Organophosphate and organophosphorothionate esters: Application of linear free energy relationships to estimate hydrolysis rate constants for use in environmental fate assessment

Hydrolysis rate constants required for assessing the environmental fate of certain organophosphate and organophosphorothionate esters may be estimated by use of linear free energy relationships (LFERs). LFERs for the second-order alkaline hydrolysis rate constants and the pKa of the conjugate acid of the leaving groups were established for 0,0-dimethyl- and 0,0-diethyl-0-substituted phosphates and phosphorothionates. Also, the second-order alkaline hydrolysis rate constants of selected triaryl phosphates were correlated with the Hammett-sigma constants. Existing LFERs for diaryl phosphate ester anions along with monoaryl phosphate ester mono- and dianions were used to predict hydrolytic half-lives under reaction conditions that are characteristic of aquatic environments.     

Potential Remobilization of Toxic Anions during Reduction of Arsenated and Chromated Schwertmannite by the Dissimilatory Fe(III)-Reducing Bacterium Acidiphilium cryptum JF-5

Schwertmannite, an iron(III)-oxyhydroxysulfate formed in acidic mining-impacted stream or lake waters often contaminated with toxic elements like arsenate or chromate, is able to incorporate high amounts of these oxyanions. Detoxification of the water might be achieved if precipitated arsenated or chromated schwertmannite is fixed in the sediment. However, under reduced conditions, reductive dissolution of iron oxides mediated by the activity of Fe(III)-reducing bacteria might mobilize arsenate and chromate again. In this study, the reduction of synthesized arsenated or chromated schwertmannite by the acidophilic Fe(III)-reducer Acidiphilium cryptum JF-5, isolated from an acidic mining-impacted sediment, was investigated. In TSB medium at pH 2.7 with glucose as electron donor, A. cryptum JF-5 reduced about 10% of the total Fe(III) present in pure synthetic schwertmannite but only 5% of Fe(III) present in arsenated schwertmannite. In contrast to sulfate that was released during the reductive dissolution of pure schwertmannite, arsenate was not released during the reduction of arsenated schwertmannite probably due to the high surface complexation constant of arsenate and Fe(III). In medium containing chromated schwertmannite, no Fe(II) was formed, and no glucose was consumed indicating that chromate might have been toxic to cells of A. cryptum JF-5. Both As(V) or Cr(VI) could not be utilized as electron acceptor by A. cryptum JF-5. A comparison between autoclaved (121 °C for 20 min) and non-autoclaved schwertmannite samples demonstrated that nearly 100%of the bound sulfate was released during heating, and FTIR spectra indicated a transformation of schwertmannite to goethite. This structural change was not observed with autoclaved arsenated or chromated schwertmannite. These results suggest that the mobility of arsenate and chromate is not enhanced by the activity of acidophilic Fe(III)-reducing bacteria in mining-impacted sediments. In contrast, the presence of bound arsenate and chromate seemed to stabilize schwertmannite against reductive dissolution and its further transformation to goethite that is an ongoing process in those sediments.     

Topographically generated fronts,very nearshore oceanography,and the distribution of chlorophyll,detritus, and selected diatom and dinoflagellate taxa

