Stable chlorine intramolecular kinetic isotope effects from the abiotic dehydrochlorination of DDT

INTENTION, GOAL, SCOPE, BACKGROUND: Identifying different sources and following reaction pathways of chlorinated organic contaminants in the environment can be challenging, especially when only their concentrations are available. Compound-specific stable chlorine measurements of some contaminants have recently been shown to provide additional information and an increased understanding of their biogeochemistry. These studies, however, have been generally limited to volatile molecules. OBJECTIVE: Here, the stable chlorine isotope ratios of the semi-volatile pesticide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) were investigated. Specifically, the intramolecular stable chlorine isotopic compositions of DDT and the kinetic isotope effect (KIE) for the abiotic dehydrochlorination of DDT to 2,2-bis(p-chlorophenyl)-1,1-dichloroethene (DDE) were determined. METHODS: Selective chemical oxidation of DDT to dichlorobenzophenone (DCBP) and analysis of each compound was used to calculate the stable chlorine isotope ratios of the alkyl and aromatic chlorines in DDT. To determine the KIE for dehydrochlorination, DDT was reacted in a basic solution to yield DDE at 52 degrees C, 60 degrees C, and 72 degrees C for 3, 5, and 5 days, respectively. RESULTS AND DISCUSSION: Significant intramolecular stable chlorine isotopic differences were observed in one sample of DDT where the alkyl and aromatic delta 37Cl values were -5.76 +/- 0.45 and -2.21 +/- 0.24%@1000, respectively. Dehydrochlorination of DDT to DDE in basic solutions at 52, 60, and 70 degrees C resulted in a substantial intramolecular KIE where the alkyl chlorines of DDE shifted by approximately 3%@1000 relative to the alkyl chlorines in DDT. However, no temperature dependence was observed. The KIE, calculated by an iterative program, was 1.009. CONCLUSIONS: Intramolecular differences in the stable chlorine isotope ratios were observed in DDT and this is the first such finding. Dehydrochlorination of DDT yields a measurable and distinct intramolecular stable chlorine KIE. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate the existence of significant intramolecular differences in chlorinated organic compounds. Many other chlorinated semi-volatile and volatile organic contaminants are synthesized from multiple sources of chlorine, and we recommend that similar studies be performed on many such molecules in order to attain a clear understanding of their intramolecular chlorine isotopic differences. The existence of a measurable KIE for the dehydrochlorination of DDT to DDE shows the potential strength of using isotopic measurements to investigate the biogeochemistry of these important compounds. For example, the isotopically depleted aqueous chloride produced by dehydrochlorination of DDT to DDE may be a useful tracer of these reactions in freshwater environments.     

Economics of dairy waste use as fertilizer in central Texas

Dairy manure is an unavoidable natural, but negative, byproduct of milk production. Its nitrogen, phosphate, and potash contents represent a potential substitute for commercial fertilizers on field crops. In the absence of subsidies, manure transportation and land application costs limit its utilization as a substitute for chemical fertilizer. The results from a study of the economics of manure use in Central Texas suggest that, at the current costs for loading, hauling, and spreading, dairy manure cannot be economically transported from surplus to deficit areas within the study area. The estimated breakeven transport distance for manure application to four crops varied from 28 to 41 km; however, the distances between manure-surplus and manure-deficit counties in the study region varied from 40 to 90 km. An analysis of potential subsidies paid by the government or dairy farmers showed that the breakeven distance could increase by up to 30 km. A decrease in the assumed moisture content of the manure from 50% to 40% is shown to increase the breakeven distance by 10 km. The study suggests that dairy manure loading, transportation, and land application, with appropriate subsidies or reductions in moisture content, has the potential to be profitably substituted for chemical fertilizers.     

Grassland songbirds in a dynamic management landscape: behavioral responses and management strategies.

