Biological Activity in a Heavily Organohalogen-Contaminated River Sediment (8 pp)

Background, Aims and Scope Sediments of the Spittelwasser creek are highly polluted with organic compounds and heavy metals due to the discharge of untreated waste waters from the industrial region of Bitterfeld-Wolfen, Germany over the course of more than one century. However, relatively few data have been published about the chloroorganic contamination of the sediment. This paper reports on the content of different (chloro)organic compounds with special emphasis on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F), and chlorobenzenes. Existing concepts for the remediation of Spittelwasser sediment include the investigation of natural attenuation processes, which largely depend on the presence of an intact microbial food web. In order to gain more insight in terms of biological activity, we analyzed the capacity of sediment microflora to degrade organic matter by measuring the activities of extracellular hydrolytic enzymes involved in the biogeochemical cycling of carbon, nitrogen, phosphorus and sulfur. Furthermore, the detection of physiologically active bacteria in the sediment, particularly of those known for their capability to reductively dehalogenate organochlorine compounds, illustrates the potential for intrinsic bioremediation processes. Methods PCDD/F and chlorobenzenes were analyzed by gas chromatography(GC)/mass spectrometry and GC/flame ionization detection, respectively. The activities of hydrolytic enzymes were determined from freshly sampled sediment layers using 4-methylumbelliferyl (MUF) or 7-amino-4-methylcoumarin-conjugated model compounds and kinetic fluorescence measurements. Physiologically active bacteria from different sediment layers were microscopically visualized by fluorescence in situ hybridization (FISH). Specific bacteria were identified by 16S rRNA gene amplification and sequencing. Results and Discussion The PCDD/F congener profile was dominated by dibenzofurans. In addition, the presence of specific tetra and pentachlorinated dibenzofurans supported the assumption that extensive magnesium production was one possible source for the high contamination. A range of other chloroorganic compounds, including several isomers of chlorobenzenes, hexachlorocyclohexane and 1,1,1-trichloro-2,2-bis (p-chloro-phenyl)ethane (DDT), was present in the sediment. Activities of extracellular hydrolytic enzymes showed a strong decrease in those sediment layers that were characterized by high contents of absorbable organic halogen (AOX), indicating disturbed organic matter decay. Interestingly, an abnormal increase of cellulolytic enzyme activities below the organochlorine-rich layers was observed, possibly caused by residual cellulose from discharges of sulfite pulping wastes. FISH revealed physiologically active bacteria in most sediment layers from the surface down to the depth of about 60 cm, including members of Desulfitobacterium (D.) and Sulfurospirillum. The presence of D. dehalogenans was confirmed by its partial 16S rRNA gene sequence. Conclusions Results of chemical sediment analyses demonstrated high loads of organochlorine compounds, particularly of PCDD/F. Several years after stopping the waste water discharge to Spittelwasser creek, this sediment remains a main source for pollution of the downstream river system by way of the ongoing mobilization of sediment during high floods. As indicated by our enzyme activity measurements, the decomposition potential for organic matter is low in organochlorine-rich sediment layers. In contrast, the comparably higher enzyme activities in less organochlorine-polluted sediment layers as well as the presence of physiologically active bacteria suggest a considerable potential for natural attenuation. Recommendations and Perspectives From our data we strongly recommend to explore the degradative capacity of sediment microorganisms and the limits for in situ activity towards specific sediment pollutants in more detail. This will give a sound basis for the integration of bioremediation approaches into general concepts to reduce the risk that permanently radiates from this highly contaminated sediment. Submission Editor: Dr. Henner Hollert (Henner.Hollert@urz.uniheidelberg.de)     

Distribution patterns of plants explained by human movement behaviour

Distribution patterns of plants are affected by human activities such as creation, destruction or modification of habitats. However, another important question is to what extent humans shape plant distributions by acting as dispersal vectors. In order to answer this question we developed a simulation model for the spread of plant species between human settlements. This was done on the basis of extensive sociological and ecological data on a regional scale. With regard to the sociological data, human movement behaviour defined the amount of exchange between the settlements. Gardening types represented the potential habitat in our model. The ecological data was derived from a vegetation survey carried out in 2003, which was a repeat of a survey between 1974 and 1981 along the same transects. From these surveys, we studied the distributions of 13 species in 67 settlements. In our model, the earlier survey provided the data for the initial distribution. The simulated pattern was consequently compared with the distribution pattern in 2003. In the model, dispersal kernels based on patterns of human movement between settlements led to a better match with the distribution patterns than a null model simulating pure distance dependent dispersal for all species. This was statistically significant for seven of the thirteen species. A striking result was that alien species seem to benefit more from human dispersal than native species. We emphasize the importance of the sociological data on human movement behaviour in parameterizing our regional scale model. This study provides quantitative evidence on the impact of human movement behaviour on the distribution of plant species in suburban areas.     

