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Environmental science & technology 56(23), 16546-16566 (2022). doi:10.1021/acs.est.2c02976, Published by American Chemical Society, Columbus, Ohio

Chemosphere : chemistry, biology and toxicology as related to environmental problems 232, 164-170 (2019). doi:10.1016/j.chemosphere.2019.05.038, Published by Elsevier Science, Amsterdam [u.a.]

The influence of an ionic functional group on the fate of chemicals in the environment, especially the formation of non-extractable residues (NER), has not been systematically investigated. Using 4-n-dodecylphenol[phenylring

Fish are warned about the presence of predators via an alarm cue released from the skin of injured conspecifics. The detection of this odor inherently initiates an antipredator response, which increases the chance of survival for the individual. In the present study, we assessed the effect of three commonly used pesticides on the antipredator response of zebrafish (Danio rerio). For this, we analyzed the behavioral response of zebrafish to a conspecific skin extract following 24 h of exposure to the respective contaminants. Results demonstrate that fish exposed to 20 μg/L of the organophosphate insecticide chlorpyrifos significantly reduced bottom-dwelling and freezing behavior, suggesting an impairment of the antipredator response. For the urea-herbicide linuron and the pyrethroid insecticide permethrin, no statistically significant effects could be detected. However, linuron-exposed fish appeared to respond in an altered manner to the skin extract; some individuals failed to perform the inherent behaviors such as erratic movements and instead merely increased their velocity. Furthermore, we determined whether zebrafish would avoid the pesticides in a choice maze. While fish avoided permethrin, they behaved indifferently to chlorpyrifos and linuron. The study demonstrates that pesticides may alter the olfactory-mediated antipredator response of zebrafish in distinct ways, revealing that particularly fish exposed to chlorpyrifos may be more prone to predation.

Global demand for alternative energy sources increases due to concerns regarding energy security and greenhouse gas emissions. However, little is known regarding the impacts of biofuels to the environment and human health even though the identification of such impacts is important to avoid biofuels leading to undesired effects. In this study mutagenicity and genotoxicity of the three biofuel candidates ethyl levulinate (EL), 2-methyltetrahydrofuran (2-MTHF) and 2-methylfuran (2-MF) were investigated in comparison to two petroleum-derived fuels and a biodiesel. None of the samples induced mutagenicity in the Ames fluctuation test. However, the Micronucleus assay revealed significant effects in Chinese hamster (Cricetulus griseus) V79 cells caused by the potential biofuels. 2-MF revealed the highest toxic potential with significant induction of micronuclei below 20.0 mg/L. EL and 2-MTHF induced micronuclei only at very high concentrations (>1000.0 mg/L). In regard to the genotoxic potential of 2-MF, its usage as biofuel should be critically discussed.

The population vulnerability of a species to pesticides is determined by the risk of its exposure to the pollutant, its sensitivity to the toxicant and the potential to sustain its populations if adversely affected (population resilience). This study uses population modelling to link the life cycle traits of a set of fish species which are highly susceptible to pesticide exposure, to their population resilience as a contribution to the needed identification of representative vulnerable species for higher-tier ecological risk assessment (ERA) of pesticides in Europe. Leslie matrix models for 21 species were parametrized using data from literature on field populations whose resilience was assessed. Phoxinus phoxinus was identified as the species with the least resilient populations for effects on fertility, Lampetra planeri for effects on juvenile survival and Esox lucius for effects on adult survival. Combining the measured effects from standard fish bio-tests with population models of these species would result in an ecologically relevant and protective risk assessment for field conditions in Europe.

