Comparative toxicities of 10 widely used biocides in three freshwater invertebrate species

Owing to their widespread use in wooden products, industrial products, cosmetics, and personal care products, biocides are frequently detected in wastewater and surface water. In this study, I examined the acute toxicities of 10 commonly used biocides, namely methylisothiazolinone, benzisothiazolinone, octylisothiazolinone, dichlorooctylisothiazolinone, iodopropynyl butylcarbamate, triclosan, azoxystrobin, pyraclostrobin, climbazole, and clotrimazole, in the water flea (Daphnia similis), freshwater planarians (Dugesia japonica) and green neon shrimp (Neocaridina denticulata). Among the 10 tested biocides, dichlorooctylisothiazolinone was the most toxic to both D. similis and N. denticulata, whereas pracolstrobin was the most toxic to Du. japonica. By contrast, the least toxic biocides for D. similis, Du. japonica, and N. denticulata were climbazole, iodopropynyl butylcarbamate, and methylisothiazolinone, respectively. The 48-h nominal LC₅₀ values of all the biocides, except for benzisothiazolinone and climbazole, in D. similis were mostly less than 1 mg/L. In addition, the 96-h nominal LC₅₀ values of all the biocides, except for methylisothiazolinone and iodopropynyl butylcarbamate, in Du. japonica was less than 1 mg/L. These results indicate the biocides with low LC₅₀ values are relatively toxic to freshwater organisms.     

Incomplete aerobic degradation of the antidiabetic drug Metformin and identification of the bacterial dead-end transformation product Guanylurea

Active pharmaceutical ingredients as well as personal care products are detected in increasing prevalence in different environmental compartments such as surface water, groundwater and soil. Still little is known about the environmental fate of these substances. The type II antidiabetic drug Metformin has already been detected in different surface waters worldwide, but concentrations were significantly lower than the corresponding predicted environmental concentration (PEC). In human and mammal metabolism so far no metabolites of Metformin have been identified, so the expected environmental concentrations should be very high.To assess the aerobic biodegradability of Metformin and the possible formation of degradation products, three Organisation of Economic Cooperation and Development (OECD) test series were performed in the present study.In the Closed Bottle test (OECD 301 D), a screening test that simulates the conditions of an environmental surface water compartment, Metformin was classified as not readily biodegradable (no biodegradation). In the Manometric Respiratory test (OEDC 301 F) working with high bacterial density, Metformin was biodegraded in one of three test bottles to 48.7% and in the toxicity control bottle to 57.5%. In the Zahn-Wellens test (OECD 302 B) using activated sludge, Metformin was biodegraded in both test vessels to an extent of 51.3% and 49.9%, respectively.Analysis of test samples by high performance liquid chromatography coupled to multiple stage mass spectrometry (HPLC-MS(n)) showed in the tests vessels were biodegradation was observed full elimination of Metformin and revealed Guanylurea (Amidinourea, Dicyandiamidine) as single and stable aerobic bacterial degradation product. In another Manometric Respiratory test Guanylurea showed no more transformation. Photodegradation of Guanylurea was also negative.A first screening in one of the greatest sewage treatment plant in southern Germany found Metformin with high concentrations (56.8 μg L⁻¹) in the influent (PEC = 79.8 μg L⁻¹), but effluent concentration was much lower (0.76 μg L⁻¹) whereas Guanylurea was detected in a low influent and high effluent concentration (1.86 μg L⁻¹). These data support the experimental findings in the OECD tests and analytical results of other studies, that Metformin under aerobic conditions can bacterially be degraded to the stable dead-end transformation product Guanylurea.     

