Total concentrations of mercury in Wisconsin (USA) lakes and rivers

We analyzed surface waters from 30 Wisconsin lakes and rivers for total mercury ([Hg]_T) and total suspended particulates (TSP) on a state-wide basis with trace-metal ‘ultraclean’ techniques. Mercury concentrations ranged from 0.3 to 2.9 ng L^?1 in lakes and from 0.7 to 8.9 ng L^?1 in rivers. TSP concentrations ranged from 0.9 to 6.6 mg L^?1 in lakes and from 3.1 to 31.4 mg L^?1 in rivers. Spatial trends were weak; however, [Hg] _T was generally higher in the spring than in the autumn of 1991. Total mercury concentration was weakly dependent on TSP with the coefficient of determination (r ²) ranging 0.06 to 0.49 across seasonal and geophysical differences.     

Toxicity of uranium to Daphnia magna

The toxicity of U to Daphnia magna was determined in acute and chronic tests. The 48-hr LC₅₀ of U (VI) in Columbia River water was 6 mg L^?1. Acute toxicity diminished by a factor of 7.5 as mean water hardness and alkalinity values increased from 70 mg L^?1. and 57 mg L^?1. to 195 mg L^?1. and 130 mg L^?1. respectively. This effect was most likely the result of complexation of uranyl ion with carbonate ions. D. magna reproduction was suppressed in Columbia River water at U concentrations between 0.5 and 3.5 mg L^?1. Potential hazards of U to aquatic life are discussed as they relate to mining practices.     

Trends in the Chemistry of Acidified Bohemian Lakes from 1984 to 1995: I. Major Solutes

Temporal changes in major solute concentrations in six Czech Republic lakes were monitored during the period 1984–1995. Four chronically-acidic lakes had decreasing concentrations of strong-acid anions (C_SA = SO₄ ^2- + NO^{3 -} + Cl^-), at rates of 3.0 to 9.0 μeq L^-1 yr^-1. Decreases in SO₄ ^2-, NO₃ ^-, and Cl^- (at rates up to 5.1 μeq L^-1 yr^-1, 3.2 μeq L^-1 yr^-1, and 0.6 μeq L^-1 yr^-1, respectively) occurred. The response to the decrease in deposition of S was rapid and annual decline of SO₄ ^2- in lake water was directly proportional to SO₄ ^2- concentrations in the acidified lakes. Changes in NO₃ ^- concentrations were modified by biological consumption within the lakes. The decline in C^SA was accompanied in the four most acidic lakes by decreases in Al_T, increases in pH at rates of 0.011 to 0.016 pH yr^{- 1}, and decreases of Ca²⁺ and Mg²⁺ (but not Na⁺) in three lakes. The acid neutralizing capacity (ANC) increased significantly in all six lakes. Increases in base cation concentrations (CB = Ca²⁺ + Na⁺ + Mg²⁺ + K⁺) were the principal contributing factor to ANC increases in the two lakes with positive ANC, whereas decrease in C_SA was the major factor in ANC increases in the four chronically-acidic lakes. The continued chemical recovery of these lakes depends on the uncertain trends in N deposition, the cycling of N in the lakes and their catchments, and the magnitude of the future decrease in S deposition.     

Low Success Rate in Re-Establishing European Perch in Some Highly Acidified Lakes in Southernmost Norway

In order to test whether major reductions in acid inputs had improved water quality sufficiently for fish populations to recover, we stocked wild European perch (Perca fluviatilis) in three highly acidified lakes that had previously supported this species, and in one limed lake. The fish, which were introduced from a local lake (donor lake), generally ranged from 12 to 16 cm in total length, and were stocked at densities of 117–177 fish ha^?1. The untreated lakes were highly acid, with minimum pH values and maximum inorganic aluminium concentrations (Al_i) during the spring of 4.6–4.7 and 118–151 µg L^?1 respectively. In the limed lake, the corresponding values for pH and Al_i ranged between 5.8 and 6.6 and 5 and 19 µg L^?1 respectively. Gill-netting in two subsequent years after the introduction yielded only a few recruits (0+) and one adult in one of the three acidified lakes in one year only. However, stocked perch reproduced successfully in both years in the limed lake. There was a significant linear relationship between the catches (CPUE) of juvenile perch (age 0+) in the different lakes in the autumn and the water quality in May (time of hatching), both in terms of Al_i (r ²=0.934, P<0.05) and pH (r ²=0.939, P<0.05). Our data suggest unsuccessful recruitment in waters of pH <5.1 and Al_i>60 µg L^?1.     