In the present study we demonstrate the rhizoremediation potential of a biodiesel plant Jatropha curcas L. against lindane and discuss the field applicability of Jatropha based remediation techniques and future research prospects. Six different experimental approaches were conducted to evaluate the phytoremediation potential of Jatropha under glasshouse conditions. For this, Jatropha plants were grown in garden soil spiked with four increasing concentration of lindane (5, 10, 15 and 20 mg kg(-1)) and harvested after 45, 180 and 300 d. One set of control plants were grown in lindane free soil and another set of spiked soils were kept without Jatropha plants. At every harvesting, plant growth, lindane accumulation in plant parts, residual lindane concentration in soil as well as percentage lindane dissipation from soil were calculated. After 300 d, the accumulation of lindane in Jatropha grown in four simulated soils reached up to 5.42, 10.83, 15.95 and 20.85 mu g g(-1) plant dry matter, respectively. Correspondingly, the residual lindane soil concentrations in the above four treatments were reduced to 89, 82, 77 and 72% with respect to the applied lindane amounts, respectively. We conclude that Jatropha enhances the dissipation of lindane in simulated soil and is useful for onsite remediation. (C) 2013 Elsevier Ltd. All rights reserved.

The low-cost, plant-based phytoextraction technique has often been described as a promising technique to remediate heavy metal contaminated agricultural land. The application of chelating agents has shown positive effects in increasing the solubility of heavy metals in soil and therefore in enhancing phytoextraction. This paper gives an overview of the chelating agents applied in recent studies. Various synthetic aminopolycarboxylic acids, such as ethylene diamine tetraacetic acid, and natural ones such as, ethylene diamine disuccinate and nitrilotriacetic acid, are described. Additionally, results of the application of natural low molecular weight organic acids, such as citric and tartaric acid are given. The effectiveness of these different chelating agents varies according to the plant and the heavy metals used. Furthermore, a focus is laid on the chelating agents fate after application and on its toxicity to plants and soil microorganisms, as well as it degradation. The rate of degradation is of great importance for the future of chelate assisted phytoextraction as it has a direct impact on the leaching probability. An effective prevention of leaching will be crucial for the acceptance and the economic breakthrough of enhanced phytoextraction, but a satisfactory solution to this key issue has so far not been found. Possibly further experiments in the field of enhanced phytoextraction will be able to solve this major problem, but over decades various greenhouse experiments and recently field experiments have resulted in different observations. Therefore, it is questionable if further research in this direction will lead to a promising solution. Phytoextraction has possibly reached a turning point in which it should distance itself from chelate assisted phytoextraction and focus on alternative options.

Phytoextraction, the use of plants to extract contaminants from soils and groundwater, is a promising approach for cleaning up soils contaminated with heavy metals. In order to enhance phytoextraction the use of chelating agents has been proposed. This study aims to assess whether ethylene diamine disuccinate (EDDS), a biodegradable chelator, can be used for enhanced phytoextraction purposed, as an alternative to ethylene diamine tetraacetate (EDTA). EDDS revealed a higher toxicity to tobacco ( Nicotiana tabacum ) in comparison to EDTA, but no toxicity to microorganisms. The uptake of Cu was increased by the addition of EDTA and EDDS, while no increase was observed in the uptake of Cd. Both chelating agents showed a very low root to shoot translocation capability and the translocation factor was lower than the one of the control. Heavy metals where significantly more phytoavailable than in the control, even after harvesting, resulting in a high heavy metal leaching possibility, probably owing to a low biodegradation rate of EDDS. New seedlings which were transplanted into the EDDS treated pots 7 d after the phytoextraction experiment, showed signs of necrosis and chlorosis, which resulted in a significantly lower biomass in comparison to the control. The seedlings on the EDTA treated pots showed no toxicity signs. Contrary to previous opinions the results of this study revealed the chelating agents EDTA and EDDS as unsuitable for enhanced phytoextraction using tobacco.

