, arguing that while “good in principle” it has little practical value because it is nearly impossible to develop supportable probabilities. The E2137 principles and processes have been used for more than a decade in the context of addressing future environmental costs, yet their view of E2137 renders the standard meaningless. We conclude that the deficiency is not in the ASTM standard, and that when properly constructed, probabilistic analyses can be used to develop expected values with supportable probabilities. ©2015 Wiley Periodicals, Inc.     

Integrating the Social Dimension in Remediation Decision‐Making: State of the Practice and Way Forward

Sustainable remediation guidance, frameworks, and case studies have been published at an international level illustrating established sustainability assessment methodologies and successful implementation. Though the terminology and indicators evaluated may differ, one common theme among international organizations and regulatory bodies is more comprehensive and transparent methods are needed to evaluate the social sphere of sustainable remediation. Based on a literature review and stakeholder input, this paper focused on three main areas: (1) status quo of how the social element of sustainable remediation is assessed among various countries and organizations; (2) methodologies to quantitatively and qualitatively evaluate societal impacts; and (3) findings from this research, including challenges, obstacles, and a path forward. In conclusion, several existing social impact assessment techniques are readily available for use by the remediation community, including rating and scoring system evaluations, enhanced cost benefit analysis, surveys/interviews, social network analysis, and multicriteria decision analysis. In addition, a list of 10 main social indicator categories were developed: health and safety, economic stimulation, stakeholder collaboration, benefits community at large, alleviate undesirable community impacts, equality issues, value of ecosystem services and natural resources, risk‐based land management and remedial solutions, regional and global societal impacts, and contributions to other policies. Evaluation of the social element of remedial activities is not without challenges and knowledge gaps. Identification of obstacles and gaps during the project planning process is essential to defining sustainability objectives and choosing the appropriate tool and methodology to conduct an assessment. Challenges identified include meaningful stakeholder engagement, risk perception of stakeholders, and trade‐offs among the various triple bottom line dimensions. ©2015 Wiley Periodicals, Inc.     

Assessing ecological risk on a regional scale

Society needs a quantitative and systematic way to estimate and compare the impacts of environmental problems that affect large geographic areas. This paper presents an approach for regional risk assessment that combines regional assessment methods and landscape ecology theory with an existing framework for ecological risk assessment. Risk assessment evaluates the effects of an environmental change on a valued natural resource and interprets the significance of those effects in light of the uncertainties identified in each component of the assessment process. Unique and important issues for regional risk assessment are emphasized; these include the definition of the disturbance scenario, the assessment boundary definition, and the spatial heterogeneity of the landscape. Although the research described in this article has been funded wholly or in part by the United States Environmental Protection Agency (EPA) through Interagency Agreement Number DW89932112-01-2 to the U.S. Department of Energy, it has not been subjected to EPA review and therefore does not necessarily reflect the views of EPA and no official endorsement should be inferred.     

LEAD AND CADMIUM ASSOCIATED WITH SALTWATER INTRUSION IN A NEW JERSEY AQUIFER SYSTEM1

ABSTRACT: The U.S. Geological Survey collected ground-water samples from the upper and middle aquifers of the Potomac-Raritan-Magothy aquifer system in a 400-square-mile area of New Jersey from 1984 through 1986. Concentrations of lead were greater than the U.S. Environmental Protection Agency maximum contaminant level (MCL) of 50 micrograms per liter in water from 16 of 239 wells. The cencentrations of cadmium were greater than the MCL of 10 micrograms per liter in water from 10 to 241 wells. One-half of the wells that exceeded the lead MCL were in known areas of saltwater intrusion, as were all 10 wells that exceeded the cadmium MCL. The association of elevated concentrations of these metals with elevated concentrations of chloride indicates a mochanism related to saltwater intrusion.     

Economic incentives for TQEM: Are they in your future?

Traditional command-and-control regulations provide few opportunities for total quality environmental management because they usually do not take into account cost and efficiency factors. However, in the past several years both Congress and EPA have shown increasing interest in using incentive-type approaches to regulate the environment. These include taxes, marketable pollution privileges, deposits and refunds, information disclosure provisions, and subsidies. The author details examples of each and discusses how they can effectively complement a quality program.     

Improving older driver knowledge and self-awareness through self-assessment: the driving decisions workbook

PURPOSE: This study aims to assess whether the Driving Decisions Workbook, a self-assessment instrument for older drivers, increased self-awareness and general knowledge. This study also assessed perceptions regarding its usefulness, particularly as a tool for facilitating discussions within families of older drivers. A secondary purpose of the study was to determine if problems identified by drivers in the workbook related to problems they had with actual driving. DESIGN AND METHODS: The Driving Decisions Workbook was administered along with a questionnaire and a road test. A convenience sample of 99 licensed drivers aged 65 and above was used. RESULTS: After completing the workbook, about three fourths of the participants reported being more aware of changes that could affect driving. Fourteen percent reported that they had discovered a change in themselves of which they had not been previously aware. All respondents found the workbook to be at least a little useful and thought the workbook could help facilitate family discussions. Workbook responses were positively correlated with overall road test scores. Significant correlations were also noted between the road test and a majority of workbook subsection responses. IMPLICATIONS: This study indicates that the workbook may be a useful first-tier assessment instrument and educational tool for the older driver. It may encourage an older driver to drive more safely and/or to seek clinical assessment, and help in facilitating discussions about driving within their families.     

Aluminium speciation in effluents and receiving waters

The respective speciation of aluminium in sewage effluent and in river water receiving effluent, has been examined. Results showed that concentrations of reactive aluminium changed over a timescale of hours and were controlled predominantly by pH. A minimum concentration of reactive aluminium occurred at a pH of approximately 6.8, coinciding with the prevalence of non-reactive, insoluble Al(OH)3 species. For receiving waters of low pH value, typically < pH 5, a large proportion of the 'naturally present' aluminium can be present in a reactive form at concentrations higher than the proposed Environmental Quality Standard (EQS). Mixing of waters of this type with effluent of a higher pH value leads to the precipitation of aluminium hydroxide. Mixing of effluent of pH value in the range 7.5-8.0 with river water in the same (or slightly higher) pH range appears to result in no appreciable change in the proportion of reactive aluminium; the change in concentration tends to be related simply to dilution. On the basis of a theoretical knowledge of aluminium speciation, results obtained in this work indicate that it is possible to make predictions about the proportion of reactive aluminium present in a receiving water, based on the pH values of the effluent water mixture and the concentration in the effluent. Reasonable comparisons between measured and predicted values were obtained at higher pH values, but the relationship was less certain at pH values less than 6.5 for which levels of reactive metal tended to be higher than the quality standard value.