Copper Release, Speciation, and Toxicity Following Multiple Floodings of Copper Enriched Agriculture Soils: Implications in Everglades Restoration

This study characterizes the effects of water–soil flooding volume ratio and flooding time on copper (Cu) desorption and toxicity following multiple floodings of field-collected soils from agricultural sites acquired under the Comprehensive Everglades Restoration Plan (CERP) in south Florida. Soils from four field sites were flooded with three water–soil ratios (2, 4, and 6 [water] to 1 [soil]) and held for 14 days to characterize the effects of volume ratio and flooding duration on Cu desorption (volume ratio and flooding duration study). Desorption of Cu was also characterized by flooding soils four times from seven field sites with a volume ratio of 2 (water) to 1 (soil) (multiple flooding study). Acute toxicity tests were also conducted using overlying waters from the first flooding event to characterize the effects of Cu on the survival of fathead minnows (Pimephales promelas), cladocerans (Daphnia magna), amphipods (Hyalella azteca), midges (Chironomus tentans), duckweed (Lemna minor), and Florida apple snails (Pomacea paludosa). Acute tests were also conducted with D. magna exposed to overlying water from the second and third flooding events. Results indicate that dissolved Cu concentrations in overlying water increased with flooding duration and decreased with volume ratio. In the multiple flooding study, initial Cu concentrations in soils ranged from 5 to 223 mg/kg (dw) and were similar to Cu concentration after four flooding events, indicating retention of Cu in soils. Copper desorption was dependent on soil Cu content and soil characteristics. Total Cu concentration in overlying water (Cu_w) was a function of dissolved organic carbon (DOC), alkalinity, and soil Cu concentration (Cu_s): log(Cu_w)?=?1.2909?+?0.0279 (DOC)?+?0.0026 (Cu_s)???0.0038 (alkalinity). The model was validated and highly predictive. Most of the desorbed Cu in the water column complexed with organic matter in the soils and accounted for 99% of the total dissolved Cu. Although total dissolved Cu concentrations in overlying water did not significantly decrease with number of flooding events, concentrations of free Cu²⁺ increased with the number of flooding events, due to a decrease in DOC concentrations. The fraction of bioavailable Cu species (Cu²⁺, CuOH⁺, CuCO₃) was also less than 1% of the total Cu. Overlying water from the first flooding event was only acutely toxic to the Florida apple snail from one site. However, overlying water from the third flooding of six out of seven soils was acutely toxic to D. magna. The decrease in DOC concentrations and increase in bioavailable Cu²⁺ species may explain the changes in acute toxicity to D. magna. Results of this study reveal potential for high Cu bioavailability (Cu²⁺) and toxicity to aquatic biota overtime in inundated agricultural lands acquired under the CERP.     

Toxicity of Sb and Cu in Sewage Sludge to Terrestrial Plants (Lettuce,Oat, Radish), and of Sludge Elutriate to Aquatic Organisms (Daphnia and Lemna) and its Interaction

Antimony (Sb) and Copper (Cu) are two metals of major concern in sewage sludge. Antimony because its use in society is increasing and this might lead to increased Sb concentrations in sludge. Copper because its total volume in use in society is large and because of corrosion from water pipes it is most difficult to reduce the Cu concentrations in sludge. Fresh digested sewage sludge was spiked with Cu or Sb and the sludge was cultivated with oat (Avena sativa), lettuce (Lactuca sativa) or radish (Raphanus sativus). Elutriates from the cultivated sludge were tested for toxicity with Lemna minor (7-d growth) and Daphnia magna (48 h immobility). Before cultivation the elutriates were toxic to Lemna and Daphnia due to high concentrations of ammonia (NH₃) and nitrite (NO₂ ^-). Cultivation decreased the concentrations of both NH₃ and NO₂ ^-, thereby reducing the impact of these compounds in the toxicity tests. Cultivation also decreased the metal concentrations and pH. Daphnia magna was the most sensitive test organism in this study with a 48 h EC₅₀ of 1130 mg Cu kg^-1 dry wt and 5 mg Sb kg^-1 dry wt in elutriates from sludge cultivated with oat. In sludge cultivated with radish the 48 h EC₅₀ was 1700 mg Cu kg^-1 dry wt and 22 mg Sb kg^-1 dry wt. The effect of Cu could be predicted by pH and Cu concentrationin the elutriate, but the effect of Sb could not solely be explained by its concentration in the elutriate.     

