Sibylle Mothes

Toxicity assessment of sediments from three European river basins using a sediment contact test battery

The toxicity of four polluted sediments and their corresponding reference sediments from three European river basins were investigated using a battery of six sediment contact tests representing three different trophic levels. The tests included were chronic tests with the oligochaete Lumbriculus variegatus, the nematode Caenorhabditis elegans and the mudsnail Potamopyrgus antipodarum, a sub-chronic test with the midge Chironomus riparius, an early life stage test with the zebra fish Danio rerio, and an acute test with the luminescent bacterium Vibrio fischeri. The endpoints, namely survival, growth, reproduction, embryo development and light inhibition, differed between tests. The measured effects were compared to sediment contamination translated into toxic units (TU) on the basis of acute toxicity to Daphnia magna and Pimephales promelas, and multi-substance Potentially Affected Fractions of species (msPAF) as an estimate for expected community effects. The test battery could clearly detect toxicity of the polluted sediments with test-specific responses to the different sediments. The msPAF and TU-based toxicity estimations confirmed the results of the biotests by predicting a higher toxic risk for the polluted sediments compared to the corresponding reference sediments, but partly having a different emphasis from the biotests. The results demonstrate differences in the sensitivities of species and emphasize the need for data on multiple species, when estimating the effects of sediment pollution on the benthic community.

Dynamics of mercury fluxes and their controlling factors in large Hg-polluted floodplain areas.

Environmental pollution by mercury (Hg) is a considerable environmental problem world-wide. Due to the occurrence of Hg volatilization from their soils, floodplains can function as an important source of volatile Hg. Soil temperature and soil water content related to flood dynamics are considered as important factors affecting seasonal dynamics of total gaseous mercury (TGM) fluxes. We quantified seasonal variations of TGM fluxes and conducted a laboratory microcosm experiment to assess the effect of temperature and moisture on TGM fluxes in heavily polluted floodplain soils. Observed TGM emissions ranged from 10 to 850 ng m(-2) h(-1) and extremely exceeded the emissions of non-polluted sites. TGM emissions increased exponentially with raised air and soil temperatures in both field (R(2): 0.49-0.70) and laboratory (R(2): 0.99) experiments. Wet soil material showed higher TGM fluxes, whereas the role of soil water content was affected by sampling time during the microcosm experiments.

Detection of arsenic-containing hydrocarbons in canned cod liver tissue

Arsenic is a metalloid well known to be potentially toxic depending of its species. Lipid-soluble arsenicals (arsenolipids) are present in a wide range of biological samples in which they could play a role in the biosynthesis of organoarsenic compounds from inorganic arsenic compounds. Arsenolipids have recently attracted considerable interest. In order to gain deeper insights into the impact of arsenolipids new analytical approaches for reliable determination of this class of arsenic-containing hydrocarbons in various matrices are needed. High concentrations of arsenolipids were found in seafood which served as sample material in this study. We report the investigation of three arsenolipids found in canned cod liver from which they were extracted and purified by solid phase extraction (SPE) using a silica gel column and ethyl acetate/methanol as eluent. Analytical studies were conducted by means of gas chromatography coupled with ICP-MS, MIP-AES and EI-qMS and by TOF-MS. The results obtained by GC-ICP-MS and GC-MIP-AES showed the existence of numerous arsenic compounds in the SPE fractions collected. Three major peaks were found within a retention time window between 10 and 25 min. The presence of arsenic compounds in the fish tissue could be confirmed using GC-EI-qMS analysis. Corresponding information of the molecular weights of the major arsenic species were provided by TOF-MS which allows highly accurate mass determinations. The results showed the presence of the arsenic-containing hydrocarbons with the following molecular formulas: C(17)H(37)AsO (calculated for [M+H](+) 333.2133; found 333.2136; Deltam=0.90 ppm); C(19)H(41)AsO (calculated for [M+H](+) 361.2446; found 361.2446; Deltam=0.00 ppm); C(23)H(37)AsO (calculated for [M+H](+) 405.2133; found 405.2145; Deltam=2.96 ppm). Suggestions for the corresponding structures are discussed.

Mercury Volatilization from Three Floodplain Soils at the Central Elbe River, Germany

Wetlands at the riverside of the UNESCO Biosphere Reserve “Central Elbe” are highly contaminated by heavy metals, especially mercury (Hg). The Hg-polluted Elbe floodplain soils turn out to be a source of gaseous mercury via Hg volatilization from soil into the atmosphere. A modified field sampling method was used to measure total gaseous mercury (TGM) volatilization from three different sites at the Elbe River. The modified setup had a reduced chamber size and contained an internal gas circulation system. An in-ground stainless steel cylinder minimizes Hg volatilization from adjacent soil air. Cold vapor atomic absorption spectrometry (CV-AAS) was used to determine TGM amalgamated on gold traps. Sampled TGM amounts ranged between 0.02 and 0.63 ng (absolute), whereas the calculated Hg fluxes varied from 2.0 to 63.3 ng m−2 h−1. The modified system should allow measurements of Hg volatilization at various sites with a high spatial resolution, which should enable the study of interrelations between TGM emission and several key factors influencing Hg emission from floodplain soils at the Elbe River and other riverine ecosystems in the near future.

