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The intensive development of medical science has led to an increase in the availability and use of pharmaceutical products. However, nowadays, most of scientific attention has been paid to the native forms of pharmaceuticals, while the transformation products (TPs) of these substances, understood herein as metabolites, degradation products, and selected enantiomers, remain largely unexplored in terms of their characterization, presence, fate and effects within the natural environment. Therefore, the main aim of this study was to evaluate the toxicity of seven native compounds belonging to different therapeutic groups (non-steroidal anti-inflammatory drugs, opioid analgesics, beta-blockers, antibacterial and anti-epileptic drugs), along with the toxicity of their 13 most important TPs. For this purpose, an ecotoxicological test battery, consisting of five organisms of different biological organization was used. The obtained data shows that, in general, the toxicity of TPs to the tested organisms was similar or lower compared to their parent compounds. However, for example, significantly higher toxicity of the R form of ibuprofen to algae and duckweed, as well as a higher toxicity of the R form of naproxen to luminescent bacteria, was observed, proving that the risk associated with the presence of drug TPs in the environment should not be neglected. Electronic supplementary material The online version of this article (10.1007/s11356-020-08881-3) contains supplementary material, which is available to authorized users.

Wastewater from pharmaceutical and related industries contains many residual pharmaceutical components rich in color and high COD contents, which cannot be removed through the traditional wastewater treatment processes. Recently, microbial electrolysis ultraviolet cell (MEUC) process has shown its promising potential to remove recalcitrant organics because of its merits of wide pH range, iron-free, and without complications of iron sludge production. However, its application to the real pharmaceutical-rich industrial wastewater is still unknown. In this study, the MEUC process was validated with real ciprofloxacin-rich (6863.79 ± 2.21 µg L−1) industrial wastewater (6840 ± 110 mg L−1 of COD). The MEUC process achieved 100% removal of ciprofloxacin, 100% decolorization, and 99.1% removal of COD within 12, 60 and 30 h, respectively, when it was operated at pH-controlled at 7.8, applied voltage of 0.6 V, UV intensity of 10 mW cm−2, and cathodic aeration velocity of 0.005 mL min−1 mL−1. Moreover, fluorescence analysis showed that protein- and humic-like substances in such wastewater were effectively removed, providing further evidence of its high treatment efficiency. Furthermore, eco-toxicity testing with luminescent bacteria Vibro Feschri confirmed that the treated effluent was utterly non-toxic. The results demonstrated the broad application potential of MEUC technology for treating industrial wastewater.

In the bioethanol industry, per liter of the produced alcohol 9 to 14 liters of vinasse are obtained as a byproduct. If the vinasse is directly shed into bodies of water without an adequate treatment, it may have negative effects on the existing biota and human health due to its high turbidity and color, low pH and high content of organic material. The purpose of this study was to assess the acute toxicity of vinasse by means of a rapid test with Aliivibrio fischeri and compare it with a standard immobilization assay with Daphnia magna. The standard assay of D. magna by means of its EC50 of 4.7% showed that organism was more sensitive to the contaminant, in comparison with the 69.6% obtained with the A. fischeri which suggests that it should be continuesly used as one of the organisms of first choice for the evaluation of the acute toxicity of this effluent.

The humic-like substances were the main organic components in most wastewater (e.g. domestic sewage, toilet wastewater and landfill leachate). Two types of actual humic-like substances (fulvic acid (FA) and biologically treated landfill leachate (BTLL)) were selected to describe the changes in the properties of humic-like substances (complexation ability, aromaticity and mobility) during electrochemical oxidation. Meanwhile, the acute cytotoxicity of FA and BTLL was also tested by acute toxicological test of luminescent bacteria. The results showed that the consumption of coordinating groups such as phenolic groups and hydrogen bonds reduced the complexation ability of FA and BTLL. The functional groups were degraded with the removal order of quinone group, phenolic group and aromatic group, and finally realized the molecular saturation and aromaticity decrease for humic-like substances. The mobility of FA and BTLL was decreased because of the enhancement of hydrophobicity during electrolysis process. Furthermore, the available chlorine produced during electrochemical oxidation was the main acute cytotoxicity substance, therefore, it is necessary to remove it before discharge in order to reduce ecological risks. This study provides a basis for understanding and evaluating the electrochemical degradation process of humic-like substances in detail.

