The identification of readily bioavailable pollutants in lake shkodra/skadar using semipermeable membrane devices (SPMDs), bioassays and chemical analysis

GOAL, SCOPE AND BACKGROUND: Lake Shkodra/Skadar is the largest lake in the Balkans region and located on the border between Albania to the south and Montenegro to the north. Because of the wide range of endemic, rare or endangered plant and animal species it supports, Lake Shkodra/Skadar and its extensive associated wetlands are internationally recognised as a site of significance and importance (Ramsar site). In recent years, social and economic changes in both Albania and Montenegro have lead to unprecedented levels of urban and industrial effluent entering the lake. Of particular concern is the increasing input of toxic hydrophobic organic pollutants (HOPs) into the lake and the degree to which these compounds are available for uptake by aquatic biota. Semipermeable membrane devices (SPMDs) have been shown to sample the readily bioavailable fraction (dissolved phase) of waterborne HOPs and in doing so provide relevant data for exposure assessment. The aim of the current study was to use SPMD-based sampling in conjunction with appropriate bioassays and chemical analysis to identify readily bioavailable HOPs in the lake. METHODS: SPMDs were constructed and deployed at three sites in the Albanian sector and three sites in the Montenegrin sector of Lake Skadar/Shkodra for 21 days. Following the dialytic recovery of target analytes and size exclusion chromatographic clean-up, aliquots of SPMD samples were subjected to GC-MS scan analysis for major components, GC-MS SIM analysis for 16 priority pollutant polycyclic aromatic hydrocarbons (PP-PAHs) and assayed for EROD-inducing, estrogenic and mutagenic potential using rainbow trout liver cells (RTL-W1), the yeast estrogen screen (YES) and the Ames Test, respectively. RESULTS AND DISCUSSION: A total of 39 compounds were tentatively identified in SPMD samples from the six sampling sites. Alkylated PAHs were the most abundant and ubiquitous compounds present along with various sterols and sterol derivatives. Numerous other compounds remain unidentified. 15 of the 16 targeted PP-PAHs were present in samples from one or more of the sampling sites indicating these compounds are both readily bioavailable and widely distributed in Lake Shkodra/Skadar. Total PP-PAH concentrations ranged between 3991 ng/SPMD and 10695 ng/SPMD. Bioassays carried out on SPMD samples revealed significant EROD-inducing and estrogenic potential at five of the six sampling sites indicating toxicologically relevant compounds are readily available for uptake by resident aquatic biota. EROD-inducing potential was positively correlated with targeted PP-PAH concentration (r2 = 0.74). However, comparison of bioassay- and analytically-derived toxicity equivalents revealed targeted PP-PAHs were responsible for less than 0.06% of the total EROD-inducing potential. CONCLUSIONS AND OUTLOOK: The combination of SPMD-based sampling with appropriate bioassays and chemical analysis provided an effective tool for the identification of environmentally relevant waterborne pollutants in Lake Shkodra/Skadar. Our results show that toxicologically relevant HOPs including EROD-inducing and potentially estrogenic compounds are widely distributed in the lake and readily available for uptake by aquatic biota. Our results also suggest that alkylated PAHs rather than parent compounds may be of greater toxicological relevance in the lake. As anthropogenic influences continue to increase, SPMD-based sampling is expected to play a central role in future research concerned with the identification, monitoring and assessment of the risk posed by HOPs to Lake Shkodra/Skadar's aquatic biota.     

Lead pollution in a large, prairie-pothole lake (Rush Lake, WI, USA): effects on abundance and community structure of indigenous sediment bacteria

Rush Lake (WI, USA), the largest prairie-pothole lake east of the Mississippi River, has been contaminated with lead pollution as a result of over 140 years of waterfowl hunting. We examined: (1) the extent of lead pollution in Rush Lake sediments and (2) whether lead pollution in Rush Lake is affecting the abundance and community structure of indigenous sediment bacteria. Sediment lead concentrations did not exceed 59 mg Pb kg(-1) dry sediment. No relationship was observed between sediment lead concentration and the abundance of aerobic (P=0.498) or anaerobic (P=0.416) heterotrophic bacteria. Similarly, lead did not appear to affect bacterial community structure when considering both culturable and nonculturable community members. In contrast, the culturable fraction of sediment bacteria in samples containing 59 mg Pb kg(-1) exhibited a unique community structure. While factors other than lead content likely play roles in determining bacterial community structure in the sediments of Rush Lake, these data suggest that the culturable fraction of sediment bacterial communities is affected by elevated lead levels.     