Trends in Water Chemistry of Acidified Bohemian Lakes from 1984 to 1995: II. Trace Elements and Aluminum

The concentrations of Al, Be, Cd, Cu, F, Fe, Mn, Pb, and Zn were monitored in five glacial lakes and one man-made lake in the southwestern part of the Czech Republic. The lakes had median pHs of 4.4 to 6.5 during 1984 to 1995. Decreases in the concentrations of Mn and Pb occurred in five acidified lakes. The concentrations of Al_T, Be, Cd, and F decreased in the four chronically acidified lakes, Zn decreased in two lakes. Concentrations of Cu and Fe remained unchanged. The decreases in Be, Mn, and Zn concentrations were proportional to the decrease in C_SA (C_SA = SO₄ ^2- + NO₃ ^-+ Cl^-); decreases in Al_T, Cd, and Pb concentrations were proportionately higher, while F was lower. The greater decrease in the Pb concentrations (61 to 79%, at a rate up to 0.15 μg L^-1yr^-1) was caused by pronounced decreases in deposition of Pb derived from mobile sources. The decrease of Al_T concentrations was dominated by a decrease in Al³⁺, whose concentration decreased by 51 to 86%. The concentrations of complexes Al(OH)²⁺, Al(OH)₂ ⁺, AlF²⁺, and AlH₃SiO₄ ²⁺ also decreased. The decrease in the concentrations of inorganic forms of Al (Al_i) compensated 65% of the decrease in C_SA. The Cd concentrations were highly variable in the years 1986 to 1988 because of variable amounts of accumulation on particles.     

Bio-accumulation and metabolic effects of zinc on marine fouling dreissinid bivalve,Mytilopsis sallei (Recluz)

Zinc (Zn) toxicity to a marine fouling dreissinid bivalveMytilopsis sallei was investigated and the safe concentration of Zn was determined for this bivalve. In acute toxicity tests onM. sallei the 96 h LC₅₀ value for Zn is found to be 8.364 mg 1^?1. The results suggest that Zn has the lowest toxic effect onM. sallei when compared to copper and mercury. Effect of Zn on the oxygen consumption ofM. sallei was studied. Sub-lethal concentrations of Zn functioned as respiratory depressants. Accumulation of Zn was investigated in relation to exposure period and concentration inM. sallei. Zn accumulation was found to be sensitive to both concentration of Zn and exposure time. The effect of exposure time and concentration on body biochemical components was also studied inM. sallei. This accumulated Zn has resulted in impairment of carbohydrate metabolism and protein utilisation.     

Seasonal and long-term temporal patterns in the chemistry of Adirondack lakes

There is considerable interest in the recovery of surface waters from acidification by acidic deposition. The Adirondack Long-Term Monitoring (ALTM) program was established in 1982 to evaluate changes in the chemistry of 17 Adirondack lakes. The ALTM lakes exhibited relatively uniform concentrations of SO₄ ^2?. Lake-to-lake variability in acid neutralizing capacity (ANC) was largely due to differences in the supply of basic cations (Ca²⁺, Mg²⁺, K⁺, Na⁺; C_B) to drainage waters. Lakes in the western and southern Adirondacks showed elevated concentrations of NO₃ ^?, while lakes in the central and eastern Adirondacks had lower NO₃ ^? concentrations during both peak and base flow periods. The ALTM lakes exhibited seasonal variations in ANC. Lake ANC was maximum during the late summer or autumn, and lowest during spring snowmelt. In general Adirondack lakes with ANC near 100 Μeq L^?1 during base flow periods may experience decreases in ANC to near or below 0 Μeq L^?1 during high flow periods. The ALTM lakes have exhibited long-term temporal trends in water chemistry. Most lakes have demonstrated declining SO₄ ^2?, consistent with decreases in SO₂ emissions and SO₄ ^2? in precipitation in the eastern U.S. Reductions in SO₄ ^2? have not coincided with a recovery in ANC. Rather, ANC values have declined in some ALTM lakes. This pattern is most likely due to increasing concentrations of NO₃ ^? that occurred in most of the ALTM drainage lakes.     

