Dechlorination and organohalide-respiring bacteria dynamics in sediment samples of the Yangtze Three Gorges Reservoir

Several groups of bacteria such as Dehalococcoides spp., Dehalobacter spp., Desulfomonile spp., Desulfuromonas spp., or Desulfitobacterium spp. are able to dehalogenate chlorinated pollutants such as chloroethenes, chlorobenzenes, or polychlorinated biphenyls under anaerobic conditions. In order to assess the dechlorination potential in Yangtze sediment samples, the presence and activity of the reductively dechlorinating bacteria were studied in anaerobic batch tests. Eighteen sediment samples were taken in the Three Gorges Reservoir catchment area of the Yangtze River, including the tributaries Jialing River, Daning River, and Xiangxi River. Polymerase chain reaction analysis indicated the presence of dechlorinating bacteria in most samples, with varying dechlorinating microbial community compositions at different sampling locations. Subsequently, anaerobic reductive dechlorination of tetrachloroethene (PCE) was tested after the addition of electron donors. Most cultures dechlorinated PCE completely to ethene via cis-dichloroethene (cis-DCE) or trans-dichloroethene. Dehalogenating activity corresponded to increasing numbers of Dehalobacter spp., Desulfomonile spp., Desulfitobacterium spp., or Dehalococcoides spp. If no bacteria of the genus Dehalococcoides spp. were present in the sediment, reductive dechlorination stopped at cis-DCE. Our results demonstrate the presence of viable dechlorinating bacteria in Yangtze samples, indicating their relevance for pollutant turnover.     

Chemical- and effect-oriented exposomics: Three Gorges Reservoir (TGR)

Exposomic studies of the rapidly changing environment of the Three Gorges Reservoir (TGR) after its impounding is elaborated as a novel field of human and environmental research. Molecular exposomics is focused on the measure of all exposures to molecules and especially persistent organic pollutants-like compounds are of emerging interest due to their lifetime existence in the environment and humans. Theoretical considerations in general and particular for the TGR are deduced and presented using quantitative approaches for this research field. Since exposomics is strongly time-dependent, a theory is presented to link extension of exposure, time, and related effects. Similarity to the first law of thermodynamics is outlined. On top of this, the integrated use of biomarkers is presented employing chemical analysis for biomarkers of exposure and effects, biomarkers in vivo, in vitro approaches and the link between chemical mixtures, and the onset of disease and lethality. Besides real organisms, also virtual organisms are favored to act as well-defined sub-compartments such as fat of biota and with respect to time of exposure. Exposomics is the perspective of risk evaluation and chronic exposures in the running century. It needs novel theories, approaches, and integrated action between medical and environmental disciplines. The existing knowledge about molecular stressors has to be assembled and put into a context especially with respect not only to time resp. lifetime exposure of humans but also eco-toxicological findings by using highly conserved phylogenetic mechanisms to enable links between human and risks of environmental biota. The TGR is a good example not only to employ biomonitoring of real but also virtual organisms due to the lack of established ecotopes in this changing environment so far. Progress in understanding long-term risks requires a proper theory as well as novel tools such as virtual organisms. On top, multidisciplinary approaches and the utilization of existing knowledge about the exposure of the environment and humans have to be merged and directed into mutual concepts. Effect-oriented and chemical analysis must be designed time-oriented to determine lifetime exposures of mankind and nature. Perspectively, a first attempt about exposomic theory and concepts is proposed and has to be developed experimentally further enclosing virtual besides of real organisms and compartments. Environmental and human exposomics have to be considered as a unified global issue in order to effectively utilize their mutual existing knowledge most effectively. The TGR is a challenging model system aiming this objective.     

Capacity of biochar application to maintain energy crop productivity: soil chemistry, sorghum growth, and runoff water quality effects

Pyrolysis of crop biomass generates a by-product, biochar, which can be recycled to sustain nutrient and organic C concentrations in biomass production fields. We evaluated effects of biochar rate and application method on soil properties, nutrient balance, biomass production, and water quality. Three replications of eight sorghum [ (L.) Moench] treatments were installed in box lysimeters under greenhouse conditions. Treatments comprised increasing rates (0, 1.5, and 3.0 Mg ha) of topdressed or incorporated biochar supplemented with N fertilizer or N, P, and K fertilizer. Simulated rain was applied at 21 and 34 d after planting, and mass runoff loss of N, P, and K was measured. A mass balance of total N, P, and K was performed after 45 d. Returning 3.0 Mg ha of biochar did not affect sorghum biomass, soil total, or Mehlich-3-extractable nutrients compared to control soil. Yet, biochar contributed to increased concentration of dissolved reactive phosphorus (DRP) and mass loss of total phosphorus (TP) in simulated runoff, especially if topdressed. It was estimated that up to 20% of TP in topdressed biochar was lost in surface runoff after two rain events. Poor recovery of nutrients during pyrolysis and excessive runoff loss of nutrients for topdressed biochar, especially K, resulted in negative nutrient balances. Efforts to conserve nutrients during pyrolysis and incorporation of biochar at rates derived from annual biomass yields will be necessary for biochar use in sustainable energy crop production.     