This study investigated the degradation of benzophenone-4 (BP-4) in a UV/chlorine disinfection process, with chlorination and UV disinfection as comparisons. With a degradation efficiency of 80% after 10 s, the UV/chlorine process significantly enhanced the degradation of BP-4. However, a rebound of 36% of the initial concentration was observed in the UV/chlorine process ([free active chlorine (FAC)]0:[BP-4]0 = 1:1, pH = 7). The same tendency appeared under the addition of alkalinity, Cl−, and humic acid (HA). This work interpreted this interesting kinetic tendency from the perspective of mechanism. In fact, the transformation between the chlorinated product P1 and BP-4 was reversible under certain conditions. The inhomogeneous charge distribution of the C Cl bond in P1 led to the photolytic dechlorination of P1. This transformation caused an increase in BP-4 concentration. In addition, the increase in the UV light power promoted the photodecomposition of P1 under the experimental condition. In addition, this study evaluated the change in absorbable organic halogens (AOX) and three kinds of toxicity changes in the BP-4 solution after chlorination and the UV/chlorine process, including the acute toxicity of luminescent bacteria, endocrine disrupting effect and cytotoxicity. The UV/chlorine process exhibited lower ecotoxicity than chlorination in water treatment.

Previous studies demonstrated long-term stimulation of some commercial personal care products (PCPs) on freshwater luminescent bacteria Vibrio qinghaiensis sp .-Q67 (Q67). However, whether a certain component can affect mixture's hormetic effect is still unknown. In this paper, two of ingredients in PCPs, 2-phenoxyethanol (PhE) and polyethylene glycol 400 (PEG400), were selected as object compounds to explore the relationship between concentration-response (CR) of mixtures and that of a single component. It was found that PEG400 has monotonic CR (MCR) on Q67 both at the short-term (0.25 h) and long-term (12 h) exposures while PhE has MCR at 0.25 h and hormetic CR (HCR) at 12 h. Here, the concentration-response curves (CRCs) of PEG400 at 0.25 and 12 h are overlapped each other and the CRCs of PEG400 are on the right of PhE. If the pEC 50 is taken as a toxic index, the toxicities of PEG400 at two times are basically the same, and those of PhE are the same, too, but PhE is twice as toxic as PEG400. For the mixtures of PEG400 and PhE, all rays except R1 have MCRs at 0.25 h while all rays have HCRs at 12 h where the higher the mixture ratio of PhE is, the more negative the maximum stimulation effect is. More importantly, the E min values of all rays are more negative (1.79–3.17-fold) than that of PhE worked alone, which implies that the introduction of PEG400 significantly enhances stimulative effect of PhE. At 0.25 h, all binary mixture rays but R1 produce a low-concentration additive action and high-concentration synergism. At 12 h, all rays display additive action, antagonism, additive action, and synergism in turn when the concentration changes from low to high. The overall findings suggested toxicological interactions should be considered in the risk assessment of PCPs and their potential impacts on ecological balances.

Diclofenac was frequently found in various waters, indicating conventional wastewater treatment methods ineffective in its removal. In this study, LaFeO3 (LFO) was synthesized and its catalytic activity of LFO as the activator of different oxidants such as persulfate (PS), hydrogen peroxide and peroxylmonosulfate (PMS) was evaluated in terms of DCF degradation. The influence of calcination temperature was examined on the catalytic activity of LFO. The effects of various parameters including pH levels, PMS concentration, LFO dose and initial DCF concentration were investigated on DCF degradation rate. The marginal effects of PMS concentration and LFO dose were compared. Langmuir-Hinshelwood (LH) model was used to quantitatively describe DCF degradation reaction in LFO/PMS system. The two constants, k (Limiting reaction rate at maximum coverage) and K (Equilibrium adsorption constant), were determined on the basis of LH model. The performance of LFO/PMS process was also estimated in the presence of various inorganic anions. The potential toxicity of LFO and PMS were evaluated using phytoplankton and the toxicity evolution during DCF degradation was also investigated using luminescent bacteria. This contribution provides a basic study regarding the potential application of heterogeneous PMS activation by perovskite LFO for both DCF removal and toxicity elimination.