Development of QSAR's in soil ecotoxicology: Earthworm toxicity and soil sorption of chlorophenols,chlorobenzenes and chloroanilines

Soil adsorption and the toxicity of four chloroanilines for earthworms were investigated in two soil types. The toxicity tests were carried out with two earthworm species, Eisenia andrei and Lumbricus rubellus. LC₅₀ values in mg kg^?1 dry soil were recalculated towards molar concentrations in pore water using data from soil adsorption experiments. An attempt has been made to develop Quantitative Structure Activity Relationships (QSAR's) using these results and data on five chlorophenols and dichloroaniline in four soils and five chlorobenzenes in two soils published previously (Van Gestel and Ma, 1988, 1990; Van Gestel et al., 1991). Significant QSAR relationships were obtained between 1) adsorption coefficients (log K _om ) and the octanol/water partition coefficient (log k _ow ), and 2) LC₅₀ values (in itμmol L^?1 soil pore water) and log K _ow . It can be concluded that both earthworm species tested are equally sensitive to chlorobenzenes and chloroanilines, E. andrei is more sensitive than L. rubellus to chlorophenols.     

Response to a smelter closure in Cascade mountain lakes

A statistically significant decrease in sulfate was observed in high elevation Cascade lakes during 1983 through 1988. The total decrease averaged 2.2 μeq L^?1 in two slow-flush lakes and 4.2 μeq L^?1 in three fast-flush lakes for 1983–1985 vs 1986–1988, respectively. Coincident with these changes in sulfate concentrations were a sharp decrease of SO₂ emissions from the ASARCO smelter (100 km SE of the lakes), from 87 to 70 kt yr^?1 during 1983–1984 to 12 in 1985, the year of its closure, and a gradual change in SO₂ emissions from Mt. St. Helens, from 39 to 27 during 1983–1984 to 5 in 1988. The sharpest decreases occurred in non-marine sulfate in fast-flush lakes from 1984 to 1985 (about 2 μeq L^?1) and in slow-flush lakes from 1985 to 1986 (1 μeq L^?1, which point to the ASARCO closure as the sole cause. However, some of the more gradual decline in non-marine sulfate observed during 1983 through the 1988 sampling periods may have been due to a slow washout of sulfate enriched ash from the 1980 Mt. St. Helens' eruption. Sulfate concentrations in precipitation also declined significantly by about 2 μeq L^?1, but changes in volume-weighted sulfate content were not significant. Lake alkalinity did not show a consistent increase in response to decreased sulfate. This was probably due to either watershed neutralization of acidic deposition or the greater variability in alkalinity measurements caused by small changes in acidic deposition making it difficult to detect changes.     

Acute toxicity of water soluble fractions derived from a coal liquid (SCR-II) to three aquatic organisms

Acute toxicity screening tests were conducted with water soluble fractions (WSFs) of a solvent refined coal (SRC-II) liquid from a pilot plant and three reference organisms: the cladoceran Daphnia magna, the fathead (FH) minnow Pimephales promelas, and larvae of the midge fly Chironomus tentans. Stock WSFs typically contained 900 to 1100 mg l^?1 total carbon (TC) and 700 to 800 mg l^?1 total dye complexable phenolics, with lower concentrations of aromatic and saturate hydrocarbons and N compounds. Under standard test conditions (temperature 20 °C, pH 7.3 to 8.2 and hardness 65 to 80 mg l^?1 CaCO₃), mean LC50 values in mg l^? TC were 3.3 for daphnia, 11.l for FH minnow, and 13.7 for midge larvae. Acute toxicity was also examined under other water quality conditions (temperature 10 or 25 °C, pH 6.0 or 6.5, and hardness ? 180 to 220 mg 1^?1 CaCO₃). The coal liquid was less toxic to daphnids at 10 °C than at 20 or 25 °C, but response of other organisms at different temperatures varied. The pH of the liquid had little effect on toxicity values. All organisms were less susceptible in hard water. Chemical compositions of stock WSFs were similar, suggesting that temperature, pH, and hardness had little effect on solubility of major synfucl components. Dilution indexes for stock WSFs were higher than for petroleum oils, and reflect the greater solubility of chemicals from the liquified coal in freshwater.     

