Nowadays trace metal contamination of soils represents an important environmental hazard. Nevertheless, the use of some secondary waste products as amendments may restore the common soil functions. This paper focuses on the chemical and biological influence of wood biochar (BC), wood ash (WA) and humic substances (HS), alone and in the mixtures, on a heavily multi-contaminated sandy loam soil. The soil was amended by above-mentioned materials to follow a pH-increasing design (pHCa from 6.0 to 6.5, 7.0 and 7.5); soil samples were analyzed after 3, 30, and 60 days using a set of variables, namely the plant-available trace element concentrations (Cu, Cd, and Zn), microbial biomass carbon (Cmic), and microbial quotient (qCO2), as well as toxicity to Sinapis alba and Daphnia magna. Wood ash and WA + HS were the most efficient treatments to decrease mobile Cd and Zn concentrations in the soil, while HS, BC, and BC + HS combinations were the most effective in reducing the Cu mobility. The effect of BC and WA on the Cmic and qCO2 was mostly negative, whereas adding HS markedly increased Cmic and reduced qCO2 in soil. After amendment applications, the root elongation of mustard was significantly increased in HS and combined treatments (BC + HS, WA + HS). Additionally, BC + HS, WA + HS and WA 8.4% significantly decreased the toxicity of leachates to D. magna to the low-, or non-toxic levels. Our results suggest that the combination of amendments with HS can be a suitable remediation strategy for heavily contaminated soils.

Given their increasingly widespread application, the toxic effects of ionic liquids (ILs) have become the subject of significant attention in recent years. Therefore, the present study assessed the acute toxic effects of 1-alkyl-3-methylimidazolium nitrate ([Cnmim]NO3 (n = 2, 4, 6, 8, 10, 12)) on Chlorella vulgaris and Daphnia magna. The sensitivity of the tested organism Daphnia magna and the investigated IL concentrations in water using high-performance liquid chromatography (HPLC) were also evaluated to demonstrate the reliability of the present study. The results illustrated that Daphnia magna is indeed sensitive to the reference toxicant and the investigated ILs were stable in the aquatic environment. The 50% effect concentration (EC50) was used to represent the acute toxic effects on Chlorella vulgaris and Daphnia magna. With the increasing alkyl-chain lengths, the toxicity of the investigated ILs increased in both the test organisms. Accordingly, the alkyl-chain lengths can cause significantly toxic effects on aquatic organisms, and Daphnia magna are much more sensitive than Chlorella vulgaris to the imidazolium-based ILs used in the present study. Furthermore, the present study provides more information on the acute toxic effects of 1-alkyl-3-methylimidazolium nitrate.

Understanding the processes that regulate contaminant impacts in nature is an increasingly important challenge. For insecticides in surface waters, the ability of aquatic plants to sorb, or bind, hydrophobic compounds has been identified as a primary mechanism by which toxicity can be mitigated (i.e. the sorption-based model). However, recent research shows that submerged plants can also rapidly mitigate the toxicity of the less hydrophobic insecticide malathion via alkaline hydrolysis (i.e. the hydrolysis-based model) driven by increased water pH resulting from photosynthesis. However, it is still unknown how generalizable these mitigation mechanisms are across the wide variety of insecticides applied today, and whether any general rules can be ascertained about which types of chemicals may be mitigated by each mechanism. We quantified the degree to which the submerged plant Elodea canadensis mitigated acute (48-h) toxicity to Daphnia magna using nine commonly applied insecticides spanning three chemical classes (carbamates: aldicarb, carbaryl, carbofuran; organophosphates: malathion, diazinon, chlorpyrifos; pyrethroids: permethrin, bifenthrin, lambda-cyhalothrin). We found that insecticides possessing either high octanol-water partition coefficients (log Kow) values (i.e. pyrethroids) or high susceptibility to alkaline hydrolysis (i.e. carbamates and malathion) were all mitigated to some degree by E. canadensis, while the plant had no effect on insecticides possessing intermediate log Kow values and low susceptibility to hydrolysis (i.e. chlorpyrifos and diazinon). Our results provide the first general insights into which types of insecticides are likely to be mitigated by different mechanisms based on known chemical properties. We suggest that current models and mitigation strategies would be improved by the consideration of both mitigation models.