Using deuterated PAH amendments to validate chemical extraction methods to predict PAH bioavailability in soils

Validating chemical methods to predict bioavailable fractions of polycyclic aromatic hydrocarbons (PAHs) by comparison with accumulation bioassays is problematic. Concentrations accumulated in soil organisms not only depend on the bioavailable fraction but also on contaminant properties. A historically contaminated soil was freshly spiked with deuterated PAHs (dPAHs). dPAHs have a similar fate to their respective undeuterated analogues, so chemical methods that give good indications of bioavailability should extract the fresh more readily available dPAHs and historic more recalcitrant PAHs in similar proportions to those in which they are accumulated in the tissues of test organisms. Cyclodextrin and butanol extractions predicted the bioavailable fraction for earthworms (Eisenia fetida) and plants (Lolium multiflorum) better than the exhaustive extraction. The PAHs accumulated by earthworms had a larger dPAH:PAH ratio than that predicted by chemical methods. The isotope ratio method described here provides an effective way of evaluating other chemical methods to predict bioavailability.     

The early warning of aquatic organophosphorus pesticide contamination by on-line monitoring behavioral changes of Daphnia magna

In this paper, the movement behavior of Daphnia magna was studied as a bio-indicator of organophosphorous pesticide (OP) contamination, using an on-line bio-monitoring method, the Multispecies Freshwater Biomonitor. A static test of acute toxicity test revealed the 24-h and 48-h LC(50) values (95% confidence limit) for Daphnia magna to be respectively 0.45 microg/l and 0.21 microg/l for dipterex 3.80 microg/l and 0.90 microg/l for malathion, and 1.25 microg/l and 0.38 microg/l for parathion. The behavior strength of Daphnia magna was a sensitive indicator of sublethal OP stress and resulted in significant concentration-response relationships for the three OPs. Increasing OP concentration will result in more intensive behavioral responses of Daphnia magna and shorter response time, which could be described by the Stepwise Stress Model (SSM). Therefore movement behavior can be effectively applied in early warning of environment quality by on-line bio-monitoring. The intensive changes in behavior strength of Daphnia magna over a short time follow the SSM concept and can be used as an indicator of early stress response to OP accidental contamination.     

基于水生生物的湖泊营养类型评价

对乌梁素海的水生生物进行了评价分析。结果表明:乌梁素海浮游动物共有4大类62种,平均生物量为3.75 mg/L,底栖动物11种,隶属3门3纲4科。底栖动物平均生物量为71.7 g/m2,属于富营养类型。     

Summer total phosphorus in lakes: A map of Minnesota,Wisconsin, and Michigan,USA

A map of summer total phosphorus in lakes has been compiled for Minnesota, Wisconsin, and Michigan to clarify regional patterns in attainable lake trophic state. Total phosphorus was used as a measure of lake trophic state because: (1) phosphorus plays a central role in controlling the overall fertility of most lakes, (2) total phosphorus values are available for a great number of lakes, and (3) phosphorus is measured in a consistent manner. The maps were compiled using patterns of total phosphorus data and observed associations between these data and geographic characteristics including physiography, land use, geology, and soils. Regions depicted on the map represent areas of similarity in phosphorus concentrations in lakes, or similarity in the mosaic of values, as compared to adjacent areas. Within each region, differences in total phosphorus can be compared to natural and anthropogenic factors to determine the types of lakes representative of each region, the factors associated with differences in quality, and the realistically attainable phosphorus levels for each type of lake.     

Phototransformation of methabenthiazuron in the presence of nitrate and nitrite ions

The influence of nitrate and nitrite ions on the degradation of methabenzthiazuron upon irradiation using artificial solar light has been investigated. The rate of degradation of methabenzthiazuron (1 microM) was accelerated by NO3- (0.1 mM) by a factor of 10. The irradiation of methabenzthiazuron (0.1 mM) in the presence of NO3- (1 mM) or NO2- (0.1 mM) yielded numerous intermediary photoproducts. Mineralization was achieved after prolonged exposure. Some were identified with the help of LC-ESI-MS and flow injection APCI-MS techniques. Both oxidations of the aromatic ring and of the urea chain were observed. The former started by hydroxylation of the ring. Further oxidation of the ring led to cleavage of the benzenic ring with formation of dialdehydic, diacidic and anhydric compounds. Complete removal of the lateral urea chain took place subsequently to demethylation of the terminal methyl group and loss of the CO-NH2 group. Nitration was a minor process. This work shows that the photodegradation of methabenzthiazuron in the presence of nitrate or nitrite ions is highly non-specific.     