At four sites (Sunset Bay, Miller's Cove, and Shore Acres 43° 20.13 N; 124° 22.40 W, Nellies Cove 42° 44.75 N; 124° 29.75 W) along the Oregon coast, USA, relationships between fronts associated with shore-parallel foam lines and the distributions of chlorophyll, selected phytoplankters, and detritus were investigated. Sampling dates at the study sites were as follows: Sunset Bay, 1 August 1997, 25 June 1999 and 20 July 1999; Miller's Cove, 24 August 2000; Shore Acres, 19 July 1999 and 16 August 2000; Nellies Cove 17 August 2000 and 31 August 2000. Conductivity, temperature and depth data were used to describe the water masses on either side of the fronts, and vertical plankton tows with a 53-m mesh net were used to describe the distribution of selected phytoplankters and detritus. At the cove sites during upwelling, fronts marked the presence of warm water within the bay and cooler water offshore. Chlorophyll a (Chl a) and phytoplankton concentrations were generally lower within the coves than seaward while detritus concentrations were higher. From 3 July 2000 to 15 September 2000, a period when upwelling winds from the north prevail, a time series of samples was collected at Sunset Bay. The front was only present during periods of upwelling favorable winds. During these periods there were significantly higher concentrations of Chl a, Pseudo-nitzschia spp., and Protoperidinium spp. seaward of the front than landward. During downwelling winds the front was absent and there were no significant differences in the concentrations inside and outside the mouth of the bay. At Shore Acres, an exposed, relatively straight stretch of shoreline, the shore-parallel front appears to be formed by boundary mixing. Chl a and phytoplankton from the coastal ocean spread well shoreward of the boundary-mixing front. When present, the front at the mouth of the coves and bay indicated the presence of water masses with distinct physical and biological characteristics, but not at Shore Acres. Alongshore differences in the very nearshore oceanography, by altering the availability of continental shelf phytoplankton production, may affect both the growth rates of intertidal benthic suspension feeders and community structure.Electronic Supplementary Material Supplementary material is available in the online version of this article at .Communicated by J.P. Grassle, New Brunswick     

Measuring environmental performance: Theory and practice at ontario hydro

When an organization embarks on the path of environmental leadership, how does it track and quantify its efforts? This article describes a system for identifying, tracking, and communicating environmental efforts.

1 Anita Wolfe wishes to recognize Richard P. Wells'S article, “Point of View: Environmental Management in Mexico,” TQEM, Vol. 2, No. 3, as an invaluable source in helping to develop this system.

In addition, it examines the experience of Ontario Hydro, Canada'S largest public utility, within a similar framework.     

Reactive nitrogen and human health: acute and long-term implications

Reactive-nitrogen (Nr) has a wide variety of beneficial and detrimental effects on human health. The most important of the beneficial effects are increasing global and regional food supplies and increased nutritional quality of available foods. However, lack of adequate dietary intake of amino acids and proteins is a serious cause of malnutrition when food supplies are inadequate because of poverty, drought, floods, wars, and displacements of people as refugees. There is sufficient, though limited, quantitative data indicating that increased circulation of Nr in the environment is responsible for significant human health effects via other exposure pathways. Nr can lead to harmful health effects from airborne occupational exposures and population-wide indoor and outdoor air pollution exposures to nitrogen dioxide and ozone. Nr can also affect health via water pollution problems, including methemoglobinemia from contaminated ground water, eutrophication causing fish kills and algal blooms that can be toxic to humans, and via global warming. The environmental pollutants stemming from reactive nitrogen are ubiquitous, making it difficult to identify the extent to which Nr exerts a specific health effect. As all populations are susceptible, continued interdisciplinary investigations are needed to determine the extent and nature of the beneficial and harmful effects on human health of nitrogen-related pollutants and their derivatives.     

Europe-wide survey of estrogenicity in wastewater treatment plant effluents: the need for the effect-based monitoring

A pan-European monitoring campaign of the wastewater treatment plant (WWTP) effluents was conducted to obtain a concise picture on a broad range of pollutants including estrogenic compounds. Snapshot samples from 75 WWTP effluents were collected and analysed for concentrations of 150 polar organic and 20 inorganic compounds as well as estrogenicity using the MVLN reporter gene assay. The effect-based assessment determined estrogenicity in 27 of 75 samples tested with the concentrations ranging from 0.53 to 17.9 ng/L of 17-beta-estradiol equivalents (EEQ). Approximately one third of municipal WWTP effluents contained EEQ greater than 0.5 ng/L EEQ, which confirmed the importance of cities as the major contamination source. Beside municipal WWTPs, some treated industrial wastewaters also exhibited detectable EEQ, indicating the importance to investigate phytoestrogens released from plant processing factories. No steroid estrogens were detected in any of the samples by instrumental methods above their limits of quantification of 10 ng/L, and none of the other analysed classes of chemicals showed correlation with detected EEQs. The study demonstrates the need of effect-based monitoring to assess certain classes of contaminants such as estrogens, which are known to occur at low concentrations being of serious toxicological concern for aquatic biota.     