Due to their widespread use and harmful effects on aquatic environment, sulfonamide antibiotics (SAs) have become an emerging pollutant of great concern around the world. In this study, we investigated the degradation process and mechanism of sulfamerazine (SMR), sulfadiazine (SDZ), and sulfapyridine (SPD) by electron-beam irradiation (EBI). The results showed that the three SAs were well suited to the pseudo-first-order reaction kinetics, and they could be almost completely removed with high efficiency (5 kGy). Among the environmental factors, pH (3.0) and O2 atmosphere can further enhance the removal of the sulfonamides (SAs), while NO2− has the most pronounced degrading inhibitory effects among the many ions, these results illustrate that hydroxyl radicals play a dominant role. Compared with SMR and SDZ, the degree of mineralization of lower molecular weight SPD is obvious (45%). LC-MS and DFT calculations indicate that the concentrations of degradation products of the three SAs show a tendency to increase and then decrease, demonstrating that EBI can achieve efficient removal and further mineralization of SAs. Meanwhile, the results of the common product 4-Aminophenol produced during the degradation process further indicate that HO is the predominant reactive oxygen species (ROS). In addition, acute toxicity experiments with luminescent bacteria and predictions of ECOSAR procedures proved the toxic effects greatly decreased after the degradation. This study provides new ideas for achieving efficient and profound removal of emerging pollutants from the aquatic environment.

In this paper, the releasing characteristics and biological toxicity of Tl, Hg, As and Sb in waste of Lanmuchang mercury-thallium mine were studied. The results indicated that strong acidity can significantly promote the release of Tl from waste. With the increase of pH, the release of Sb grew steadily, while Hg and As showed a trend of first increasing and then decreasing. Fe2(SO4)3 contributed less to the release of As and Sb than to that of Hg and Tl. FeCl3 significantly inhibited the release of As, Sb and Tl. In the leaching experiments of litter and root exudates, the lixiviums appeared neutral, and the litter and root exudates solution significantly reduced the release of Tl, and showed less toxicity to luminescent bacteria. However, they promoted the release of Hg, As and Sb at different levels.

Trans-resveratrol becomes more and more popular all over the world as a powerful antioxidant. Since its positive properties, including antioxidant, anti-inflammatory, anti-tumor are indisputable, nowadays trans-resveratrol is used as a component of various products from nutriceutics to body care formulations, where it is supposed to behave as natural antioxidant and anti-aging compound. It is also added to food packaging materials to increase their stability or/and prevent oxidation. Nevertheless, being released to the environment resveratrol easily forms various transformation products with potentially negative environmental and health effects. The present paper deals with transformation of pure resveratrol and its formulation used as UV-protectors in conditions of aquatic chlorination. Over 80 transformation products were tentatively identified using gas chromatography-high resolution mass spectrometry (GC-HRMS) and ultra pressure liquid chromatography-high resolution mass spectrometry (UPLC-HRMS). Chlorinated phenols and biphenyls are the most relevant among them. Estimation of toxicity of resveratrol products was carried out using luminescent bacteria V. fischeri tests.

The production of biodegradable plastics is considered to be a way to reduce plastic waste issue. Among others, oxo-degradant additives enable a faster degradation of plastics in the environment. However, the introduction of these new materials could provoke the release of substances potentially toxic in the environment. This work determined and compared the toxicity of leachates from various additivated polymers (polyethylene, PE; polypropylene, PP; polystyrene, PS) upon different test organisms: plants (Sorghum saccharatum, Lepidium sativum, Sinapis alba, and Vicia faba), crustacean (Daphnia magna), and luminescent bacteria (Vibrio fischeri). Daphnia magna survival was mainly affected by PS and PP leachates (72% and 61% effect, respectively) while PS notably reduced the reproduction rate. On plants, only PP exerted a negative effect (S. saccharatum IG% 32.4), while V. fischeri always showed values around 50%. The data integration, through the Toxicity Test Battery Integrated Index (TBI) approach, allowed to rank the leachates toxicity as PE > PS > PP. This result could be mainly ascribable to the highest metals content in PE since no difference with organic compounds analysis was evidenced. In conclusion, since the polymers exerted dissimilar toxicity, the additive could not be considered the sole responsible of the measured toxicity, but its role in the enhancement of the virgin polymers leachates effects can be solidly hypothesized.

