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.     

An integrated approach to model the biomagnification of organic pollutants in aquatic food webs of the Yangtze Three Gorges Reservoir ecosystem using adapted pollution scenarios

The impounding of the Three Gorges Reservoir (TGR) at the Yangtze River caused large flooding of urban, industrial, and agricultural areas, and profound land use changes took place. Consequently, substantial amounts of organic and inorganic pollutants were released into the reservoir. Additionally, contaminants and nutrients are entering the reservoir by drift, drainage, and runoff from adjacent agricultural areas as well as from sewage of industry, aquacultures, and households. The main aim of the presented research project is a deeper understanding of the processes that determines the bioaccumulation and biomagnification of organic pollutants, i.e., mainly pesticides, in aquatic food webs under the newly developing conditions of the TGR. The project is part of the Yangtze-Hydro environmental program, financed by the German Ministry of Education and Science. In order to test combinations of environmental factors like nutrients and pollution, we use an integrated modeling approach to study the potential accumulation and biomagnification. We describe the integrative modeling approach and the consecutive adaption of the AQUATOX model, used as modeling framework for ecological risk assessment. As a starting point, pre-calibrated simulations were adapted to Yangtze-specific conditions (regionalization). Two exemplary food webs were developed by a thorough review of the pertinent literature. The first typical for the flowing conditions of the original Yangtze River and the Daning River near the city of Wushan, and the second for the stagnant reservoir characteristics of the aforementioned region that is marked by an intermediate between lake and large river communities of aquatic organisms. In close cooperation with German and Chinese partners of the Yangtze-Hydro Research Association, other site-specific parameters were estimated. The MINIBAT project contributed to the calibration of physicochemical and bathymetric parameters, and the TRANSMIC project delivered hydrodynamic models for water volume and flow velocity conditions. The research questions were firstly focused on the definition of scenarios that could depict representative situations regarding food webs, pollution, and flow conditions in the TGR. The food webs and the abiotic site conditions in the main study area near the city of Wushan that determine the environmental preconditions for the organisms were defined. In our conceptual approach, we used the pesticide propanil as a model substance.     

Stable isotope signatures for characterising the biological stability of landfilled municipal solid waste

Stable isotopic signatures of landfill leachates are influenced by processes within municipal solid waste (MSW) landfills mainly depending on the aerobic/anaerobic phase of the landfill. We investigated the isotopic signatures of δ¹³C, δ²H and δ¹⁸O of different leachates from lab-scale experiments, lysimeter experiments and a landfill under in situ aeration. In the laboratory, columns filled with MSW of different age and reactivity were percolated under aerobic and anaerobic conditions. In landfill simulation reactors, waste of a 25 year old landfill was kept under aerobic and anaerobic conditions. The lysimeter facility was filled with mechanically shredded fresh waste. After starting of the methane production the waste in the lysimeter containments was aerated in situ. Leachate and gas composition were monitored continuously. In addition the seepage water of an old landfill was collected and analysed periodically before and during an in situ aeration.We found significant differences in the δ¹³C-value of the dissolved inorganic carbon (δ¹³C-DIC) of the leachate between aerobic and anaerobic waste material. During aerobic degradation, the signature of δ¹³C-DIC was mainly dependent on the isotopic composition of the organic matter in the waste, resulting in a δ¹³C-DIC of ?20‰ to ?25‰. The production of methane under anaerobic conditions caused an increase in δ¹³C-DIC up to values of +10‰ and higher depending on the actual reactivity of the MSW. During aeration of a landfill the aerobic degradation of the remaining organic matter caused a decrease to a δ¹³C-DIC of about ?20‰. Therefore carbon isotope analysis in leachates and groundwater can be used for tracing the oxidation–reduction status of MSW landfills.Our results indicate that monitoring of stable isotopic signatures of landfill leachates over a longer time period (e.g. during in situ aeration) is a powerful and cost-effective tool for characterising the biodegradability and stability of the organic matter in landfilled municipal solid waste and can be used for monitoring the progress of in situ aeration.     

Concentrations of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in soil in the vicinity of a landfill

Estonia still has no waste incineration facilities, which would act as substantial sources of dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) pollution. As landfill fires may serve as sources of dioxins, we focused on the concentrations of PCDD and PCDF in soil samples taken in the vicinity of the landfill located at south-east Estonia in the course of our inventory. Concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were studied in five soil samples taken in the vicinity of the Laguja landfill in south-east Estonia. The four soil samples were taken in southern, eastern, western and northern parts not further than 300 m from the landfill, and one sample was taken at the distance of 3 km from the landfill. The PCDD/F concentrations in all soil samples were at background level (0.64-2.33 pg I-TEQ WHO/g dry weight). To maintain this situation, the administrator of the landfill must avoid landfill fires, which are one of the reasons for the generation of dioxins and furans.     

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.     