Mainly due to automobile traffic, but also due to other sources, the platinum group elements (PGE) platinum (Pt), palladium (Pd) and rhodium (Rh) are introduced into aquatic biotopes where they accumulate in sediments of lakes and rivers. However, the toxicity of these noble metals to aquatic organisms is not well understood and especially toxicity studies under standardized condition are lacking. Thus, the toxicity of Pt, Pd and Rh to Daphnia magna was tested in single metal exposure experiments according to OECD guideline 202. Immobility and lethality was recorded after 24 h and 48 h of exposure and EC50 and LC50, respectively, were determined. As the nominal exposure concentration of Pd differed significantly from the quantified concentration, the control of the real exposure concentration by chemical analysis is mandatory, especially for Pd.The toxicity decreased in the order Pd > Pt ≫ Rh with e.g. LC50(48 h) values of 14 μg/L for Pd, 157 μg/L for Pt and 56,800 μg/L for Rh. The exposure period had a clear effect on the toxicity of Pt, Pd and Rh. For Pt and Rh the endpoint immobility was more sensitive than the endpoint lethality whereas Pd toxicity was similar for both endpoints. The Hill slopes, which are a measure for the steepness of the concentration-response curves, showed no significant discrepancies between the different metals.The binary metal exposure to Pt and Pd revealed a more-than-additive, i.e. a synergistic toxicity using the toxic unit approach. The present study is a start to understand the toxicity of interacting PGE. The modes of action behind the synergistic effect are unclear.

Toxicity of Cu and Cu-based nanoparticles (NPs) to aquatic biota is usually mitigated in natural freshwater compared to organics-free artificial freshwater. The main aim of this study was to evaluate whether mitigated toxicity is accompanied by lower total copper body burden in the freshwater crustacean Daphnia magna and whether CuO NPs are more hazardous in this aspect than soluble Cu salts.Total copper body burden in different media (OECD202 artificial freshwater and two natural freshwaters) was measured by a relatively novel technique - total reflection X-ray fluorescence (TXRF) spectroscopy - which proved suitable for the analysis of individual juvenile daphnids. Mean copper body burden was 2.8–42 times higher in daphnids exposed to CuO NPs (0.05 mg Cu/L and 1 mg Cu/L) than in daphnids exposed to equal or equitoxic concentrations (0.025 mg Cu/L and 0.05 mg Cu/L) of CuSO4. Using natural freshwater instead of artificial one resulted in increased copper burden after exposure to CuO NPs but not after exposure to Cu salt. After 24 h post-exposure depuration in the presence of algae Raphidocelis subcapitata, total copper body burden in daphnids exposed to CuO NPs sharply decreased while in daphnids exposed to Cu salt it did not. Despite the CuO NP toxicity mitigating effect of natural freshwater, total copper body burden of aquatic crustaceans in natural waterbodies may be greater than could be predicted based on the results obtained using artificial freshwater as the test medium.

Increasing applications of titanium dioxide nanoparticles (nano-TiO2) have intensified the risk of environmental contamination. Since nano-TiO2 can absorb metals and be consumed as ‘food’ by zooplankton but also can interact with phytoplankton, they could significantly disturb the existing metal assimilation patterns. In the present study, we quantified the dietary assimilation of Cd and Zn from nano-TiO2 and algae (Chlamydomonas reinhardtii) at comparable particle concentrations as well as in complex food environment (variable food quality and quantity) in a freshwater zooplankton Daphnia magna using the radiotracer technique. For both nano-TiO2 and algae as food, the feeding food quality and depuration food quantity significantly affected the assimilation efficiencies (AEs) of Cd and Zn. At feeding food quantity of 1 mg/L to 10 mg/L without food in depuration, the AEs of Cd and Zn from nano-TiO2 were lower than those from algae. When food was added during depuration, the influences of nano-TiO2 on metal AEs were variable due to the differential effects of food quantity on the gut passage of nano-TiO2 and algae. Furthermore, mixed nano-TiO2 and algae had the lowest metal AEs compared to sole nano-TiO2 or algae as a result of interaction between nano-TiO2 and algae during feeding. Overall, this study showed the distinguishing metal AEs between nano-TiO2 and algae, and that nano-TiO2 could significantly reduce the existing metal AEs from algae. More attention should be paid to the potential roles of nano-TiO2 in disturbing metal assimilation in the environmental risk assessments of nanoparticles.

The complex QDs-Indolicidin (QDs-Ind) has been previously shown to be a good antimicrobial system with a low acute toxicity on Daphnia magna (D. magna). However, multigenerational effects caused by exposure to QDs-Ind and after subsequent recovery are still unknown. In this study, we performed multigenerational exposure tests and we evaluated individual fitness, population growth, DNA alteration, expression of Dhb (haemoglobin), Vtg (vitellogenin), CYP4 (cytochrome P450s CYP4 family), and CYP314 (cytochrome P450s mitochondrial family 314) genes on three generation of D. magna. Results showed that the total amount of eggs produced per female and total number of brood per female and body lengths were significantly decreased, Dhb, CYP4 were upregulated while Vtg was down-regulated except at reproduction days when it was slightly up-regulated under QDs-Ind exposure. Random Amplification of Polymorphic DNA (RAPD) method has proven to be useful to qualitative assess of DNA damage during generation and to underline modification in somatic or germinal cells. The results of the study suggest that effects of chronic exposure cannot be ignored.

