Monitoring, modelling and environmental exposure assessment of industrial chemicals in the aquatic environment

Monitoring and laboratory data play integral roles alongside fate and exposure models in comprehensive risk assessments. The principle in the European Union Technical Guidance Documents for risk assessment is that measured data may take precedence over model results but only after they are judged to be of adequate reliability and to be representative of the particular environmental compartments to which they are applied. In practice, laboratory and field data are used to provide parameters for the models, while monitoring data are used to validate the models' predictions. Thus, comprehensive risk assessments require the integration of laboratory and monitoring data with the model predictions. However, this interplay is often overlooked. Discrepancies between the results of models and monitoring should be investigated in terms of the representativeness of both. Certainly, in the context of the EU risk assessment of existing chemicals, the specific requirements for monitoring data have not been adequately addressed. The resources required for environmental monitoring, both in terms of manpower and equipment, can be very significant. The design of monitoring programmes to optimise the use of resources and the use of models as a cost-effective alternative are increasing in importance. Generic considerations and criteria for the design of new monitoring programmes to generate representative quality data for the aquatic compartment are outlined and the criteria for the use of existing data are discussed. In particular, there is a need to improve the accessibility to data sets, to standardise the data sets, to promote communication and harmonisation of programmes and to incorporate the flexibility to change monitoring protocols to amend the chemicals under investigation in line with changing needs and priorities.     

Accumulation pattern and biotransformation enzyme induction in rainbow trout embryos exposed to sublethal aqueous concentrations of 3,3',4,4'-tetrachlorobiphenyl

Accumulation pattern of 3,3',4,4'-tetrachlorobiphenyl (PCB 77) and the exposure time needed to activate the monooxygenase (EROD) and conjugation (GST) enzyme systems of fish at the advanced embryonic stage were studied. Eyed stage embryos of rainbow trout (Oncorhynchus mykiss) were exposed to sublethal doses (0, 1, 10, and 100 micrograms/l) of PCB 77. Results indicated direct accumulation of the chemical into the eggs, but the exposure time was not long enough for PCB 77 to reach constant steady state. However, at the two lowest test concentrations (1 microgram/l and 10 micrograms/l) a temporary plateau at chemical accumulation was reached at the third exposure day (185 and 1221 ng PCB/g egg w.w). At the highest concentration (100 micrograms/l) the decrease in the accumulation rate was already evident after the first day (2182 ng PCB/g egg w.w). The chemical uptake increased again at day 7 in all the exposure groups. That event could have been caused by the increased metabolic rate of the embryos in preparation for the upcoming hatching event. The microsomal CYP1A monooxygenase system (EROD) was shown to be a sensitive indicator of embryonic exposure, being induced at the low (1 microgram/l, 182 ng/g egg) PCB concentration and after a short (3 day) exposure time. The conjugation enzyme system (GST) was shown to be functioning already at the advanced embryonic stage, although no response to the studied chemical stress was detected.     

Microplastic abundance in beach sediments of the Kiel Fjord,Western Baltic Sea

Environmental Science and Pollution Research - We assessed the abundance of microplastics (0.2–5 mm) in drift line sediments from three sites in Kiel Fjord, Western Baltic...     

Biosensors for detection of mercury in contaminated soils

Biosensors based on whole bacterial cells and on bacterial heavy metal binding protein were used to determine the mercury concentration in soil. The soil samples were collected in a vegetable garden accidentally contaminated with elemental mercury 25 years earlier. Bioavailable mercury was measured using different sensors: a protein-based biosensor, a whole bacterial cell based biosensor, and a plant sensor, i.e. morphological and biochemical responses in primary leaves and roots of bean seedlings grown in the mercury-contaminated soil. For comparison the total mercury concentration of the soil samples was determined by AAS. Whole bacterial cell and protein-based biosensors gave accurate responses proportional to the total amount of mercury in the soil samples. On the contrary, plant sensors were found to be less useful indicators of soil mercury contamination, as determined by plant biomass, mercury content of primary leaves and enzyme activities.     

Occurrence and abatement of volatile sulfur compounds during biogas production

Volatile sulfur compounds (VSCs) in biogas originating from a biogas production plant and from a municipal sewage water treatment plant were identified. Samples were taken at various stages of the biogas-producing process, including upgrading the gas to vehicle-fuel quality. Solid-phase microextraction was used for preconcentration of the VSCs, which were subsequently analyzed using gas chromatography in combination with mass spectrometry. Other volatile organic compounds present also were identified. The most commonly occurring VSCs in the biogas were hydrogen sulfide, carbonyl sulfide, methanethiol, dimethyl sulfide, and dimethyl disulfide, and hydrogen sulfide was not always the most abundant sulfur (S) compound. Besides VSCs, oxygenated organic compounds were commonly present (e.g., ketones, alcohols, and esters). The effect of adding iron chloride to the biogas reactor on the occurrence of VSCs also was investigated. It was found that additions of 500-g/m3 substrate gave an optimal removal of VSCs. Also, the use of a prefermentation step could reduce the amount of VSCs formed in the biogas process. Moreover, in the carbon dioxide scrubber used for upgrading the gas, VSCs were removed efficiently, leaving traces (ppbv levels). The scrubber also removed other organic compounds.     