Nocturnal boundary layer characteristics and land breeze development in Houston,Texas during TexAQS II

The nocturnal boundary layer in Houston, Texas was studied using a high temporal and vertical resolution tethersonde system on four nights during the Texas Air Quality Study II (TexAQS II) in August and September 2006. The launch site was on the University of Houston campus located approximately 4 km from downtown Houston. Of particular interest was the evolution of the nocturnal surface inversion and the wind flows within the boundary layer. The land–sea breeze oscillation in Houston has important implications for air quality as the cycle can impact ozone concentrations through pollutant advection and recirculation. The results showed that a weakly stable surface inversion averaging in depth between 145 and 200 m AGL formed on each of the experiment nights, typically within 2–3 h after sunset. Tethersonde vertical winds were compared with two other Houston data sets (High Resolution Doppler Lidar and radar wind profiler) from locations near the coastline and good agreement was found, albeit with a temporal lag at the tethersonde site. This comparison revealed development of a land breeze on three nights which began near the coastline and propagated inland both horizontally and vertically with time. The vertical temperature structure was significantly modified on one night at the tethersonde site after the land breeze wind shift, exhibiting near-adiabatic profiles below 100 m AGL.     

Determination of 10 particle-associated multiclass polar and semi-polar pesticides from small streams using accelerated solvent extraction

A new analytical method using accelerated solvent extraction was developed for the determination of 10 particle-associated polar and semipolar pesticides. In addition, six deuterated analogues of the target compounds were evaluated as internal standards. The method yielded acceptable accuracy (73–103% recovery) and precision (<25% relative standard deviation) for eight compounds. Using size exclusion chromatography (SEC) as cleanup step resulted in higher recoveries compared to solid phase extraction (SPE) cleanup.

Deuterated standards with 10 or more deuterium atoms performed well as internal standards concerning similar recovery and correlation with the target analytes.

The method was employed to extract particle-associated pesticides from 16 streams located in an area with intense agriculture in France. Acetochlor, pirimicarb, tebuconazole, fenpropidin, -endosulfan and chlorfenvinphos were detected at concentrations up to 1 mg kg⁻¹ dry weight. A comparison with aquatic toxicity data indicated potential risk to the benthic fauna exposed to these concentrations of pirimicarb, -endosulfan and chlorfenvinphos.

We suggest that the method presented here be used for the extraction and quantitation of particle-associated polar pesticides.     

Application of microbial hot spots enhances pesticide degradation in soils

Through transfer of an active, isoproturon degrading microbial community, pesticide mineralization could be successfully enhanced in various soils under laboratory and outdoor conditions. The microbes, extracted from a soil having high native ability to mineralize this chemical, were established on expanded clay particles and distributed to various soils in the form of microbial "hot spots". Both, diffusion controlled isoproturon mass flow towards these "hot spots" (6microg d(-1)) as well as microbial ability to mineralize the herbicide (approximately 5microg d(-1)) were identified as the main processes enabling a multiple augmentation of the native isoproturon mineralization even in soils with heavy metal contamination. Soil pH-value appears to exert an important effect on the sustainability of this process.     

Reducing Fertilizer‐Nitrogen Losses from Rowcrop Landscapes: Insights and Implications from a Spatially Explicit Watershed Model

We present conceptual and quantitative models that predict changes in fertilizer‐derived nitrogen delivery from rowcrop landscapes caused by agricultural conservation efforts implemented to reduce nutrient inputs and transport and increase nutrient retention in the landscape. To evaluate the relative importance of changes in the sources, transport, and sinks of fertilizer‐derived nitrogen across a region, we use the spatially explicit SPAtially Referenced Regression On Watershed attributes watershed model to map the distribution, at the small watershed scale within the Upper Mississippi‐Ohio River Basin (UMORB), of: (1) fertilizer inputs; (2) nutrient attenuation during delivery of those inputs to the UMORB outlet; and (3) nitrogen export from the UMORB outlet. Comparing these spatial distributions suggests that the amount of fertilizer input and degree of nutrient attenuation are both important in determining the extent of nitrogen export. From a management perspective, this means that agricultural conservation efforts to reduce nitrogen export would benefit by: (1) expanding their focus to include activities that restore and enhance nutrient processing in these highly altered landscapes; and (2) targeting specific types of best management practices to watersheds where they will be most valuable. Doing so successfully may result in a shift in current approaches to conservation planning, outreach, and funding.     

Extensive aerosol optical properties and aerosol mass related measurements during TRAMP/TexAQS 2006 – Implications for PM compliance and planning

Extensive aerosol optical properties, particle size distributions, and Aerodyne quadrupole aerosol mass spectrometer measurements collected during TRAMP/TexAQS 2006 were examined in light of collocated meteorological and chemical measurements. Much of the evident variability in the observed aerosol-related air quality is due to changing synoptic meteorological situations that direct emissions from various sources to the TRAMP site near the center of the Houston-Galveston-Brazoria (HGB) metropolitan area. In this study, five distinct long-term periods have been identified. During each of these periods, observed aerosol properties have implications that are of interest to environmental quality management agencies. During three of the periods, long range transport (LRT), both intra-continental and intercontinental, appears to have played an important role in producing the observed aerosol. During late August 2006, southerly winds brought super-micron Saharan dust and sea salt to the HGB area, adding mass to fine particulate matter (PM_2.5) measurements, but apparently not affecting secondary particle growth or gas-phase air pollution. A second type of LRT was associated with northerly winds in early September 2006 and with increased ozone and sub-micron particulate matter in the HGB area. Later in the study, LRT of emissions from wildfires appeared to increase the abundance of absorbing aerosols (and carbon monoxide and other chemical tracers) in the HGB area. However, the greatest impacts on Houston PM_2.5 air quality are caused by periods with low-wind-speed sea breeze circulation or winds that directly transport pollutants from major industrial areas, i.e., the Houston Ship Channel, into the city center.