Phytoplankton Community and Chlorophyll a as Trophic State Indices of Lake Skadar (Montenegro,Balkan) (7 pp)

Background, Aims and Scope Phytoplankton, as a first step in trophic cascades of lakes, can be a good indicator of trophic states, considering that every environmental change affects this community and many species of this community are sensitive to changes, and that they response very quickly. In this study, we tried to assess and predict the trophic state of Lake Skadar according to phytoplankton data.Methods Water samples were collected using Ruttner sampling bottle. Temperature, dissolved oxygen, ph, conductivity and transparence were measured in situ using portable equipment. Nutrients and chlorophyll a were measured using standard spectrophotometric methods. A determination of phytoplankton species was performed using relevant keys and the counting of cells was performed using sedimentation methods.Results and Discussion The species composition of Lake Skadar revealed 95 taxa, with Chlorophyceae and Bacillariophyceae being represented best. According to an average chlorophyll a concentration of 5.9 µg/l, Lake Skadar belongs to the mesotrophic level of the trophic scale. Developed prediction equation for chlorophyll a revealed a good prediction (R2=0.71) and the parameter Secchi depth was primarily correlated with chlorophyll a concentration. Trophic state indices derived from chlorophyll a and transparency, were close together, but both were below the phosphorous index. Values of trophic state indices rank the Lake Skadar as being mesotrophic. This study also showed that indices of diversity based on phytoplankton are weak indicators of trophic status and that they can well characterize only differences between assemblages and associations. According to calculated saprobic indices (ranging from 1.5 to 2.15), Lake Skadar is on betamesosaprobic level of saprobity, which means that it is moderately polluted with organic compounds. Conclusions Total phosphorus is not the main limiting factor for the phytoplankton community in Lake Skadar. Disagreements between chlorophyll and the transparency index, on the one hand, and the total phosphorus index, on the other, suggest that the phytoplankton in Lake Skadar is probably limited by other factors than phosphorus, such as nitrogen, toxic substances or intense zooplankton grazing. According to the majority of investigated parameters and indices derived from phytoplankton data, Lake Skadar is mesotrophic, with tendencies toward eutrophic levels during the summer period. Recommendations and Outlook Long-term monitoring is required for a better estimation of state and the conditions of Lake Skadar. Further studies on factors influencing the phytoplankton community, especially zooplankton grazing and toxic substances, which were not included in this study, should be continued in the future to improve the efficiency of phytoplankton usage in estimating the ecological and trophic conditions of Lake Skadar.     

Isolation and characterization of mesotrione-degrading Bacillus sp. from soil

Dissipation kinetics of mesotrione, a new triketone herbicide, sprayed on soil from Limagne (Puy-de-Dôme, France) showed that the soil microflora were able to biotransform it.Bacteria from this soil were cultured in mineral salt solution supplemented with mesotrione as sole source of carbon for the isolation of mesotrione-degrading bacteria. The bacterial community structure of the enrichment cultures was analyzed by temporal temperature gradient gel electrophoresis (TTGE). The TTGE fingerprints revealed that mesotrione had an impact on bacterial community structure only at its highest concentrations and showed mesotrione-sensitive and mesotrione-adapted strains. Two adapted strains, identified as Bacillus sp. and Arthrobacter sp., were isolated by colony hybridization methods.Biodegradation assays showed that only the Bacillus sp. strain was able to completely and rapidly biotransform mesotrione. Among several metabolites formed, 2-amino-4-methylsulfonylbenzoic acid (AMBA) accumulated in the medium. Although sulcotrione has a chemical structure closely resembling that of mesotrione, the isolates were unable to degrade it.     