It was examined in this study that magnetic beads, which are assumed to be environmentally functional, could be effective in processing heavy metals that are water pollutants. For the purpose, magnetic beads containing carboxyl groups, which has strong binding force with heavy metals, are mixed with each Cd, Pb, Ni, Cu and Cr(III) solution, then stirred in pH 6. As a results of the process, it was proven that heavy metals bind quickly with magnetic beads through the reaction. In order to analyze heavy metal concentration, magnetic beads bind with heavy metal were collected by external magnetic force and dissolved in acid. The graphite furnace AAS was used to get heavy metal concentration melted in the acid solution. The results showed that heavy metal extractions by magnetic beads were influenced by the type and the concentration of a heavy metal, and over 90% of a heavy metal can be extracted in ppm level save for Cr(III). It was also examined in the study whether heavy metal extraction is influenced when other ions exist in each heavy metal solution. According to experiment, adding other heavy metals to a solution did have little influence on extracting an intended heavy metal. But in case salt or heavy metal chelate was added, Ni extraction changed sensitively although extracting other heavy metals were influenced only when the concentration of an added substance is high. In conclusion, it was shown that magnetic beads could be used to treat wastewater with relatively high heavy metal concentration.

Phytoremediation, the use of plants to extract contaminants from soils and groundwater, is a promising approach for cleaning up soils contaminated with heavy metals. However its use is limited by the time required for plant growth, the nutrient supply and, moreover, by the limited metal uptake capacity. Synthetic chelators have shown positive effects in enhancing heavy metal extraction, but they have also revealed several negative side-effects. The objective of this study was to investigate the use of three natural low molecular weight organic acids (NLMWOA) (citric, oxalic, and tartaric acid) as an alternative to synthetic chelators. Slurry-, column-, toxicity- and phytoextraction experiments were performed. For the phytoextraction experiment the three NLMWOA were applied to a copper- and a lead-contaminated soil respectively. A significant increase in copper uptake was visible only in the citric acid treatment (67 mg kg-1) in comparison to the EDTA treatment (42 mg kg-1). The NLMWOA application showed no enhanced effect concerning the lead phytoextraction. A possible explanation for this lack of significance could be the rate of the degradation of NLMWOA. This rate might well be too high for these heavy metals with low mobility and bioavailability such as lead. The amounts of NLMWOA applied to the soil were very high (62.5 mmol kg-1 of soil) and the effect was too little. In this respect EDTA, which was applied in very small amounts (0.125 mmol kg-1) was more efficient. Thus making NLMWOA unsuitable to enhance phytoextraction of heavy metals from soil.

The analytic possibility of mobile lead contained in soil has been studied using carboxylated magnetic beads. Extraction of heavy metal was performed to contaminated soil that has been collected and supplied for tests. As experiment materials, soil sample, distilled water and magnetic beads were only used. It means that the lead was extracted under neutral condition. In this condition, only the mobile fraction of lead could be extracted by magnetic beads. The mobile lead in the soil was quickly combined with magnetic beads in the mixture process. Then, the magnetic beads were dissolved into acids after collection by external magnetic force, and the lead combined with the beads was eluted and analyzed by Graphite Furnace Atomic Absorption Spectroscopy (GFAAS). In the results of extraction experiments for 3 sandy soils, the efficiency using beads was similar to or higher than that of EDTA (Ethylendiamintetraacetic acid), which is normally used for analyzing mobile heavy metal concentration in soil. With this, it was shown that this method is a more accurate and simple method to analyze mobile lead when analyzing mobile heavy metal concentration in sandy soil, rather than conventional method using EDTA.

14C-labelled simazine was composted together with biowaste on a pilot (m3) scale. The herbicide was quickly bound to the compost matrix. By aqueous extraction of 29 and 200 days old compost (equivalent to thermophilic and mesophilic phase of composting) only 4.2% and 3.1% respectively of the radioactivity in the compost samples could be extracted with water. Analysis of the extracts using high-performance size exclusion chromatography (HPSEC) revealed that the dissolved organic matter (DOM) had molecular weights ranging between 2 and 28 kDa. The amount of DOM-associated radioactivity increased from 53% (day 29) to 65% (day 200) of total extractable radioactivity. The type of binding of the 14C-labelled residues and the DOM was elucidated by silylation of humic matter and subsequent HPSEC. The data demonstrated that besides polar metabolites also intact simazine was bound to the DOM. A distinct shift from rather weak interactions to strong covalent linkages of simazine and its metabolites with increasing age of the compost was observed. The results showed that only low amounts of free simazine and its degradates can be extracted with water. We concluded that the shift towards stable covalent linkages is equivalent to a detoxification of the contaminant in aged compost. Consequently, the use of the analysed compost in its mature stage should not pose an environmental risk to the groundwater or the subsoil.