Development of a accelerated solvent extraction and gel permeation chromatography analytical method for measuring persistent organohalogen compounds in adipose and organ tissue analysis

A new analytical method has been developed for the quantification of 59 different persistent organohalogen compounds, such as polybrominated diphenyl ethers (PBDEs), polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs), PCB metabolites, organochlorine pesticides (OCPs) in biological organ tissues. The optimum extraction and cleanup procedures were examined using accelerated solvent extraction (ASE), automated gel permeation chromatography (GPC) on Biobeads S-X3 and automated solid phase extraction (SPE) on silica-gel. The target compounds were divided into two fractions, non-polar compounds and more polar compounds, which in the latter fraction was subsequently methylated using diazomethane. Detection can be achieved by GC/MS in negative chemical ionization (NCI) mode. The average recoveries of the compounds spiked in swine liver, heart, kidney, and cattle adipose tissues were considered satisfactory, and it was confirmed that the method could be used in routine analysis.     

Synthesis of effects in four Arctic subregions

An assessment of impacts on Arctic terrestrial ecosystems has emphasized geographical variability in responses of species and ecosystems to environmental change. This variability is usually associated with north-south gradients in climate, biodiversity, vegetation zones, and ecosystem structure and function. It is clear, however, that significant east-west variability in environment, ecosystem structure and function, environmental history, and recent climate variability is also important. Some areas have cooled while others have become warmer. Also, east-west differences between geographical barriers of oceans, archipelagos and mountains have contributed significantly in the past to the ability of species and vegetation zones to relocate in response to climate changes, and they have created the isolation necessary for genetic differentiation of populations and biodiversity hot-spots to occur. These barriers will also affect the ability of species to relocate during projected future warming. To include this east-west variability and also to strike a balance between overgeneralization and overspecialization, the ACIA identified four major sub regions based on large-scale differences in weather and climate-shaping factors. Drawing on information, mostly model output that can be related to the four ACIA subregions, it is evident that geographical barriers to species re-location, particularly the distribution of landmasses and separation by seas, will affect the northwards shift in vegetation zones. The geographical constraints--or facilitation--of northward movement of vegetation zones will affect the future storage and release of carbon, and the exchange of energy and water between biosphere and atmosphere. In addition, differences in the ability of vegetation zones to re-locate will affect the biodiversity associated with each zone while the number of species threatened by climate change varies greatly between subregions with a significant hot-spot in Beringia. Overall, the subregional synthesis demonstrates the difficulty of generalizing projections of responses of ecosystem structure and function, species loss, and biospheric feedbacks to the climate system for the whole Arctic region and implies a need for a far greater understanding of the spatial variability in the responses of terrestrial arctic ecosystems to climate change.     

Uncertainties and recommendations

An assessment of the impacts of changes in climate and UV-B radiation on Arctic terrestrial ecosystems, made within the Arctic Climate Impacts Assessment (ACIA), highlighted the profound implications of projected warming in particular for future ecosystem services, biodiversity and feedbacks to climate. However, although our current understanding of ecological processes and changes driven by climate and UV-B is strong in some geographical areas and in some disciplines, it is weak in others. Even though recently the strength of our predictions has increased dramatically with increased research effort in the Arctic and the introduction of new technologies, our current understanding is still constrained by various uncertainties. The assessment is based on a range of approaches that each have uncertainties, and on data sets that are often far from complete. Uncertainties arise from methodologies and conceptual frameworks, from unpredictable surprises, from lack of validation of models, and from the use of particular scenarios, rather than predictions, of future greenhouse gas emissions and climates. Recommendations to reduce the uncertainties are wide-ranging and relate to all disciplines within the assessment. However, a repeated theme is the critical importance of achieving an adequate spatial and long-term coverage of experiments, observations and monitoring of environmental changes and their impacts throughout the sparsely populated and remote region that is the Arctic.     

Biodegradation of trifluralin in Harran soil

Degradation of trifluralin (alpha, alpha, alpha-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine) was investigated in soils taken from three different locations at Harran region of Turkey under laboratory conditions. Surface (0-10 cm) soils, which were taken from a pesticide untreated field Gürgelen, Harran-1 and Ikizce regions in the Harran Plain. were incubated in biometer flasks for 350 days at 25 degrees C. Ring-UL-14C-trifluralin was applied at the rate of 2 microg g(-1) with 78.7 kBq radioactivity per 100 g soil flask. Evolved (14)CO2 was monitored in KOH traps throughout the experiment. Periodically, soil sub-samples were removed and extracted by supercritical fluid extraction (SFE). Unextractable soil-bound 14C residues were determined by combustion. During the 350 days incubation period 6.6, 5.4, and 3.3/' of the applied radiocarbon was evolved as (14)CO2 from the Harran-1, Gürgelen, and Ikizce soil, respectively. At the end of 350 days the SFE-extractable and bound 14C-trifluralin residues were 39.0 and 29.2% of the initially applied herbicide in Gürgelen soil. The corresponding values for Harran-1 and Ikizce soils were 36.2, 28.4% and 41.6, 18.5% respectively.     

Oxidative dealkylation of five phenylurea herbicides by the fungus CunninghamellaechinulataThaxter

Microorganisms isolated from soil degrade phenylurea herbicides via two major pathways: (i) direct hydrolysis by an amidase leading to N,O-dimethylhydroxylamine, CO₂ and aniline¹ and (ii) N-dealkylation, which has been described as the first step in urea herbicide degradation by a variety of organisms including mammals, plants and microbial systems (for a review see reference 2).Until now no attempts have been made to investigate the mechanism of N-demethylation of substituted ureas in soil microorganisms, due to the instability of the N-hydroxymethyl intermediates. This reaction mechanism has only been described in detail in green plants^3–5. As among soil fungi Phycomycetes are known to demethylate phenylurea herbicides^6,7 this study has been made to identify intermediate hydroxymethyl compounds from urea herbicides, when incubated with the fungus $\text{Cunninghamella echinulata Thaxter}$.