Effects of seasonal succession and water pollution on the protozoan community structure in an eutrophic lake

The purpose of the research is to study the seasonal succession of protozoa community and the effect of water quality on the protozoa community to characterize biochemical processes occurring at a eutrophic Lake Donghu, a large shallow lake in Wuhan City, China. Samples of protozoa communities were obtained monthly at three stations by PFU (polyurethane foam unit) method over a year. Synchronously, water samples also were taken from the stations for the water chemical quality analysis. Six major variables were examined in a principal component analysis (PCA), which indicate the fast changes of water quality in this station I and less within-year variation and a comparatively stable water quality in stations II and III. The community data were analyzed using multivariate techniques, and we show that clusters are rather mixed and poorly separated, suggesting that the community structure is changing gradually, giving a slight merging of clusters form the summer to the autumn and the autumn to the winter. Canonical correspondence analysis (CCA) was used to infer the relationship between water quality variables and phytoplankton community structure, which changed substantially over the survey period. From the analysis of cluster and CCA, coupled by community pollution value (CPV), it is concluded that the key factors driving the change in protozoa community composition in Lake Donghu was water qualities rather than seasons.     

Assessment of nematode community structure as a bioindicator in river monitoring

Nematode communities from river water and sediments were assessed for the abundance, feeding types, maturity indices and nematode channel ratio (NCR). The sampling sites studied included different levels of pollution and contamination from agricultural, industrial and sewage sources. The nematode abundance found in the sediment samples was more than that in the water samples. The lowest nematode abundance in sediment samples and the lowest NCR in water samples were both found at the industrial pollution site. Water samples showed positive correlation between the NCR and river pollution index (RPI). Mean maturity indices in sediment samples were inversely correlated with RPI. The pollutant source determined the relationship between NCR and pollution level, while maturity index always showed negative correlation with pollutant level regardless of the pollutant sources. The nematode abundance and its community structure were both reliable bioindicators for monitoring long-term river pollution in both qualitative and quantitative aspects.     

Development of a new biotic index to assess freshwater pollution

We developed a new biotic index of species pollution value (SPV) and community pollution value (CPV) based on the correlation of protozoan communities with chemical water quality to assess freshwater pollution. Five hundred and twenty-three species of protozoa SPV were established based on the data of River Hangjiang and Lake Donghu. The present research was conducted in order to further consummate the biotic index. Protozoa of the water system in Changde City were collected from 16 stations using the PFU method and the water chemical parameters of the stations were analyzed. The results showed that CPV calculated from SPV had a close correlation with the degree of water pollution (p < 0.00001), which indicated that the method is reliable. By combining the data of River Hangjiang, Lake Donghu and Changde City, the final form of SPV was accomplished and the SPV list increased to 757. The ultimate water standard evaluated by CPV calculated from SPV was proposed.     

Analysis of river pollution data from low-flow period by means of multivariate techniques

The oil-shale industry has created serious pollution problems in northeastern Estonia. Untreated, phenol-rich leachate from semi-coke mounds formed as a by-product of oil-shale processing is discharged into the Baltic Sea via channels and rivers. An exploratory analysis of water chemical and microbiological data sets from the low-flow period was carried out using different multivariate analysis techniques. Principal component analysis allowed us to distinguish different locations in the river system. The riverine microbial community response to water chemical parameters was assessed by co-inertia analysis. Water pH, COD and total nitrogen were negatively related to the number of biodegradative bacteria, while oxygen concentration promoted the abundance of these bacteria. The results demonstrate the utility of multivariate statistical techniques as tools for estimating the magnitude and extent of pollution based on river water chemical and microbiological parameters. An evaluation of river chemical and microbiological data suggests that the ambient natural attenuation mechanisms only partly eliminate pollutants from river water, and that a sufficient reduction of more recalcitrant compounds could be achieved through the reduction of wastewater discharge from the oil-shale chemical industry into the rivers.     