Increased use of nanomaterials in everyday products leads to their environmental release and therefore, the information need on their fate and behaviour. Nanomaterials have to be suspended with high repeatability and comparability for studies on environmental effects. They also have to be well characterised with a focus on the state of agglomeration and particle size distribution. Dynamic light-scattering (DLS) is a common technique used for these measurements. If suspensions are prepared in different laboratories, then concern has risen about the comparability of the measured results, especially when different DLS instruments are used. Therefore, for quality assurance, a round-robin test was conducted to assess the comparability of different DLS instruments and a dispersion protocol in ten independent laboratories. Polystyrene and TiO2 were chosen as test (nano)materials. For the comparability of the DLS instruments, the average sizes of the PSL and a stabilised TiO2 suspension were measured. The measured average hydrodynamic diameter shows an overall good inter-laboratory comparability. For the PSL suspension, an average hydrodynamic diameter of 201 ± 13 nm and for the TiO2 suspension an average diameter of 224 ± 24 nm were detected. For the TiO2 suspension that was prepared at each laboratory following an established suspension preparation protocol, an average hydrodynamic diameter of 211 ± 11 nm was detected. The measured average particle size (mode) increased up to 284 nm with a high standard deviation of 119 nm if the preparation protocol could not established and different procedures or different equipment were employed. This study shows that no significant differences between the employed DLS instrument types were determined. It was also shown that comparable measurements and suspension preparation could be achieved if well-defined suspension preparation protocols and comparable equipment can be used.

The fate assessment of nanomaterials in municipal sewage treatment plants (STP) is a crucial step for their environmental risk assessment and may be assessed by monitoring full scale STP, dosage to medium scale pilot STP or by laboratory testing. For regulatory purposes preferably standardised test protocols such as the OECD guidelines for testing of chemicals should be used. However, these test protocols have not yet been specifically designed for nanoparticles. Therefore, the fate and behavior of a TiO2 nanomaterial (P25, average hydrodynamic diameter250 nm) was investigated in laboratory sewage treatment plants according to the OECD Guideline for the Testing of Chemicals 303 A. It is concluded that this guideline is applicable for the testing of nanomaterials if modifications regarding the dosage, nitrifying conditions, and a characterisation of the nanoparticles in the effluent are applied. A compilation of the cumulative mass balance by comparison of the total dosage added with the amount in the outflow and in the activated sludge is recommended. In this study, the majority of the TiO2 nanomaterial (95%) was retained in the sewage sludge and only 3-4% was found in the effluent. No effect of the TiO2 nanomaterials on the biodegradation or nitrification was observed.

After 22 years of aging under natural conditions in an outdoor lysimeter the bioaccessibility of C-14-labeled atrazine soil residues to bacteria was tested. Entire soil samples as well as sand-sized, silt-sized, and clay-sized aggregates (> 20, 20-2, and < 2 mu m aggregate size, respectively) were investigated under slurried conditions. The mineralization of residual radioactivity in the outdoor lysimeter soil reached up to 4.5% of the total C-14-activity after 16 days, inoculated with Pseudomonas sp. strain ADP. The control samples without inoculated bacteria showed a mineralization maximum of only about 1% after 44 days of incubation. Mineralization increased in the clay-sized aggregates up to 6.2% of the total residual 14C-activity within 23 days. With decreasing soil aggregate sizes, residual C-14-activity increased per unit of weight, but only minor differences of the mineralization in the soil and soil size aggregates using mineral-media for incubation was observed. Using additional Na-citrate in the incubation,the extent of mineralization increased to 6.7% in soil after 23 days following incubation with Pseudomonas sp. strain ADP. These results show that long-term aged IT-atrazine residues are still partly accessible to the atrazine degrading microorganism Pseudomonas sp. strain ADP.