Equivalent roaded area as a measure of cumulative effect of logging

A watershed disturbance index developed by the USDA Forest Service called equivalent roaded area (ERA) was used to assess the cumulative effect from forest management in California's Sierra Nevada and Klamath mountain ranges. The basins' ERA index increased as logging and road-building occurred and then decreased over time as management ceased and vegetation recovered. A refinement of the standard index emphasized disturbances in sensitive, near-channel areas, and evaluated recovery periods of 20, 30, and 50 years. Shorter recovery periods yielded better correlations between recovering forest systems and aquatic response than the longer recovery period, as represented by ERA and diversity or dominance, respectively. The refined ERA index correlated more closely with macroinvertebrate dominance and diversity information that was available for part of the study period. A minimum ERA threshold of 5% was detected, below which no effect to the macroinvertebrate community was observed. Above this threshold, elevated ERA values were associated with a decline in macroinvertebrate diversity and an increase in dominance of the top five taxa. Use of an ERA technique that emphasizes near-channel areas and biological thresholds would contribute to the Forest Service's implementation of ecosystem management.     

Acid deposition in aquatic ecosystems: Setting limits empirically

The problem of acid deposition and its harmful effects on aquatic ecosystems has created a new branch of science that is called upon to provide the knowledge on which legislative controls can be based. However, because of the nature of existing legislation, which requires evidence of cause and effect between industrial emissions and pollution, and because of science's inability to provide this information over the short term, considerable controversy has arisen about whether sufficient information exists to warrant control measures at this time. Among those who advocate controls, there is genuine divergence of opinion about how stringent the controls must be to achieve any desired level of protection.The controversy has led to an impasse between the scientific and political participants, which is reflected in the slow pace of progress toward an effective management strategy. Resolution of the impasse, at least in the short term, may demand that science and politics rely on empirical models rather than explanatory ones. The empirical model, which is the major proposal in this article, integrates all of the major variables and many of the minor ones, and constructs a three-dimensionally curved surface capable of representing the status of any waterbody subjected to the effects of acid deposition. When suitably calibrated—a process involving the integration of knowledge and data from aquatic biology, geochemistry, meteorology, and limnology—it can be used to depict limits to the rate of acid deposition required for any level of environmental protection. Because it can generate a pictorial display of the effects of management decisions and legislative controls, the model might serve as a basis for enhancing the quality of communication among all the scientific and political participants and help to resolve many of their controversies.     

Levels of polycyclic aromatic hydrocarbons and dibenzothiophenes in wetland sediments and aquatic insects in the oil sands area of Northeastern Alberta, Canada

An immense volume of tailings and tailings water is accumulating in tailings ponds located on mine leases in the oil sands area of Alberta, Canada. Oil sands mining companies have proposed to use tailings- and tailings water-amended lakes and wetlands as part of their mine remediation plans. Polycyclic aromatic hydrocarbons (PAHs) are substances of concern in oil sands tailings and tailings water. In this study, we determined concentrations of PAHs in sediments, insect larvae and adult insects collected in or adjacent to three groups of wetlands: experimental wetlands to which tailings or tailings water had been purposely added, oil sands wetlands that were located on the mine leases but which had not been experimentally manipulated and reference wetlands located near the mine leases. Alkylated PAHs dominated the PAH profile in all types of samples in the three categories of wetlands. Median and maximum PAH concentrations, especially alkylated PAH concentrations, tended to be higher in sediments and insect larvae in experimental wetlands than in the other types of wetlands. Such was not the case for adult insects, which contained higher than expected levels of PAHs in the three types of ponds. Overlap in PAH concentrations in larvae among pond types suggests that any increase in PAH levels resulting from the addition of tailings and tailings water to wetlands would be modest. Biota-sediment accumulation factors were higher for alkylated PAHs than for their parent counterparts and were lower in experimental wetlands than in oil sands and reference wetlands. Research is needed to examine factors that affect the bioavailability of PAHs in oil sands tailings- or tailings water-amended wetlands.