In this study, the applicability of UV absorbance at 254 nm (UV254) and volatile fatty acids (VFAs) to serve as reliable surrogates to predict acute toxicity of traditional Chinese medicine (TCM) wastewater was investigated. The medicine residues and VFAs were identified as main components of the TCM wastewater, and their individual and joint toxicity assays were operated with luminescent bacteria. The median effective concentration (EC50) values of medicine residues and VFAs were in the range of 26.46-165.55 mg/L and 11.45-20.58 g/L, respectively. The joint toxicity action modes of medicine residues, VFAs and medicine residues-VFAs were identified as additive, additive and synergistic respectively. UV254 and VFAs showed better correlations with acute toxicity according to the correlation analysis, compared with other conventional parameters. The regression model was a good fit for toxic unit (TU50) as a function of UV254 and VFAs according to the stepwise regression method (adjusted R2 = 0.836). Validation of the model to the pilot-scale samples provided satisfactory prediction results in the influent and hydrolysis acidification effluent samples tests, but for EGSB effluent and final effluent samples, the model needed further optimization. Surrogates prediction using UV254 and VFAs provided a valuable and cost-saving tool for rapid or on-line monitoring of acute toxicity of TCM wastewater.

Additional control indexes should be considered for the operation and design of post-treatment systems, as the wastewater treatment objectives are developing toward protecting the safety of ecological environments. In this study, two control indexes were selected and examined systematically in pilot-scale shallow open-water unit (SOWU) ponds for domestic effluent polishing: micropollutants and biotoxicities. The total risk quotient (RQTotal ≤ 1) and effect-based trigger value (EBT) were set as the thresholds for known micropollutants and biological effects, respectively. The results showed that RQTotal of micropollutants (n = 46) could be mitigated to an acceptable level and the luminescent bacteria toxicity was in compliance with the EBT after SOWU polishing in the warm season. The reduction of micropollutants and biotoxicities in the SOWUs both fit the k–C* model well (R2 > 0.9) in the warm and cold seasons. Finally, the k–C* model integrated with the control indexes was developed to design the SOWU dimensions, and the results indicated that a pond area of 21.7–108.5 m2 was required for every 1 m3/d of effluent when micropollutants were set as the control index, while a pond area of 3.6–18.2 m2 was required when luminescent bacteria toxicity was set as the control index.

Although magnetic ionic liquids (MILs) are not yet industrially applied, their continued development and eventual commercial use may lead to their appearance into the aquatic ecosystem through accidental spills or effluents, consequently promoting aquatic contaminations. Furthermore, the deficient information and uncertainty surrounding the environmental impact of MILs could be a major barrier to their widespread industrial application and international registration. Thus, in the present work, a range of cholinium salt derivatives with magnetic properties was synthesized and their ecotoxicity was evaluated towards the luminescent bacteria Vibrio fischeri. The results suggest that all MILs structures tested are moderately toxic, or even toxic, to the bacteria. Furthermore, their toxicity is highly dependent on the structural modifications of the cation, namely the alkyl side chain length and the number of hydroxyethyl groups, as well as the atomic number of the metal anion. Finally, from the magnetic anions evaluated, the [MnCl4]2- is the less toxic. In order to improve the knowledge for the prospective design of environmentally safer MILs, it is important to expand this study to other aquatic organisms at different trophic levels. published