Bioanalytical characterisation of multiple endocrine- and dioxin-like activities in sediments from reference and impacted small rivers

A comprehensive evaluation of organic contamination was performed in sediments sampled in two reference and three impacted small streams where endocrine disruptive (ED) effects in fish have been evidenced. The approach combined quantitative chemical analyses of more than 50 ED chemicals (EDCs) and a battery of in vitro bioassays allowing the quantification of receptor-mediated activities, namely estrogen (ER), androgen (AR), dioxin (AhR) and pregnane X (PXR) receptors. At the most impacted sites, chemical analyses showed the presence of natural estrogens, organochlorine pesticides, parabens, polycyclic aromatic hydrocarbons (16 PAHs), bisphenol A and alkylphenols, while synthetic steroids, myco-estrogens and phyto-estrogens were not detected. Determination of toxic-equivalent amounts showed that 28-96% of estrogenic activities in bioassays (0.2-6.3 ng/g 17β-estradiol equivalents) were explained by 17β-estradiol and estrone. PAHs were major contributors (20-60%) to the total dioxin-like activities. Interestingly, high PXR and (anti)AR activities were detected; however, the targeted analysed compounds could not explain the measured biological activities. This study highlighted the presence of multiple organic EDCs in French river sediments subjected to mixed diffuse pollution, and argues for the need to further identify AR and PXR active compounds in the aquatic environment.     

Decomposer animals and bioremediation of soils

Although microorganisms are degrading the contaminants in bioremediation processes, soil animals can also have important--while usually an indirect--role in these processes. Soil animals are useful indicators of soil contamination, both before and after the bioremediation. Many toxicity and bioavailability assessment methods utilizing soil animals have been developed for hazard and risk-assessment procedures. Not only the survival of the animals, but also more sensitive parameters like growth, reproduction and community structure have often been taken into account in the assessment. The use of bioassays together with chemical analyses gives the most reliable results for risk analyses. This is because physical, chemical and biological properties of the remediated soil may be changed during the process, and it is possible that transformation rather than mineralization of the contaminants has taken place. In addition, the soil may contain other harmful substances than those searched in chemical analyses. Finally, because the ultimate goal of the bioremediation should be--together with mineralization of the harmful substances--the ecological recovery of the soil, development of diverse decomposer community as a basis of the functioning ecosystem should be ensured. Soil animals, especially the large ones, can also actively take part in the ecological recovery processes through their own activity. The potential risk of transfer of contaminants accumulated in soil animals to the above-ground food webs should be borne in mind.     

Sediment quality in littoral regions of the Gulf of Cádiz: a triad approach to address the influence of mining activities

To evaluate sediment quality in different areas in the Gulf of Cádiz affected by mining activities, an integrative approach to assessment was used: the Sediment Quality Triad (SQT). Sediment samples were collected at six stations and subjected to replicated sediment acute and chronic toxicity tests, and comprehensive sediment chemistry analyses. Organisms collected synoptically at the same stations were analyzed for histopathological lesions and chemical concentrations in their tissues to determine 'in situ' alteration and bioavailability, in place of benthic community structure. The results obtained for each component were linked to the SQT using different methodologies of interpretation and expression of the integrated approach: (a) multivariate analysis, (b) significant statistical differences compared to the reference stations, (c) ANOVA-based pie charts, and (d) classical methods using triangles and the SQT index of pollution. SQT results indicated that the highest pollution was mainly associated with metals from mining activities and polyaromatic hydrocarbons in the Ría of Huelva. The use of histopathological measures and bioaccumulation of metals, improved the characterization of 'gray areas' of pollution and in the determination of the bioavailability of metals.     

产业结构演变的流域水环境响应研究——以社渎港流域为例

以太湖15个入湖河流之一的社渎港为研究对象,利用社渎港流域的水环境质量监测数据、工业企业污染排放调查数据、环境统计数据及社会经济统计数据,对社渎港流域产业结构的合理性进行了诊断,并采用典型相关分析方法探讨了产业结构演变对水环境的影响。结果表明,研究区的工业污染总体上得到了较好控制,其中屺亭街道的工业污染排放最为严重;城乡生活污染和农业面源污染是研究区水环境质量恶化的主要原因,城乡生活污染对COD和氨氮入河量的贡献率较高,分别为46.59%和60.55%,农业面源污染对TN和TP入河量的贡献率突出,分别为64.05%和76.50%;研究区产业结构与钱纳里三次产业结构模式(产业结构合理程度的参照标准)的Hamming贴近度从2001年的0.83下降到2007年的0.77,产业结构不尽合理,且不合理程度逐渐加剧;研究区第一产业对TN和TP入河量的影响最为显著,第三产业对氨氮和COD入河量的影响最为明显;可通过优化产业结构来减轻研究区的水环境污染状况,产业结构调整的主要目标应为降低第二产业产值比例及增加第三产业产值比例。     