Analysis of organophosphorus insecticides in natural waters by use of stir-bar-sorptive extraction then gas chromatography with atomic emission detection

SummaryA procedure has been developed for the determination of eight organophosphorus insecticides in natural waters by use of stir-bar-sorptive extraction (SBSE) combined with thermal desorption-GC-atomic emission detection (AED). Optimization of the extraction and thermal desorption conditions showed that an extraction time of 50 min and a desorption time of 6 min were sufficient. Addition of salt and adjustment of the pH were not necessary. Recoveries of seven of the compounds investigated were between 62% and 88%. For fenamiphos, which is highly water-soluble, recovery was only 15%. The very low limits of detection, between 0.8 ng L−1 (ethion) and 15.4 ng L−1 (fenamiphos) indicate that the SBSE-GC-AED procedure is suitable for sensitive detection of OPP in natural waters. The procedure was evaluated with real water samples.

Pollution-Induced Community Tolerance To Diagnose Hazardous Chemicals in Multiple Contaminated Aquatic Systems

Aquatic ecosystems are often contaminated with large numbers of chemicals, which cannot be sufficiently addressed by chemical target analyses. Effect-directed analysis (EDA) enables the identification of toxicants in complex contaminated environmental samples. This study suggests pollution-induced community tolerance (PICT) as a confirmation tool for EDA to identify contaminants which actually impact on local communities. The effects of three phytotoxic compounds local periphyton communities, cultivated at a reference (R-site) and a polluted site (P-site), were assessed to confirm the findings of a former EDA study on sediments. The sensitivities of R- and P-communities to prometryn, tributyltin (TBT) and N-phenyl-2-naphthylamine (PNA) were quantified in short-term toxicity tests and exposure concentrations were determined. Prometryn and PNA concentrations were significantly higher at the P-site, whereas TBT concentrations were in the same range at both sites. Periphyton communities differed in biomass, but algal class composition and diatom diversity were similar. Community tolerance of P-communities was significantly enhanced for prometryn, but not for PNA and TBT, confirming site-specific effects on local periphyton for prometryn only. Thus, PICT enables in situ effect confirmation of phytotoxic compounds at the community level and seems to be suitable to support confirmation and enhance ecological realism of EDA.

Determination of moderately polar arsenolipids and mercury speciation in freshwater fish of the River Elbe (Saxony, Germany).

Arsenic and mercury are frequent contaminants in the environment and care must be taken to limit their entrance into the food chain. The toxicity of both elements strongly depends upon their speciation. Total amounts of As and Hg as well as their species were analyzed in muscle and liver of 26 fishes of seven freshwater fish species caught in the River Elbe. The median concentrations of As were 162 μg kg(-1) w.w. in liver and 92 μg kg(-1) w.w. in muscle. The median concentrations of total Hg were 241 μg kg(-1) w.w. in liver and 256 μg kg(-1) w.w. in muscle. While this level of Hg contamination of the freshwater fish in the River Elbe is significantly lower than 20 years ago, it exceeds the recommended environmental quality standard of 20 μg Hg kg(-1) w.w. by a factor of 5-50. However, the European maximum level of 500 μg Hg kg(-1) for fish for human consumption is rarely exceeded. Arsenic-containing fatty acids and hydrocarbons were determined and partially identified in methanolic extracts of the fish by HPLC coupled in parallel to ICP-MS (element specific detection) and ESI-Q-TOF-MS (molecular structure detection). While arsenobetaine was the dominant As species in the fish, six arsenolipids were detected and identified in the extracts of liver tissue in common bream (Abramis brama), ide (Leuciscus idus), asp (Aspius aspius) and northern pike (Esox lucius). Four arsenic-containing fatty acids (AsFA) and two arsenic-containing hydrocarbons (AsHC) are reported in freshwater fish for the first time. With respect to mercury the more toxic MeHg(+) was the major species in muscle tissue (>90% of total Hg) while in liver Hg(2+) and MeHg(+) were of equal importance. The results show the high relevance of element speciation in addition to the determination of total element concentrations to correctly assess the burden of these two elements in fish.