Effect of fulvic acids on lead-induced oxidative stress to metal sensitive Vicia faba L. plant

Lead (Pb) is a ubiquitous environmental pollutant capable to induce various morphological, physiological, and biochemical functions in plants. Only few publications focus on the influence of Pb speciation both on its phytoavailability and phytotoxicity. Therefore, Pb toxicity (in terms of lipid peroxidation, hydrogen peroxide induction, and photosynthetic pigments contents) was studied in Vicia faba plants in relation with Pb uptake and speciation. V. faba seedlings were exposed to Pb supplied as Pb(NO₃)₂ or complexed by two fulvic acids (FAs), i.e. Suwannee River fulvic acid (SRFA) and Elliott Soil fulvic acid (ESFA), for 1, 12, and 24?h under controlled hydroponic conditions. For both FAs, Pb uptake and translocation by Vicia faba increased at low level (5?mg?l^?1), whereas decreased at high level of application (25?mg?l^?1). Despite the increased Pb uptake with FAs at low concentrations, there was no influence on the Pb toxicity to the plants. However, at high concentrations, FAs reduced Pb toxicity by reducing its uptake. These results highlighted the role of the dilution factor for FAs reactivity in relation with structure; SRFA was more effective than ESFA in reducing Pb uptake and alleviating Pb toxicity to V. faba due to comparatively strong binding affinity for the heavy metal.     

Sulfur vs. silica retention in oligotrophic lake sediments: Test of a simple residence time model

Limnologists have modeled solute retention (% of input) in lake sediments using the parameter: 100 k _s {(z:t _w +k _s}^?1, wherek _s is an empirical mass transfer coefficient or ‘sedimentation velocity’ (m yr^?1), z is lake mean depth (m), andt _w is lake hydraulic residence time (yr). This flushing or residence time model was tested against sulfate and silica concentrations in lakes of the northeastern and northcentral U.S.A., using data collected during the U.S. EPA's Eastern Lake Survey. This parameter failed to predict intra-regional variations in lake sulfate at fall turnover, but was consistently negatively correlated with silica in each of the regional lake populations. However, except in the western section of the Upper Peninsula of Michigan, lake sulfate was everywhere inversely dependent on DOC [mean slope=?0.020(SE=0.03) meq mM^?1]. Sulfur retention in aquatic environments appears more closely coupled to organic carbon and trophic state, than to variations in hydraulic residence time.     

Critical Loads of Acid Deposition for Wilderness Lakes in the Sierra Nevada (California) Estimated by the Steady-State Water Chemistry Model

Major ion chemistry (2000–2009) from 208 lakes (342 sample dates and 600 samples) in class I and II wilderness areas of the Sierra Nevada was used in the Steady-State Water Chemistry (SSWC) model to estimate critical loads for acid deposition and investigate the current vulnerability of high elevation lakes to acid deposition. The majority of the lakes were dilute (mean specific conductance?=?8.0 μS cm^?1) and characterized by low acid neutralizing capacity (ANC; mean?=?56.8 μeq L^?1). Two variants of the SSWC model were employed: (1) one model used the F-factor and (2) the alternate model used empirical estimates of atmospheric deposition and mineral weathering rates. A comparison between the results from both model variants resulted in a nearly 1:1 slope and an R ² value of 0.98, suggesting that the deposition and mineral weathering rates used were appropriate. Using an ANC_limit of 10 μeq L^?1, both models predicted a median critical load value of 149 eq ha^?1 year^?1 of H⁺ for granitic catchments. Median exceedances for the empirical approach and F-factor approach were ?81 and ?77 eq ha^?1 year^?1, respectively. Based on the F-factor and empirical models, 36 (17 %) and 34 (16 %) lakes exceeded their critical loads for acid deposition. Our analyses suggest that high elevation lakes in the Sierra Nevada have not fully recovered from the effects of acid deposition despite substantial improvement in air quality since the 1970s.     