Algal growth inhibition by river water pollutants in the agricultural area around Lake Biwa, Japan

An ecotoxicological study of river water discharged from the agricultural area around Lake Biwa was performed by using algal bioassays to guide chemical analysis. Water samples were collected once a week, at least, for 1 year starting in April 1997 and continuing until April 1998. The toxicities of the dissolved and particulate-adsorbed extracts of water samples were evaluated by the algal growth inhibition test and concentrations of individual pesticides were determined. Most of the river water that was collected during the periods when pesticides were applied to the paddy fields caused algal growth inhibition. Some extracts were found to contain herbicides (molinate, mefenacet, simetryn, or esprocarb) as major compounds. According to chemical assay and bioassay, simetryn was identified as the most toxic compound that caused algal growth inhibition.     

Macroinvertebrate community as a biological indicator of ecological and toxicological factors in Lake Saint-François (Québec)

To assess the potential of the macroinvertebrate community for monitoring variation in the environmental quality of large rivers, the response of littoral macrobenthos in Lake Saint-Fran?ois, a fluvial lake of the St Lawrence River (Québec) are described. First, the composition of total macroinvertebrate communities and important taxonomic groups as well as the biotic ICI-SL index in 16 littoral stations varying in sedimentology, water chemistry and contamination are described to define indicator species groups and environmental quality ranks. Thereafter, the relative contribution of ecological and toxicological factors in explaining the variation observed in macroinvertebrate assemblages and biotic index were quantified using partial canonical correspondence analysis. Cluster analyses based on taxonomic composition separated five groups of stations where macroinvertebrate assemblages varied in density, composition and tolerance to pollution. The ICI-SL biotic index varied from 7.2 to 27.2 with a mean value of 19 +/- 6. The ICI-SL values determined for the macroinvertebrate communities in Lake Saint-Fran?ois did not reflect an important deterioration in environmental quality, and there was some agreement between the environmental quality ranking of the stations expressed either by the ICI-SL index or the community cluster analysis. Water conductivity and phosphorus concentration, followed by macrophyte types (Chara, Ceratophyllum) and sediment grain size, were the most significant ecological variables to explain variation in macroinvertebrate communities and derived ICI-SL index in Lake Saint-Fran?ois. Among the toxicological factors, metals in water (Fe, Cr, Pb, Mn, Zn) and sediment (Mn, Pb, Se), as well as the composite indices of metal and organic contamination (water CI, sediment CI, sediment total PAHs) were the most important factors. The contamination factors selected in our models represented contaminant sorption processes rather than direct toxicological effects. The lack of clear relationships between contaminants and macroinvertebrate variables reflected the relative low level of contamination in the stations sampled in Lake Saint-Fran?ois. There were some interactions between toxicological and ecological variables that should be considered in the planning of sampling and interpretation of biomonitoring studies. However, the large amount of unexplained variance (49.2-86.6%) in the CCA models underlined the limitations of the use of the indices of macroinvertebrate community structure that were assessed in this study for biomonitoring purposes in the absence of a contrasting pollution gradient.     

Nematode communities in contaminated river sediments

Nematode communities of eight sites from three river catchments were investigated in terms of the genera composition, feeding types, and life-history strategists. The sampling sites showed a gradient of anthropogenic contamination with heavy metals and organic pollutants being important factors in differentiating the sites. Nematode community structure was related to sediment pollution and the hydro-morphological structure of the sampling sites. Heavily contaminated sites were characterized by communities with high relative abundances of omnivorous and predacious nematodes (Tobrilus, c-p 3; Mononchus, c-p 4), while sites with low to medium contamination were dominated by bacterivorous nematodes (Monhystera, Daptonema; c-p 2) or suction feeders (Dorylaimus, c-p 4). The relatively high Maturity Index values in the heavily polluted sites were surprising. Nematodes turned out to be a suitable organism group for monitoring sediment quality, with generic composition being the most accurate indicator for assessing differences in nematode community structure.     