Investigating the distribution and fate of Al, Cd, Cr, Cu, Mn, Ni, Pb and Zn in sewage-impacted mangrove-fringed creeks of Kenya, Tanzania and Mozambique

PurposeCoastal towns in the developing world are faced with the challenge of wastewater treatment. Most of the domestic wastewater generated in these urban areas is discharged raw into the surrounding mangrove forest. The local communities living near mangrove-fringed creeks are artisanal fishers and rely on fish as a source of protein. It is therefore important to determine the impact of sewage input on metal mobility/bioavailability in these mangrove systems.Materials and methodsThe fate of heavy metals was investigated in peri-urban mangrove systems of Kenya, Tanzania and Mozambique. Enrichment factors (EF) and pollution factors (PF) were applied to investigate the pollution status of selected metals in sewage-impacted creeks of the three countries. The spatial distribution patterns of metals in sediments and in the water column were determined. A sewage factor (SF) index was derived to determine the impact of sewage input on the water column.Results and discussionData obtained from sediment analysis revealed that Cd was highly depleted (EF 0.1) at Costa do Sol in Mozambique, inferring that it is highly labile under the prevailing onsite physicochemical parameters. Comparatively, Cr was more enriched in Mozambique sediments than in Kenya and Tanzania. In Tanzania; Zn showed the highest pollution levels (PF, 3.20), with reference to Ras Dege. While in Kenya, zinc was the most polluting metal in all of the sediment segments at Tudor Creek with reference to Gazi Creek. There was a conservative mixing of sediment/particulate-hosted heavy metals at Tudor and Ras Dege. This behaviour was observed for all the metals analysed. At Mtoni, however, the conservative behaviour was only pronounced for Pb and Zn, while for all three sites in Mozambique, metals were distributed evenly across the creeks indicating sinking tendencies. Sewage discharge influenced the concentration of dissolved Cr and Pb at Fort Jesus station during both flood and ebb tide.ConclusionsChanges in physicochemical parameters strongly influence the fate of sediment-hosted Cd as observed at Costa do Sol. The preferential association of Cd onto carbonates enhances Cd enrichment in sediments rich in carbonates. Input of domestic sewage contributes to dissolved Al loading, which is attributed to the use of alumina in fresh water treatment plants.

Nitrate turnover in a peat soil under drained and rewetted conditions: results from a [15N]nitrate–bromide double-tracer study

Under natural conditions, peatlands are generally nitrate-limited. However, recent concerns about an additional N input into peatlands by atmospheric N deposition have highlighted the risk of an increased denitrification activity and hence the likelihood of a rise of emissions of the greenhouse gas nitrous oxide. Therefore, the aim of the present study was to investigate the turnover of added nitrate in a drained and a rewetted peatland using a [15N]nitrate–bromide double-tracer method. The double-tracer method allows a separation between physical effects (dilution, dispersion and dislocation) and microbial and chemical nitrate transformation by comparing with the conservative Br− tracer. In the drained peat site, low NO3− consumption rates have been observed. In contrast, NO3− consumption at the rewetted peat site rises rapidly to about 100% within 4 days after tracer application. Concomitantly, the 15N abundances of nitrite and ammonium in soil water increased and lead to the conclusion that, besides commonly known NO3− reduction to nitrite (i.e. denitrification), a dissimilatory nitrate reduction to ammonium has simultaneously taken place. The present study reveals that increasing NO3− inputs into rewetted peatlands via atmospheric deposition results in a rapid NO3− consumption, which could lead to an increase in N2O emissions into the atmosphere.

Resilience of carbon and nitrogen removal due to aeration interruption in aerated treatment wetlands

Treatment wetlands have long been used for domestic and industrial wastewater treatment. In recent decades, treatment wetland technology has evolved and now includes intensified designs such as aerated treatment wetlands. Aerated treatment wetlands are particularly dependent on aeration, which requires reliable air pumps and, in most cases, electricity. Whether aerated treatment wetlands are resilient to disturbances such as an aeration interruption is currently not well known. In order to investigate this knowledge gap, we carried out a pilot-scale experiment on one aerated horizontal flow wetland and one aerated vertical flow wetland under warm (Twater>17°C) and cold (Twater<10°C) weather conditions. Both wetlands were monitored before, during and after an aeration interruption of 6d by taking grab samples of the influent and effluent, as well as pore water. The resilience of organic carbon and nitrogen removal processes in the aerated treatment wetlands depended on system design (horizontal or vertical flow) and water temperature. Organic carbon and nitrogen removal for both systems severely deteriorated after 4-5d of aeration interruption, resulting in effluent water quality similar to that expected from a conventional horizontal sub-surface flow treatment wetland. Both experimental aerated treatment wetlands recovered their initial treatment performance within 3-4d at Twater>17°C (warm weather) and within 6-8d (horizontal flow system) and 4-5d (vertical flow system) at Twater<10°C (cold weather). In the vertical flow system, DOC, DN and NH4-N removal were less affected by low water temperatures, however, the decrease of DN removal in the vertical flow aerated wetland at Twater>17°C was twice as high as in the horizontal flow aerated wetland. The quick recovery of treatment performance highlights the benefits of aerated treatment wetlands as resilient wastewater treatment technologies.