Using the Caenorhabditis elegans soil toxicity test to identify factors affecting toxicity of four metal ions in intact soil

A previously developed soil toxicity test for rapidly determining the toxicity of chemicals to the soil-dwelling nematode Caenorhabditis elegans (Donkin and Dusenbery, 1993) was used to measure the toxicity of four metals (Zn²⁺, Cd²⁺, Cu²⁺, and Pb²⁺) added to four soils common to the southeastern United States. Nematode survival after a 24-hour exposure in the presence of a bacterial food source was assessed. All soils reduced the toxicity of most metal ions compared to solutions without soil. Pb was the most strongly affected, while Cd toxicity was not much influenced by the soils. Correlations between the LC₅₀S and various soil or metal characteristics were determined. No significant correlation was found between LC₅₀s and many soil characteristics commonly cited as having large effects on soil bioavailability of metals. Although sample size was limited, the indication was that bioavailability of metals to nematodes is determined by a complex array of many interacting soil, as well as metal, properties. Comparison of the relative mobilities of these ions in other soils with the relative toxicity measured here suggests that mobility may be a good predictor of toxicity. The C. elegans soil toxicity test is shown to be as sensitive and more rapid than the commonly used earthworm soil toxicity test.     

High Carbon Dioxide Evasion from an Alpine Peatland Lake: The Central Role of Terrestrial Dissolved Organic Carbon Input

We measured carbon dioxide (CO₂) fluxes across air?Cwater interface with floating chambers in Lake Medo (a small, shallow lake in peatland) on the eastern Tibetan Plateau in the warm season of 2009. During the study period, mean CO₂ fluxes was 488.63?±?1,036.17?mg?CO₂?m^?2?h^?1. The flux rate was high compared to those of lakes in other regions, and represented a ??hotspot?? of CO₂ evasion. Temporal variation of CO₂ flux was significant, with the peak value in the beginning and lowest point in the end of warm season. High concentration of dissolved organic carbon (DOC) in lake water (WDOC) was found to highly correlated to CO₂ flux (R?=?0.47, P?<?0.01, n?=?54). Besides, fluorescence index of WDOC showed its terrestrial origin character. In accordance with lakes in northern and boreal regions, terrestrial DOC concentration in water column was the most important regulator of CO₂ flux from this lake. We suggest that large area of peatlands in catchments support high concentration of DOC in this lake, and consequently high CO₂ evasion.     

Cadmium Aqueous Exposure and Uptake of the Estuarine Isopod Cyathura carinata

We studied the isotopic composition of organic matter in the sediments of eight mountain lakes located in the Tatra Mountains (Western Carpathians, Poland). The sediments of the lakes were fine and course detritus gyttja, mud, and sand. The total organic carbon content varied from 0.5 to 53 %. The C/N ratio indicated that in-lake primary production is the major source of the organic matter in the lakes located above the treeline, whereas terrestrial plant fragments are the major organic compounds in the sediments of dystrophic forest lakes. We also found that a clear trend of isotopic curves toward lower values of δ ¹³C and δ ¹⁵N (both ~3 ‰) began in the 1960s. This trend is a sign of the deposition of greater amounts of NO _x from the combustion of fossil fuels, mainly by vehicle engines. The combustion of fossil fuels in electric plants and other factories had a smaller influence on the isotopic composition. This trend has been weaker since the 1990s. Animal and human wastes from pastures and tourism had a surprisingly minor effect on lake environments. These data are contrary to previous data regarding lake biota and suggest the high sensitivity of living organisms to organic pollution.     

Biochemical parameters in Tubifex tubifex as an integral part of complex sediment toxicity assessment

Background, aim, and scope

Restoration of lakes and reservoirs with extensive cyanobacterial water bloom often requires evaluation of the sediment quality. Next to the chemical analysis of known pollutants, sediment bioassays should be employed to assess toxicity of the present contaminants and to make predictions of associated risk. Brno reservoir in the Czech Republic is a typical example of water bodies with long-term problems concerning cyanobacterial water blooms. Comprehensive assessment of reservoir sediment quality was conducted since successful reservoir restoration might require sediment removal. An important part of this survey focused on an examination of the utility of Tubifex tubifex and its sublethal biochemical markers for the assessment of direct sediment toxicity.