The widespread use of organic ultraviolet (UV) filters in personal care products raises concerns about their potentially hazardous effects on human and ecosystem health. In this study, the toxicities of four commonly used benzophenones (BPs) UV filters including benzophenone (BP), 2-Hydroxybenzophenone (2HB), 2-Hydroxy-4-methoxybenzophenone (BP3), and 2-Hydroxy-4-methoxybenzophenone-5-sulfonicacid (BP4) in water were assayed in vitro using Vibrio fischeri, SOS/umu assay, and yeast estrogen screen (YES) assay, as well as in vivo using zebrafish larvae. The results showed that the luminescent bacteria toxicity, expressed as logEC50, increased with the lipophilicity (logKow) of BPs UV filters. Especially, since 2HB, BP3 and BP4 had different substituent groups, namely -OH, -OCH3 and -SO3H, respectively, these substituent functional groups had a major contribution to the lipophilicity and acute toxicity of these BPs. Similar tendency was observed for the genotoxicity, expressed as the value of induction ratio=1.5. Moreover, all the target BPs UV filters showed estrogenic activity, but no significant influences of lipophilicity on the estrogenicity were observed, with BP3 having the weakest estrogenic efficiency in vitro. Although BP3 displayed no noticeable adverse effects in any in vitro assays, multiple hormonal activities were observed in zebrafish larvae including estrogenicity, anti-estrogenicity and anti-androgenicity by regulating the expression of target genes. The results indicated potential hazardous effects of BPs UV filters and the importance of the combination of toxicological evaluation methods including in vitro and in vivo assays.

Phthalates has been widely used in children's toys as plastic plasticizers and softeners. The aim of this study was to extract chemically phthalates from 20 toy samples and determine toxicity using the Vibrio fischeri luminescent bacteria test. Subsequently the (the concentration producing 50% of maximal effect) was employed to characterize the toxicity of the sample and select the appropriate solvent from methanol, ethanol or glycerol in order to assess the adverse effects of di-n-butyl phthalate (DBP) or di-2-ethylhexyl phthalate (DEHP) and not solvent interference on Vibrio fischeri. Data showed that toxicity of glycerol was relatively low when the concentration was less than 0.44 mol/L. Therefore glycerol was selected as solvent. DBP and DEHP produced toxicity on Vibrio fischeri in the order of DEHP > DBP. The was 0.437 and 0.182 mol/L, respectively. This study provides the foundation for examination of combined toxic effects of the mixture of DBP and DEHP on Vibrio fischeri which is of signif...

The removal of acetaminophen (AAP) in aqueous solution by the UV/chlorine process was evaluated. The effect of chlorine dose, the initial AAP concentration, pH value, and UV intensity on the reaction were also investigated. The degradation mechanism and the ecological risk were further discussed. The results indicated that AAP degradation fitted pseudo-first-order kinetics. Compared with UV alone or dark chlorination, the combination of UV and chlorine significantly accelerated the degradation process. The AAP degradation was positively affected by chlorine dose and UV intensity, while negatively affected by the initial AAP concentration and ammonia nitrogen concentration during the UV/chlorine process. The frontier orbital theory analysis shows that the C5 position in the benzene ring of AAP is likely to be the first site attacked by HO• and Cl• radical to form the products. Twelve intermediates were identified by Q-TOF and GC-MS. The possible degradation pathways were also proposed. Luminescent bacteria experiment and ECOSAR prediction both revealed that acute toxicity of AAP degradation could only be partially reduced. Ecological risks during the UV/chlorine process need to be further evaluated.

Predicting the crucial effect of single metal pollutants against the aquatic ecosystem has been highly debatable for decades. However, dealing with complex metal mixtures management in toxicological studies creates a challenge, as heavy metals may evoke greater toxicity on interactions with other constituents rather than individually low acting concentrations. Moreover, the toxicity mechanisms are different between short term and long term exposure of the metal toxicant. In this study, acute and chronic toxicity based on luminescence inhibition assay using newly isolated Photobacterium sp.NAA-MIE as the indicator are presented. Photobacterium sp.NAA-MIE was exposed to the mixture at a predetermined ratio of 1:1. TU (Toxicity Unit) and MTI (Mixture Toxic Index) approach presented the mixture toxicity of Hg2+ + Ag+, Hg2+ + Cu2+, Ag+ + Cu2+, Hg2+ + Ag+ + Cu2+, and Cd2+ + Cu2+ showed antagonistic effect over acute and chronic test. Binary mixture of Cu2+ + Zn2+ was observed to show additive effect at acute test and antagonistic effect at chronic test while mixture of Ni2+ + Zn2+ showing antagonistic effect during acute test and synergistic effect during chronic test. Thus, the strain is suitable and their use as bioassay to predict the risk assessment of heavy metal under acute toxicity without abandoning the advantage of chronic toxicity extrapolation.