In recent decades, earlier and more frequent harvests of agricultural grasslands have been implicated as a major cause of population declines in grassland songbirds. From 2002 to 2005, in the Champlain Valley of Vermont and New York, USA, we studied the reproductive success of Savannah Sparrows (Passerculus sandwichensis) and Bobolinks (Dolichonyx oryzivorus) on four grassland treatments: (1) early-hayed fields cut before 11 June and again in early- to mid-July; (2) middle-hayed fields cut once between 21 June and 10 July; (3) late-hayed fields cut after 1 August; and (4) rotationally grazed pastures. Both the number of fledglings per female per year and nest success (logistic-exposure method) varied among treatments and between species. Although birds initiated nests earlier on early-hayed fields compared to others, haying caused 99% of active Savannah Sparrow and 100% of active Bobolink nests to fail. Both the initial cutting date and time between cuttings influenced renesting behavior. After haying, Savannah Sparrows generally remained on early-hayed fields and immediately renested (clutch completion 15.6 +/- 1.28 days post-haying; all values are reported as mean +/- SE), while Bobolinks abandoned the fields for at least two weeks (mean clutch completion 33 +/- 0.82 days post-haying). While female Savannah Sparrows fledged more offspring per year (1.28 +/- 0.16) than female Bobolinks (0.05 +/- 0.05), reproductive success on early-hayed fields was low. The number of fledglings per female per year was greater on middle-hayed fields (Savannah Sparrows, 3.47 +/- 0.42; Bobolinks, 2.22 +/- 0.26), and late-hayed fields (Savannah Sparrows, 3.29 +/- 0.30; Bobolinks, 2.79 +/- 0.18). Reproductive success was moderate on rotationally grazed pastures, where female Savannah Sparrows and female Bobolinks produced 2.32 +/- 0.25 and 1.79 +/- 0.33 fledgling per year, respectively. We simultaneously conducted cutting surveys throughout the Champlain Valley and found that 3-8% of hayfield habitat was cut by 1-4 June, 25-40% by 12-16 June, and 32-60% by 28 June-2 July. Thus, the majority of grassland habitat was cut during the breeding season; however, late-hayed fields served as high-quality reserves for late-nesting female Bobolinks that were displaced from previously hayed fields. For fields first cut in May, a 65-day interval between cuts could provide enough time for both species to successfully fledge young.     

Capillary supply and mitochondrial volume density in the axial muscles of the mesopelagic teleost Argyropelecus hemigymnus

Quantitative measurements have been made on the ultra-structure and capillary supply to the axial muscles of the mesopelagic hatchet fish Argyropelecus hemigymnus (Cocco, 1829). Fish were collected at Eastern North Atlantic Ocean Station 10244, 32°48N; 31°15W during November 1980, from a depth of 480 to 550 m. Mitochondria with densely packed cristae occupy 44.3% of slow-fibre volume. Each myofibril is in direct contact with a mitochondrion. Compared with other fishes studied, the capillary supply to A. hemigymnus slow fibres is poorly developed. The average number of capillaries per fibre is 0.9, such that each m of capillary contact supplies 0.011 m² of fibre cross-sectional area. The capillary surface area (m²) supplying 1 m³ of slow-fibre mitochondria is 0.17 in anchovy (Engraulis encrasicolus), 0.14 in rat-fish (Chimaera monstrosa), 0.14 in tench (Tinca tinca), 0.16 in catfish (Clarias mossambica), and only 0.025 for A. hemigymnus. It is suggested that, relative to the former species, some modifications in factors determining tissue oxygenation (e.g. myoglobin concentrations, blood flow, perfusion distribution or haemoglobin) and/or mitochondrial respiration rate are required in order to match oxygen supply and demand to the slow muscle in A. hemigymnus.     

Possibilities for reducing nitrate leaching from agricultural land

Agricultural soil is a contributor of nitrate to natural waters. High nitrate levels in water leached from soils are related to high nitrate concentrations in drinking water, and excess levels change the ecological balance of rivers and lakes. In this paper, sound solutions to the major environmental issue of limiting nitrate leaching by modifying agricultural practices are discussed. The causes of nitrate leaching from agricultural land are briefly explained and existing measures for the reduction of nitrate losses are described, analyzed and evaluated. Reduction of nutrient leaching is not a question of organic or conventional farming, but rather of the introduction and use of appropriate countermeasures. We propose the following guiding principles to minimize leaching from agricultural soils. To some extent these principles require a new way of thinking: i) environmental indexing of fields and consideration of spatial variability within fields in relation to their contribution to leaching losses within a catchment; ii) reduction of nitrogen inputs to soil to levels slightly below those expected to give the optimum yield by applying less nitrogen fertilizer and by a further reduction in animal density; and iii) use of a range of counter-measures (catch crops, minimum tillage, control of biological processes, etc.) depending on how sensitive the farming system, soil and climate are to the risk of nitrate leaching.     