Combination of in vitro bioassays for the determination of cytotoxic and genotoxic potential of wastewater, surface water and drinking water samples

In this study we evaluated genotoxicity and cytotoxicity of native samples of wastewaters (15 samples), surface waters (28 samples) and potable waters (8 samples) with the SOS/umuC assay with Salmonella typhimurium TA1535/pSK1002 and MTT assay with human hepatoma HepG2 cells. The genotoxicity of selected samples was confirmed with the comet assay with HepG2 cells. In the SOS/umuC assay 13 out of the 51 samples were genotoxic: two effluent samples from chemical industry; one sample of wastewater treatment plant effluent; two hospital wastewater samples; three river water samples and four lake water samples. Six samples were cytotoxic for HepG2 cells: both effluent samples of chemical industry, two wastewater treatment plant effluent samples, and two river water samples, however, only the chemical industry effluent samples were genotoxic and cytotoxic, indicating that different contaminants are responsible for genotoxic and toxic effects. Comparing genotoxicity of river and lake water samples with the chemical analytical data of the presence of the residues of pharmaceutical and personal care products (non-steroidal anti-inflammatory drugs, UV filters and disinfectants) in these samples, indicated that the presence of UV filters might be linked to the genotoxicity of these samples. The results showed that the application of the bacterial SOS/umuC assay and mammalian cell assays (MTT and comet assay) with HepG2 cells was suitably sensitive combination of assays to monitor genotoxicity and cytotoxicity of native samples of wastewaters and surface waters. With this study we also confirmed that the toxicity/genotoxicity bioassays should be an integral tool in the evaluation of toxicity of complex wastewaters before the release into environment, as well as for the monitoring of surface water quality, providing data useful in risk assessment.     

Forest Die-Back Modified Plankton Recovery from Acidic Stress

We examined long-term data on water chemistry of Lake Rachelsee (Germany) following the changes in acidic depositions in central Europe since 1980s. Despite gradual chemical recovery of Rachelsee, its biological recovery was delayed. In 1999, lake recovery was abruptly reversed by a coincident forest die-back, which resulted in elevated terrestrial export of nitrate and ionic aluminum lasting ~5 years. This re-acidification episode provided unique opportunity to study plankton recovery in the rapidly recovering lake water after the abrupt decline in nitrate leaching from the catchment. There were sudden changes both in lake water chemistry and in plankton biomass structure, such as decreased bacterial filaments, increased phytoplankton biomass, and rotifer abundance. The shift from dominance of heterotrophic to autotrophic organisms suggested their substantial release from severe phosphorus stress. Such a rapid change in plankton structure in a lake recovering from acidity has, to the best of our knowledge, not been previously documented.     

Integrated spatial health assessment of yellow perch (<Emphasis Type="Italic">Perca flavescens</Emphasis>) populations from the St. Lawrence River,Quebec, Canada) part A: physiological parameters and pathogen assessment

A multi-disciplinary approach was used to evaluate the health of yellow perch (Perca flavescens) in the St. Lawrence River (Quebec, Canada), which is experiencing a severe population decline in the downstream portion of the river. Physiological parameters, liver alterations, trace metal concentrations, parasite prevalence and abundance, stable isotope composition, and the presence/absence of the viral hemorragic septicemia virus (VHSV) were evaluated in perch collected at six sites along the river: Lake St. François, Lake St. Louis (north and south), Beauregard Island, and Lake St. Pierre (north and south). Trace metal concentrations in surface water were higher in Lake St. Louis and downstream of a major urban wastewater treatment plant discharge, indicating that this effluent was a significant source of Cu, As, Ag, Zn, and Cd. Levels of Pb in surface water exceeded thresholds for the protection of aquatic life in Lake St. Louis and were negatively correlated with body condition index in this lake. In Lake St. Pierre, Cu, Ag, and Cd bioaccumulated significantly in perch liver and lower body condition index and greater liver damage were observed compared to upstream sites. Parasite analyses indicated a higher abundance of metacercariae of the trematodes Apophallus brevis and Diplostomum spp. in Lake St. Louis, and VHSV was not detected in the liver of yellow perch for all studied sites. Overall, results suggested that the global health of yellow perch from Lake St. Pierre is lower compared to upstream studied sites, which could contribute to the documented population collapse at this site.