Photocatalytic degradation of typical pharmaceuticals in natural sunlight and in actual water is of great significance. In this study, the oxygen or nitrogen linked heptazine-base polymer (ONLH) was successfully incorporated with TiO2 nanoparticles and formed a TiO2/ONLH nanocomposite which was responded to the natural sunlight. Under natural sunlight, the TiO2/ONLH can effectively degrade ten types of pharmaceuticals. In particular, fluoroquinolone containing N-piperazinyl, and cardiovascular drugs containing long aromatic side chains were easily degraded. The half-life of the best degradation performance of propranolol was less than 5 min. The rate constants of propranolol using the TiO2/ONLH were approximately six- and eight-fold higher than those of pristine TiO2 and ONLH, respectively. Two reactive species (OH and O2-) facilitated the rapid degradation of propranolol, which occurred primarily through the hydroxyl radical addition, ring-opening, and ipso substitution reactions. An acute toxicity test using luminescent bacteria indicated that the toxicity of the propranolol reaction solution gradually decreased with lower total organic carbon (TOC). According to the toxicity evaluation of monomer products, the TiO2/ONLH also reduced the generation of toxic transformation products. The effects of actual water/wastewater have further shown the TiO2/ONLH might be applied for the removal of pharmaceuticals in wastewater.

The antipsychotic drug quetiapine (QUT) has been frequently detected in sewage treatment plants. However, information on the fate of QUT in aquatic environments and its behavior during UV treatment is limited. In this study, QUT is shown not to be readily biodegradable in the Closed Bottle Test and the Manometric Respirometry Test according to OECD guidelines. The main biotransformation product (BTP) formed in the tests, a carboxylic acid derivative, was identified by means of high-resolution mass spectrometry. This BTP is presumably a human metabolite and showed higher detection rates than QUT in a river sampling campaign conducted in northern Germany. UV elimination kinetics of QUT at different initial concentrations (226.5, 45.3, 11.3, and 2.3 μmol L −1 ) were faster at lower initial concentrations. All seven phototransformation products (PTPs) could be still identified at initial concentration of 11.3 μmol L −1 . The photolytic mixture generated after 128 min of photolysis of QUT was not better biodegradable than QUT. Initial UV treatment of QUT led to the formation of several additional BTPs. Four of them were identified. The bacterial cytotoxicity and genotoxicity before and after phototransformation of QUT in a modified luminescent bacteria test (LBT) and the umu-test (ISO/FDIS 13829) showed cytotoxic effects in the LBT for QUT. Furthermore, PTPs had similar cytotoxic effects on luminescent bacteria. The umu-test did not reveal any genotoxic activity for QUT or PTPs. In conclusion, the release of QUT into sewage treatment plants and aquatic environments could result in the formation of a main BTP. Additional UV treatment of QUT would lead to the formation of additional BTPs. Moreover, treatment did not result in lower toxicity to tested organisms. In conclusion, UV treatment of QUT should be considered critically as a potential treatment for QUT in aquatic systems.

Explosive-contaminated soil is harmful to people’s health and the local ecosystem. The acute toxicity of its extracting solution was tested by bacterial luminescence assay using three kinds of luminescent bacteria to characterize the toxicity of the soil. An orthogonal test L 16 (45) was designed to optimize the soil extracting conditions. The optimum extracting conditions were obtained when the ultrasonic extraction time, ultrasonic extraction temperature, and the extraction repeat times were 6 h, 40 °C, and three, respectively. Fourier transform infrared spectroscopy (FTIR) results showed that the main components of the contaminated soil’s extracting solution were 2,4-dinitrotoluene-3-sulfonate (2,4-DNT-3-SO3 −); 2,4-dinitrotoluene-5-sulfonate (2,4-DNT-5-SO3 −); and 2,6-dinitrotoluene (2,6-DNT). Compared with Photobacterium phosphoreum and Vibrio fischeri, Vibrio qinghaiensis sp. Nov. is more suitable for assessing the soil extracting solution’s acute toxicity. Soil washing can remove most of the contaminants toxic to luminescent bacterium Vibrio qinghaiensis sp. Nov., suggesting that it may be a potential effective remediation method for explosive-contaminated soil.