Anaerobic biodegradation of alkylbenzenes and trichloroethylene in aquifer sediment down gradient of a sanitary landfill

The objective of this investigation was to evaluate the anaerobic biodegradability of benzene, toluene, ethylbenzene, ortho-, meta- and para-xylene (BTEX) and trichloroethylene (TCE) in aquifer sediment down gradient of an unlined landfill. The major organic contaminants identified in the shallow unconfined aquifer are cis-dichloroethylene (c-DCE) and toluene. The biodegradative potential of the contaminated aquifer was measured in three sets of microcosms constructed using anaerobic aquifer sediment from three boreholes down gradient of the landfill. The degradability of BTEX and TCE was examined under ambient and amended conditions. TCE was degraded in microcosms with aquifer material from all three boreholes. Toluene biodegradation was inconsistent, exhibiting biodegradation with no lag in one set of microcosms but more limited biodegradation in two additional sets of microcosms. TCE exhibited an inhibitory effect on toluene degradation at one location. The addition of calcium carbonate stimulated TCE biodegradation which was not further stimulated by nutrient addition. TCE was converted to ethylene, a harmless byproduct, in all tests. Benzene, ethylbenzene and xylene isomers were recalcitrant in both ambient and amendment experiments. Biodegradation occurred under methanogenic conditions as methane was produced in all experiments. Bromoethane sulfonic acid (BES), a methanogenic inhibitor, inhibited methane and ethylene production and TCE biodegradation. The results indicate the potential for intrinsic bioremediation of TCE and toluene down gradient of the Wilder's Grove, North Carolina, landfill. The low concentrations of TCE in monitoring wells was consistent with its biodegradation in laboratory microcosms.     

Environmentally stratified sampling design for the development of Great Lakes environmental indicators

Understanding the relationship between human disturbance and ecological response is essential to the process of indicator development. For large-scale observational studies, sites should be selected across gradients of anthropogenic stress, but such gradients are often unknown for a population of sites prior to site selection. Stress data available from public sources can be used in a geographic information system (GIS) to partially characterize environmental conditions for large geographic areas without visiting the sites. We divided the U.S. Great Lakes coastal region into 762 units consisting of a shoreline reach and drainage-shed and then summarized over 200 environmental variables in seven categories for the units using a GIS. Redundancy within the categories of environmental variables was reduced using principal components analysis. Environmental strata were generated from cluster analysis using principal component scores as input. To protect against site selection bias, sites were selected in random order from clusters. The site selection process allowed us to exclude sites that were inaccessible and was shown to successfully distribute sites across the range of environmental variation in our GIS data. This design has broad applicability when the goal is to develop ecological indicators using observational data from large-scale surveys.     

Heavy metals and selenium in feathers of three shorebird species from Delaware bay

Concentrations of lead, cadmium, mercury, selenium, chromium and manganese were examined in breast feathers of shorebirds migrating north through Cape May, New Jersey in 1991 and 1992. Although we predicted that metal levels would be positively correlated with weight, this was only true for mercury in red knots (Calidris canutus). Selenium was negatively correlated with weight in red knots. No other significant correlation of metal concentrations with weight were found. Lead and mercury were highest in sanderlings (C. alba). Selenium and manganese were highest in red knots, while chromium and cadmium levels were highest in semipalmated sandpipers (C. pusilus). For 1991, interspecific metals differences were significant for all metals except lead. For semipalmated sandpipers, cadmium and chromium concentrations were significantly higher in 1991 while managese concentrations were significantly higher in 1992.     

Contribution of individual components of a job cycle on overall severity of whole-body vibration exposure: a study in Indian mines

Drivers of earth-moving machines are exposed to whole-body vibration (WBV). In mining operations there can be a combination of relatively high magnitudes of vibration and long exposure times. Effective risk mitigation requires understanding of the main aspects of a task that pose a hazard to health. There are very few published studies of WBV exposure from India. This paper reports on a study that considered the contribution of the component phases of dumper operations, on the overall vibration exposure of the drivers. It shows that vibration magnitudes are relatively high, and that haulage tasks are the main contributor to the exposure. It is recommended that driver speed, haul road surfaces and vehicle maintenance/selection are optimized to ensure minimization of vibration. If this is not sufficient, operation times might need to be reduced in order to ensure that the health guidance caution zone from Standard No. ISO 2631-1:1997 is not exceeded.