Biogeochemical consequences of a changing Arctic shelf seafloor ecosystem

Unprecedented and dramatic transformations are occurring in the Arctic in response to climate change, but academic, public, and political discourse has disproportionately focussed on the most visible and direct aspects of change, including sea ice melt, permafrost thaw, the fate of charismatic megafauna, and the expansion of fisheries. Such narratives disregard the importance of less visible and indirect processes and, in particular, miss the substantive contribution of the shelf seafloor in regulating nutrients and sequestering carbon. Here, we summarise the biogeochemical functioning of the Arctic shelf seafloor before considering how climate change and regional adjustments to human activities may alter its biogeochemical and ecological dynamics, including ecosystem function, carbon burial, or nutrient recycling. We highlight the importance of the Arctic benthic system in mitigating climatic and anthropogenic change and, with a focus on the Barents Sea, offer some observations and our perspectives on future management and policy.     

Lysimeter Experiments to Investigate the Fate of Chemicals in Soils – Comparison of Five Different Lysimeter Systems

Several lysimeter scenarios and approaches exist to study the fate of agro-chemicals or contaminants from deposition in soil columns. In many systems just transport and leaching of the parent compound is followed, in some systems the leaching and transport of the metabolites is investigated as well. In more sophisticated lysimeter systems the volatilization and also the mineralization of the applied chemicals can be additionally monitored. Depending on the lysimeter system used and on the fact whether the applied chemicals are ¹⁴C-labeled or not, different results and various interpretations of the results might be achieved. Different lysimeter systems are described in this paper and a real dataset of a specific lysimeter experiment was transferred and evaluated in a virtual approach in the different lysimeter systems in order to show the advantages and disadvantages of the various systems.     

Towards quantifying the glacial runoff signal in the freshwater input to Tyrolerfjord–Young Sound,NE Greenland

Terrestrial freshwater runoff strongly influences physical and biogeochemical processes at the fjord scale and can have global impacts when considered at the Greenland scale. We investigate the performance of the HIRHAM5 regional climate model over the catchments delivering freshwater to Tyrolerfjord and Young Sound by comparing to the unique Greenland Ecological Monitoring database of in situ observations from this region. Based on these findings, we estimate and discuss the fraction of runoff originating from glacierized and non-glacierized land delivered at the daily scale between 1996 and 2008. We find that glaciers contributed on average 50–80% of annual terrestrial runoff when considering different sections of Tyrolerfjord–Young Sound, but snowpack depletion on land and consequently runoff happens about one month earlier in the model than observed in the field. The temporal shift in the model is a likely explanation why summer surface salinity in the inner fjord did not correlate to modelled runoff.     

Building resilience to water scarcity in southern Spain: a case study of rice farming in Doñana protected wetlands

Agricultural water management needs to evolve in view of increased water scarcity, especially when farming and natural protected areas are closely linked. In the study site of Doñana (southern Spain), water is shared by rice producers and a world heritage biodiversity ecosystem. Our aim is to contribute to defining adaptation strategies that may build resilience to increasing water scarcity and minimize water conflicts among agricultural and natural systems. The analytical framework links a participatory process with quantitative methods to prioritize the adaptation options. Bottom-up proposed adaptation measures are evaluated by a multi-criteria analysis (MCA) that includes both socioeconomic criteria and criteria of the ecosystem services affected by the adaptation options. Criteria weights are estimated by three different methods—analytic hierarchy process, Likert scale and equal weights—that are then compared. Finally, scores from an MCA are input into an optimization model used to determine the optimal land-use distribution in order to maximize utility and land-use diversification according to different scenarios of funds and water availability. While our results show a spectrum of perceptions of priorities among stakeholders, there is one overriding theme that is to define a way to restore part of the rice fields to natural wetlands. These results hold true under the current climate scenario and even more so under an increased water scarcity scenario.     

A qualitative sampling method for monitoring water quality in temporary channels or point sources and its application to pesticide contamination

A water-sampling device to monitor the quality of water periodically and temporarily flowing out of concrete tubes, sewers or channels is described. It inexpensively and easily enables a qualitative characterization of contamination via these point-source entry routes. The water sampler can be reverse engineered with different sizes and materials, once installed needs no maintenance, passively samples the first surge, and the emptying procedure is short. In an agricultural catchment area in Germany we monitored an emergency overflow of a sewage sewer, an outlet of a rainwater sewer and two small drainage channels as input sources to a small stream. Seven inflow events were analysed for 20 pesticide agents (insecticides, fungicides and herbicides). All three entry routes were remarkably contaminated. We found parathion-ethyl concentrations of 0.3 microg l(-1), diuron up to 17.3 microg l(-1), ethofumesate up to 51.1 microg l(-1), metamitron up to 92 microg l(-1) and prosulfocarb up to 130 microg l(-1).     