Materials and methods

This complex study included chemical analysis of contaminants (heavy metals, organic pollutants), ecotoxicity testing of sediment elutriates (tests with Daphnia magna, Pseudomonas putida, Sinapis alba, Scenedesmus subspicatus), and other parameters. We have tested in more detail the applicability of T. tubifex as a test organism for direct evaluation of contact sediment toxicity. Survival tests after 14 days of exposure were complemented by an assessment of parameters serving as biomarkers for sublethal effects [such as total glutathione content (GSH), activities of the enzymes glutathione transferase (GST), glutathione peroxidase (GPx), and glutathione reductase (GR)]. The data matrix was subjected to multivariate analysis to interpret relationships between different parameters and possible differences among locations.

Results

The multivariate statistical techniques helped to clearly identify the more contaminated upstream sites and separate them from the less contaminated and reference samples. The data document closer relationships of the detected sediment contamination with results of direct sediment exposure in the T. tubifex test regarding mortality but namely regarding the sublethal endpoints rather than the results obtained with other test organisms exposed to sediment elutriates. Aside from the reduction in T. tubifex survival, the sediments with organic pollution caused an increase in glutathione content and increased activities of glutathione S-transferase and glutathione peroxidase in the exposed T. tubifex worms.

Discussion

Results of our study confirm the suitability of T. tubifex for toxicity testing of raw waters and sediments. This longer-lasting direct contact test has proven more sensitive and appropriate to reflect a lower level of pollution than do the elutriate tests. Sensitive biochemical changes in T. tubifex, including an elevation in GSH levels and GST activities, reflect a general stimulation of detoxification metabolisms in the presence of xenobiotics. The results also suggest an important role of glutathione and related enzymes in detoxification processes and possible involvement of oxidative stress in toxicity mechanisms in benthic sediment-dwelling worms such as T. tubifex.

Conclusions

The complex assessment has identified the more contaminated samples with locally increased concentration of organic pollutants and significant ecotoxicity. The direct sediment contact test with T. tubifex and especially the biochemical parameters corresponded better to the lower level of pollution than the other tests with sediment elutriates. Despite its greater time and cost demands, the direct sediment contact test can provide a more realistic picture of exposure.

Recommendations and perspectives

Sediment bioassays should always be included as an integral part of the sediment quality assessment. The direct contact tests also take into account the more hydrophobic pollutants that are not easily available for the water elution but can still be accessible to the organisms. The T. tubifex test is a suitable option for contact sediment toxicity tests also because these animals show measurable sublethal biochemical changes that can be associated with this exposure.     

Effects of azoxystrobin,chlorothalonil, and ethoprophos on the reproduction of three terrestrial invertebrates using a natural Mediterranean soil

The potential terrestrial toxicity of three pesticides, azoxystrobin, chlorothalonil, and ethoprophos was evaluated using reproduction ecotoxicological tests with different non-target species: the collembolan Folsomia candida, the earthworm Eisenia andrei, and the enchytraeid Enchytraeus crypticus. All reproduction tests were performed with natural soil from a Mediterranean agricultural area (with no pesticide residues) in order to improve the relevance of laboratory data to field conditions. Controls were performed with natural and standard artificial soil (OECD 10% OM). The fungicide azoxystrobin showed the highest toxicity to earthworms (EC₅₀ = 42.0 mg a.i. kg⁻¹ dw soil). Collembolans were the most sensitive taxa in terms of sublethal effects of chlorothalonil with an EC₅₀ of 31.1 mg a.i. kg⁻¹ dw soil followed by the earthworms with an EC₅₀ of 40.9 mg a.i. kg⁻¹ dw soil. The insecticide ethoprophos was the most toxic to collembolans affecting their reproduction with an EC₅₀ of 0.027 mg a.i. kg⁻¹ dw soil. Enchytraeids were generally the least sensitive of the three species tested for long-term effects. Earthworms were not always the most sensitive species, emphasizing the need to increase the number of mandatory assays with key non-target organisms in the environmental risk assessment of pesticides.