Assessment of eco-toxicant using bioluminescent bacterial assay is a widely used and globally accepted method. In this work, a new luminescent bacterium was isolated from squid (Loligo duvauceli) and identified as Photobacterium leiognathi strain AK-MIE using 16S rRNA, phylogeny analysis. The predicted optimum conditions by RSM were 2.76% (w/v) NaCl, 2.28% (w/v) peptone, 0.34% (w/v) yeast extract, and pH 6.83 with 541,211.80 RLU of luminescent production whereas the predicted optimum conditions by ANN were 2.21% (w/v) NaCl, 2.27% (w/v) peptone, 0.39% (w/v) yeast extract, and pH 6.94 which produced 541,986.20 RLU. The validation analysis of both RSM and ANN show 0.60% and 0.69% deviation from the predicted results indicating that both models provided good quality predictions with ANN showing a superior data fitting capability for non-linear regression analysis. Toxicity tests show strain AK-MIE was sensitive to mercury (concentration causing 50% inhibition or IC50 of 0.00978 mg L − 1 ), followed by cadmium (IC50 of 0.5288 mg L − 1 ), copper IC50 of (0.8117 mg L − 1 ), silver (IC50 of 1.109 mg L − 1 ), and lead (IC50 of 10.71 mg L − 1 ) which are more sensitive than previously isolated luminescent bacteria, suggesting that strain AK-MIE has the potential to be used in toxicity assessment of heavy metals in the environment. Based on the field trial results, several sediment samples from industrial areas in Bangi, Selangor managed to inhibit the bioluminescence of strain AK-MIE. Validation method carried out using ICP-MS proved the presence of several toxic heavy metal elements.

Advanced oxidation processes (AOPs) can degrade heavy metal complexes in wastewater to improve the removal efficiency of metals. However, the influences of AOP treatments on toxicity induced by metal complexes are not well understood. This study compared the toxicity induced by EDTA-copper (Cu) after UV/persulfate (PS) and UV/H2O2 treatments on luminescent bacteria and human HepG2 cells. The results showed that EDTA-Cu complexes decreased Cu toxicity in luminescent bacteria but increased the cytotoxicity in HepG2 cells, indicating species-specific toxicity. The UV/PS and UV/H2O2 treatments under most pH values and [oxidant]/[EDTA-Cu] conditions decreased the toxicity of EDTA-Cu in HepG2 cells but increased the toxicity in luminescent bacteria. When the ratio of [oxidant] to [EDTA-Cu] was 10, low toxicity in treated solutions was observed in both UV treatment processes. The alkaline precipitation treatment had a significant influence on toxicity reduction after UV/PS treatment; however, it had minimal influence on the UV/H2O2 treatment system. The Cu and total organic carbon (TOC) removal efficiency cannot completely explain the results of toxicity assays. EDTA-Cu intermediates might play important roles in changing the toxicity of EDTA-Cu after both UV treatments. This study provides insights into evaluating the treatment efficiency of UV/PS and UV/H2O2 on EDTA-Cu decomplexation.

The environmental compatibility of reactive fire-retardant coatings (intumescent paints) was investigated by a combination of leaching and ecotoxicological tests. Three representative fire-retardant coating systems were tested using two leaching procedures: “Horizontal Dynamic Surface Leaching Test” (DSLT) and the “Intermittent Immersion Test” (IIT). All eluate fractions (8 for DSLT and 9 for IIT) were analyzed for pH, conductivity, concentration of total organic carbon and selected anions und cations. Additionally, a GC-MS screening of selected fractions was conducted for identification of organic compounds. Eluate fractions 1 + 2 and fraction 7 of the DSLT were analyzed in four ecotoxicological tests (algae, daphnia, fish egg, luminescent bacteria) and in one genotoxicity test (umu). Concentration of most analytes was rather low or below limit of detection for many eluates. Analytes detected in eluates of all three products are Zn, Ba, SO42− and PO43−. Release patterns do not indicate a general trend: some compounds show maximum release in the first fractions while for others the maximum was observed in later test stages. Ecotoxic effects in eluates were found, which were higher in the eluate fraction 7 (maximum lowest ineffective dilution for luminescent bacteria (LIDL) 256) than in the eluate fraction 1 + 2 (maximum LIDL = 24). The sensitivity of the test systems was very different with highest effects for luminescent bacteria, followed by algae and daphnia and without effects in the fish egg test and umu test. A biotest battery for the comprehensive assessment is therefore advisable.