Biochar as low-cost sorbent of volatile fuel organic compounds: potential application to water remediation

Pyrolysis of waste materials to produce biochar is an excellent and suitable alternative supporting a circular bio-based economy. One of the properties attributed to biochar is the capacity for sorbing organic contaminants, which is determined by its composition and physicochemical characteristics. In this study, the capacity of waste-derived biochar to retain volatile fuel organic compounds (benzene, toluene, ethylbenzene and xylene (BTEX) and fuel oxygenates (FO)) from artificially contaminated water was assessed using batch-based sorption experiments. Additionally, the sorption isotherms were established. The results showed significant differences between BTEX and FO sorption on biochar, being the most hydrophobic and non-polar contaminants those showing the highest retention. Furthermore, the sorption process reflected a multilayer behaviour and a relatively high sorption capacity of the biochar materials. Langmuir and Freundlich models were adequate to describe the experimental results and to detect general differences in the sorption behaviour of volatile fuel organic compounds. It was also observed that the feedstock material and biochar pyrolysis conditions had a significant influence in the sorption process. The highest sorption capacity was found in biochars produced at high temperature (>?400 °C) and thus rich in aromatic C, such as eucalyptus and corn cob biochars. Overall, waste-derived biochar offers a viable alternative to be used in the remediation of volatile fuel organic compounds from water due to its high sorption capacity.

     

Monoterpene emissions and carbonyl compound air concentrations during the blooming period of rape (Brassica napus)

An increasing percentage of agricultural land in Germany is used for oil seed plants. Hence, rape has become an important agricultural plant (in Saxony 1998: 12% of the farmland) in the recent years. During flowering of rape along with intensive radiation and high temperatures, a higher production and emission of biogenic VOC was observed. The emissions of terpenes were determined and more importantly, high concentrations of organic carbonyl compounds were observed during this field experiment. All measurements of interest have been carried out during two selected days with optimal weather conditions. It is found that the origin or the mechanism of formation of different group of compounds had strong influence on the day to day variation of their concentrations. The emission flux of terpenes from flowering rape plants was determined to be 16–32 μg h⁻¹ m⁻² (30–60 ng h⁻¹ per g dry plant––540–1080 ng h⁻¹ per plant), in total. Limonene, -thujene and sabinene were the most important compounds (about 60% of total terpenes). For limonene and sabinene reference emission rates (M_S) and temperature coefficients were determined: β_limonene=0.108 K⁻¹ and M_S=14.57 μg h⁻¹ m⁻²; β_sabinene=0.095 K⁻¹ and M_S=5.39 μg h⁻¹ m⁻².

The detected carbonyl compound concentrations were unexpectedly high (maximum formaldehyde concentration was 18.1 ppbv and 3.4 ppbv for butyraldehyde) for an open field. Possible reasons for these concentrations are the combination of primary emission from the plants induced by high temperature and high ozone stress, the secondary formation from biogenically and advected anthropogenically emitted VOC at high radiation intensities and furthered by the low wind speeds at this time.     

Hexabromocyclododecane diastereomers in fish and suspended particulate matter from selected European waters—trend monitoring and environmental quality standard compliance

The brominated flame retardant hexabromocyclododecane (HBCD) was monitored in fish and sediment (from one lake) or suspended particulate matter (SPM; from five rivers) at European freshwater sites to study the effects of reduction measures implemented by HBCD producers and users in recent years. Bream (Abramis brama) were sampled annually between 2007 and 2013 in the rivers Götaälv/SE, Rhône/FR, Western Scheldt/NL, Mersey/UK, and Tees/UK and in Lake Belau/DE. Sediment/SPM was taken every second year between 2008 and 2014. HBCD was analyzed by LC/MS/MS allowing the determination of the alpha-, beta-, and gamma-diastereomers. For most sites, a decrease in ∑HBCD was observed in fish (e.g., in the Rhône and Western Scheldt by about 80 and 60%, respectively, with significantly decreasing trends, p < 0.01). In the Rhône, HBCD also decreased in SPM. At the sampling site in the Tees which was impacted by a former HBCD point source, fish HBCD levels decreased only after a major flood event in 2013. While fish data indicate a decline in environmental HBCD concentrations at most sites with diffuse emissions, SPM data were less conclusive. The European environmental quality standard for HBCD in fish of 167 μg kg^?1 wet weight was met by all fish samples in 2013.