Enzymatic synthesis of bromo- and chlorocarbazoles and elucidation of their structures by molecular modeling

3-Chlorocarbazole, 3,6-dichlorocarbazole, dibromocarbazole, and 1,3,6,8-tetrabromocarbazole are emerging environmental contaminants which have been detected recently in water, sediment, and soil samples. However, their sources and occurrence have not been explained. Here, we report an enzymatic synthesis of bromo- and chlorocarbazoles by chloroperoxidase from Caldariomyces fumago in water. Density functional theory (DFT) method was used to predict the most stable products. Carbazole and chloroperoxidase were assayed in vitro in the presence of hydrogen peroxide, bromide, and chloride ions in different substrate ratio treatments against constant and varying enzyme concentrations. Halogenated carbazoles formed were identified by high-resolution gas chromatography coupled to mass spectrometry. In all treatments, bromination and chlorination took place, but the composition and concentration of compounds formed varied from one treatment to another. Mono-, di-, tri-, and tetra-substituted bromo- and chlorocarbazoles which include the reported environmental contaminants were synthesized. 3-Substituted and 3,6-substituted congeners were relatively higher in concentration. Enzyme concentration did not favor preferential formation of any of the compounds synthesized. However, their synthesis was influenced by halide concentration. Congeners with bromine and chlorine at position of C-3, C-3,6, C-1,3,6, and C-1,3,6,8 were calculated as the stable intermediate sigma complexes by DFT method. Regioselectivity in halogenation is discussed and hypothesis of the likely stable products in the environment explained. This study provides evidence that bromo- and chlorocarbazoles reported previously can be formed enzymatically in the environment, demonstrating the need to consider aromatic pollutants transformation and their potential toxicity enhancements in the management of water pollution and contaminated sites.     

Empirical models based on the universal soil loss equation fail to predict sediment discharges from Chesapeake Bay catchments

The Universal Soil Loss Equation (USLE) and its derivatives are widely used for identifying watersheds with a high potential for degrading stream water quality. We compared sediment yields estimated from regional application of the USLE, the automated revised RUSLE2, and five sediment delivery ratio algorithms to measured annual average sediment delivery in 78 catchments of the Chesapeake Bay watershed. We did the same comparisons for another 23 catchments monitored by the USGS. Predictions exceeded observed sediment yields by more than 100% and were highly correlated with USLE erosion predictions (Pearson r range, 0.73-0.92; p < 0.001). RUSLE2-erosion estimates were highly correlated with USLE estimates (r = 0.87; p < 001), so the method of implementing the USLE model did not change the results. In ranked comparisons between observed and predicted sediment yields, the models failed to identify catchments with higher yields (r range, -0.28-0.00; p > 0.14). In a multiple regression analysis, soil erodibility, log (stream flow), basin shape (topographic relief ratio), the square-root transformed proportion of forest, and occurrence in the Appalachian Plateau province explained 55% of the observed variance in measured suspended sediment loads, but the model performed poorly (r(2) = 0.06) at predicting loads in the 23 USGS watersheds not used in fitting the model. The use of USLE or multiple regression models to predict sediment yields is not advisable despite their present widespread application. Integrated watershed models based on the USLE may also be unsuitable for making management decisions.     