Phytoextraction has revealed great potential, however it is limited by the fact that plants need time and nutrient supply and have a limited metal uptake capacity. Although the use of synthetic chelators, such as EDTA, enhances heavy metal extraction, it also produces the negative side effects of high phytotoxicity, as well as leaching of essential metals. The aim of this research was to investigate the application of wool, in mobilising metals and in improving the phytoextraction of metals-contaminated soil. We performed column experiments with 14 d and 7 d partially hydrolysed wool as chelating agent on a silty-loamy sand agricultural soil. In the column experiment the 14 d wool hydrolysate mobilised 68% of Cu in soil, whereas in the case of Cd it mobilised 5.5%. The model plant selected for the phytoextraction experiments was tobacco (Nicotiana tabacum). The plant uptake of Cd and Cu, assisted by the application of 6.6 g kg(-1) wool hydrolysate was increased by 30% in comparison to the control plants. The application of 13.3 g kg(-1) wool hydrolysate enhanced the Cu uptake by up to 850%. Moreover, high leaching probability frequently observed when applying chelating agents, such as EDTA or ethylene diamine disuccinate (EDDS), were not detected. The use of hydrolysed wool therefore merits further investigation.

Although cyanide is highly toxic, it is economically attractive for extracting gold from ore bodies containing only a few grams per 1000 kg. Most of the cyanide used in industrial mining is handled without observable devastating consequences, but in informal, small-scale mining, the use is poorly regulated and the waste treatment is insufficient. Cyanide in the effluents from the latter mines could possibly be removed by the water hyacinth Eichhornia crassipes because of its high biomass production, wide distribution, and tolerance to cyanide (CN) and metals. We determined the sodium cyanide phytotoxicity and removal capacity of E . crassipes . Toxicity to 5–50 mg CN L −1 was quantified by measuring the mean relative transpiration over 96 h. At 5 mg CN L −1 , only a slight reduction in transpiration but no morphological changes were observed. The EC 50 value was calculated by probit analysis to be 13 mg CN L −1 . Spectrophotometric analysis indicated that cyanide at 5.8 and 10 mg L −1 was completely eliminated after 23–32 h. Metabolism of K 14 CN was measured in batch systems with leaf and root cuttings. Leaf cuttings removed about 40% of the radioactivity from solution after 28 h and 10% was converted to 14 CO 2 ; root cuttings converted 25% into 14 CO 2 after 48 h but only absorbed 12% in their tissues. The calculated K m of the leaf cuttings was 12 mg CN L −1 , and the V max was 35 mg CN (kg fresh weight) −1 h −1 . Our results indicate that E . crassipes could be useful in treating cyanide effluents from small-scale gold mines.

Use of municipal biowaste for composting instead of its disposal has become a major source of concern as regards contamination by hazardous substances. To elucidate the hazard potential of compost application, municipal biowaste was amended with 14C-labelled model substances (pyrene, simazine) and incubated in a pilot-scale composting simulation system. A mass balance incorporating the mineralization, metabolism and sorption of the two model substances was established over a period of 370 days. The results are quite different for the two chemicals, reflecting their intrinsic properties: more than 60% of the applied 14C-simazine resulted in non-extractable residues (NER). Silylation experiments indicated that the formation of NER from simazine and its metabolites was due to both physical entrapment in the matrix and chemical binding. The mineralization and formation of NER represented the major pathways of disappearance for pyrene during one year of composting, accounting for 60 and 26% of initially applied 14C-activity, respectively. Mineralization occurred delayed after the thermophilic phase. As regards remobilization, release of pyrene from NER during composting could be excluded, whereas simazine, data were inconclusive in this respect.