Cumulative adverse effects of offshore wind energy development on wildlife

Offshore wind energy development (OWED) is being pursued as a critical component in achieving a low-carbon energy economy. While the potential generating capacity is high, the cumulative effects of expansion of OWED on wildlife remain unclear. Since environmental regulations in many countries require analysis of the cumulative adverse effects (CAE) during permitting processes, this paper reviews the state of knowledge on CAE of OWED on wildlife. We synthesize ecological research on the effects of OWED on wildlife; delineate a framework for determining the scope of CAE assessments; describe approaches to avoiding, minimizing and compensating for CAE; and discuss critical uncertainties.     

Policy Frameworks Influencing Outdoor Water‐use Restrictions

Water‐use efficiency in the United States (U.S.) has improved in recent years. Yet continued population growth coupled with increasingly conservation‐oriented regulatory frameworks suggest that residential water suppliers will have to realize additional efficiency gains in coming decades. Outdoor water‐use restrictions (OWRs) appear to be an increasingly prevalent demand‐side management policy tool. To date little research has investigated the policy mechanisms that govern OWR adoption and influence the prevalence of OWRs. This article fills this gap with an assessment of state‐level policies influencing local‐level restrictions on residential outdoor water use in each of the 48 contiguous U.S. states, and with a detailed illustration of the cross‐scalar dynamic of one state's policy framework in practice. An examination of the implementation of OWRs in 24 neighboring towns in Massachusetts across the 2003‐2012 period indicates the interplay between state‐level and local‐level policies leads to OWRs implementation over extended time‐periods, even when drought conditions are not present. This finding suggests OWRs are being used as a tool for general‐purpose water conservation rather than as a stopgap measure justified by temporary water shortage conditions. Future research should investigate how local‐level water savings vary with differing state‐level approaches.     

Demonstrating the In Situ Biodegradation Potential of Phenol Using Bio‐Sep® Bio‐Traps® and Stable Isotope Probing

The effect of phenol concentration on phenol biodegradation at an industrial site in the south of Wales, United Kingdom, was investigated using standard Bio‐Sep^® Bio‐Traps^® and Bio‐Traps^® coupled with stable isotope probing (SIP). Unlike many ¹³C‐amendments used in SIP studies (such as hydrocarbons) that physically and reversibly adsorb to the activated carbon component of the Bio‐Sep^® beads, phenol is known to irreversibly chemisorb to activated carbon. Bio‐Traps^® were deployed for 32 days in nine site groundwater monitoring wells representing a wide range of phenol concentrations. Bio‐Traps^® amended with ¹³C‐phenol were deployed together with non‐amended Bio‐Traps® in three wells. Quantitative polymerase chain reaction (qPCR) analysis of Bio‐Traps^® post‐deployment indicated an inhibitory effect of increasing phenol concentration on both total eubacteria and aerobic phenol‐utilizing bacteria as represented by the concentration of phenol hydroxylase gene. Despite the chemisorption of phenol to the Bio‐Sep^® beads, activated carbon stable isotope analysis showed incorporation of ¹³C into biomass and dissolved inorganic carbon (DIC) in each SIP Bio‐Trap^® indicating that chemisorbed amendments are bioavailable. However, there was a clear effect of phenol concentration on ¹³C incorporation in both biomass and DIC confirming phenol inhibition. These results suggest that physical reductions of the phenol concentrations in some areas of the plume will be required before biodegradation of phenol can proceed at a reasonable rate. © 2013 Wiley Periodicals, Inc.