Watershed vulnerability predictions for the Ozarks using landscape models

Forty-six broad-scale landscape metrics derived from commonly used landscape metrics were used to develop potential indicators of total phosphorus (TP) concentration, total ammonia (TA) concentration, and Escherichia coli bacteria count among 244 sub-watersheds of the Upper White River (Ozark Mountains, USA). Indicator models were developed by correlating field-based water quality measurements and contemporaneous remote-sensing-based ecological metrics using partial least squares (PLS) analyses. The TP PLS model resulted in one significant factor explaining 91% of the variability in surface water TP concentrations. Among the 18 contributing landscape model variables for the TP PLS model, the proportions of a sub-watershed that are barren and in human use were key indicators of water chemistry in the associated sub-watersheds. The increased presence and reduced fragmentation of forested areas are negatively correlated with TP concentrations in associated sub-watersheds, particularly within close proximity to rivers and streams. The TA PLS model resulted in one significant factor explaining 93% of the variability in surface water TA concentrations. The eight contributing landscape model variables for the TA PLS model were among the same forest and urban metrics for the TP model, with a similar spatial gradient trend in relationship to distance from streams and rivers within a sub-watershed. The E. coli PLS model resulted in two significant factors explaining 99.7% of the variability in E. coli cell count. The 17 contributing landscape model variables for the E. coli PLS model were similar to the TP and TA models. The integration of model results demonstrates that forest, riparian, and urban attributes of sub-watersheds affect all three models. The results provide watershed managers in the Ozark Mountains with a broad-scale vulnerability prediction tool, focusing on TP, TA, and E. coli, and are being used to prioritize and evaluate monitoring and restoration efforts in the vicinity of the White River, a major tributary to the Mississippi River and Gulf of Mexico.     

Monitoring Contrasting Land Management in the Savanna Landscapes of Northern Australia

We compared measures of ecosystem state across six adjacent land-tenure groups in the intact tropical savanna landscapes of northern Australia. Tenure groups include two managed by Aboriginal owners, two national parks, a cluster of pastoral leases, and a military training area. This information is of relevance to the debate about the role of indigenous lands in the Australian conservation estate. The timing and frequency of fire was determined by satellite imagery; the biomass and composition of the herb-layer and the abundance of large feral herbivores by field surveys; and weediness by analysis of a Herbarium database. European tenures varied greatly in fire frequencies but were consistently burnt earlier in the dry season than the two Aboriginal tenures, the latter having intermediate fire frequencies. Weeds were more frequent in the European tenures, whilst feral animals were most abundant in the Aboriginal tenures. This variation strongly implies a signature of current management and/or recent environmental history. We identify indices suitable for monitoring of management outcomes in an extensive and sparsely populated landscape. Aboriginal land offers a unique opportunity for the conservation of biodiversity through the maintenance of traditional fire regimes. However, without financial support, traditional practices may prove unsustainable both economically and because exotic weeds and feral animals will alter fire regimes. An additional return on investment in Aboriginal land management is likely to be improved livelihoods and health outcomes for these disadvantaged communities.     

Integrated Modular Modeling of Water and Nutrients From Point and Nonpoint Sources in the Patuxent River Watershed1

Abstract: We present a simple modular landscape simulation model that is based on a watershed modeling framework in which different sets of processes occurring in a watershed can be simulated separately with different models. The model consists of three loosely coupled submodels: a rainfall‐runoff model (TOPMODEL) for runoff generation in a subwatershed, a nutrient model for estimation of nutrients from nonpoint sources in a subwatershed, and a stream network model for integration of point and nonpoint sources in the routing process. The model performance was evaluated using monitoring data in the watershed of the Patuxent River, a tributary to the Chesapeake Bay in Maryland, from July 1997 through August 1999. Despite its simplicity, the landscape model predictions of streamflow, and sediment and nutrient loads were as good as or better than those of the Hydrological Simulation Program‐Fortran model, one of the most widely used comprehensive watershed models. The landscape model was applied to predict discharges of water, sediment, silicate, organic carbon, nitrate, ammonium, organic nitrogen, total nitrogen, organic phosphorus, phosphate, and total phosphorus from the Patuxent watershed to its estuary. The predicted annual water discharge to the estuary was very close to the measured annual total in terms of percent errors for both years of the study period (≤2%). The model predictions for loads of nutrients were also good (20‐30%) or very good (<20%) with exceptions of sediment (40%), phosphate (36%), and organic carbon (53%) for Year 1.     

The influence of work‐family culture and workplace relationships on work interference with family: a multilevel model

This research tested a multilevel model examining the influence of work‐family culture and supportive workplace relationships on work interference with family. Web‐based survey data were provided by 792 information technology employees from 10 organizations. Random coefficient modeling was used to test a path model examining the relationships between work‐family culture, leader‐member exchange (LMX), coworker support, and work interference with family. The direct effects of LMX and coworker support on work interference with family were significant. The indirect effect of work‐family culture on work interference with family was also significant. Results demonstrate the value of work‐family culture in understanding supportive supervisory and coworker relationships and work interference with family and highlight the need to employ multilevel models to understand these relationships. Copyright © 2007 John Wiley & Sons, Ltd.