Little is known about the potential toxicity of Cu nanoparticles (nCu), Cr nanoparticles (nCr), and their mixtures to aquatic organisms. To fill this gap, a comprehensive toxicity assessment was conducted using Daphnia magna as a test organism, including a 48-h acute toxicity test, a 21-day chronic test, and a feeding experiment. Four biomarkers were estimated after exposure to nCu, nCr, and their mixtures for 7 days, including acetylcholinesterase (AChE), catalase (CAT), superoxide dismutase (SOD), and glutathione S-transferase (GST). The results at all endpoints showed that nCu was more toxic than nCr. The 48-h median lethal concentration values of nCu and nCr were 0.63 and 1.57 mg/L, respectively. Significant inhibition of reproduction and growth of D. magna was found, and the intrinsic rate of natural increase was a sensitive parameter for nCu and nCr during the 21-day exposure. A concentration-dependent decrease in filtration and ingestion was observed which was consistent with inhibition of reproduction and growth of D. magna. The biochemical responses revealed an increase in GST activity and decrease in AChE activity, while SOD and CAT activities were increased at low concentrations and decreased at high concentrations for all exposures. Collectively, our results confirmed that nanoscale Cu and Cr can exert negative effects at different levels on D. magna.

Currently, there are large areas of soils contaminated with hexachlorocyclohexane (HCH) isomers which are included in the group of persistent organic pollutants. For the bioremediation of such soils, a new HCH-degrading Rhodococcus wratislaviensis strain Ch628 was isolated from long-term organochlorine contaminated soils. The strain Ch628 was able to degrade 32.3% γ-hexachlorocyclohexane (γ-HCH/lindane), 25.2% hexachlorobenzene, and 100% chlorobenzene in resting cell conditions. The strain Ch628 was bioaugmented in chronically HCH-contaminated soil. The results showed that the bioaugmentation of contaminated soil with the strain Ch628 led to HCH degradation. In the bioaugmented system, the efficiency of HCH removal at the initial concentration of about 238.7 ± 4.9 mg kg⁻¹ soil was 44.8%, while the system with indigenous microflora (without R. wratislaviensis strain Ch628) and the system with abiotic control removed 33.3 and 16.4% of this compound during the same period, respectively. Strain Ch628 could effectively degrade α-, β-, and γ-isomers of HCH (77.1, 100, and 100%, respectively) and heptachlorocyclohexane (69.9%) in the model soil systems. Moreover, the bioaugmentation with the strain Ch628 led to degradation of tri-, tetra-, and penta-chlorobenzenes, which are of HCH degradation metabolites. For the first time, it was found that the bioaugmentation with the bacterial strain Rhodococcus wratislaviensis Сh628 led to a significant reduction of the toxicity of the HCH-contaminated soil for the test organisms, such as Chlorella vulgaris Beijer and Daphnia magna Straus.

A comprehensive ecotoxicity assessment of three different nanosized TiO₂ (with 16, 36 and 89 nm particle diameter) and one microscale TiO₂ suspension (with 3264 nm particle diameter) was carried out with a special emphasis on the relation between product characteristics and toxic effect. The applied test battery included the combination of modified standardized tests (Aliivibrio fischeri bioluminescence inhibition test, Lemna minor growth inhibition test), and nonstandardized bioassays with unconventional physiological endpoints (Tetrahymena pyriformis phagocytic activity, the Daphnia magna heartbeat rate). Based on the lowest significant effect values, the tested aquatic organisms were the most sensitive to the microscale TiO₂ suspension (with 3264 nm particle size). Although the three nanoscale TiO₂ particles were aggregated in the A. fischeri and the L. minor growth media, significant inhibition rates were experienced at 0.1 and at 1 μg L─¹ concentration of nTiO₂ suspensions with 16 and 36 nm primary particle size, respectively. Larger aggregates may have also high impact on biological organisms. In case of the D. magna heartbeat rate test rapid agglomeration was avoided, but lower responses were found compared to other investigated systems. The short term T. pyriformis phagocytic activity test demonstrated outstanding sensitivity; three TiO₂ suspensions were significantly toxic even at 0.1 μg L─¹. The consequences of our study clearly indicated that nanoscale TiO₂ may have an impact on the aquatic ecosystem which is strongly influenced by aggregation. The effect of exposure duration and concentration as contributing factors in nano-titanium dioxide mediated toxicity was also demonstrated.