Chlorination is essential to provide safe drinking water. However, this process leads to the formation of disinfection byproducts (DBPs). In this study, tryptophan (Trp) has been selected as a precursor to conduct the chlorine disinfection. Moreover, the factors that affect the formation of trihalomethanes (THMs) and iodinated trihalomethanes (I-THMs) are investigated. The formation pathway of Trp chlorination is proposed based on the intermediate products identified. According to the experimental results, the formation of THMs and I-THMs during Trp chlorination fitted a new first-order kinetic model. The dosage of chlorine, temperature, pH and the ratio of bromide and iodide had major influence on the formation of THMs and I-THMs during chlorination. In addition, the inhibition of luminescent bacteria Vibrio fischeri in the water sample increased during Trp chlorination.

Ultraviolet (UV) photodegradation is increasingly applied to control volatile organic compounds (VOCs) due to its degradation capabilities for recalcitrant compounds. However, sometimes the UV photodegradation products are also toxic and can affect human health. Here, 10 VOCs at 150~200 ppm in air were treated using a laboratory-scale UV reactor with 185/254 nm irradiation, and the biotoxicity of their off-gas was studied by investigating their off-gas absorption solutions. The CO2 increase and VOC decrease were 39~128 ppm and 0~42 ppm, respectively, indicating that the VOCs and their products were mineralized in off-gas absorption solutions. The total organic carbon (TOC) of the absorption solutions are 4~20 mg∙L&minus, 1. Luminescent bacteria and Daphnia magna were used to detect the acute toxicity, and an umu assay was used to determine the genotoxic potential. Trichloroethylene showed a highest toxicity to luminescent bacteria, while chlorobenzene had the lowest toxicity. Water-soluble UV photodegradation products for styrene are very toxic to Daphnia magna. In the umu assay, the genotoxicities of off-gas absorption solutions of trichloroethylene, methylbenzene, ethyl acetate, butyl alcohol, and styrene were 51.26, 77.80, 86.89, 97.20, and 273.62 mg (4-NQO)&middot, L&minus, 1 respectively. In addition, the analysis of the genotoxicity/TOC and intermediates products indicated that the off-gas absorption solutions of styrene, trichloroethylene, and butyl alcohol contain many highly toxic substances.

In this study, peroxydisulfate (PDS) was successfully activated by nanoscale zero-valent iron (nZVI) for the degradation of sulfamethoxazole (SMX, antibiotic frequently detected in the environment) in agricultural soils. The results indicated that the degradation of SMX was affected by the nZVI dose, the ratio of SMX/PDS, the ratio of soil/water and reaction temperature, and in cinnamon soils 87.6% of SMX degradation can be achieved within 4 h at 30 °C when the initial nZVI dose was 0.03 g g−1 soil, the molar ratio of SMX/PDS = 1/75 and the soil/water = 1/1. The results of radical scavenger experiments and electron spin resonance (ESR) tests showed that hydroxyl radical ( OH) was the dominant reactive species in this system. The ecotoxicity tests of the soil by germination test, luminescent bacteria experiment and enzyme activity test indicated that the ecotoxicity of soil after treatment was obviously lower than the contaminated soil. In addition, there was almost no effect on plant growth when compared with original soil. Furthermore, this system exhibited a great degradation capacity for SMX in different types of agricultural soils, and the degradation efficiencies of SMX in other four soils were 90.6% (yellow brown earths), 80.8% (brown earths), 86.5% (black soils) and 96.1% (red earths), respectively. This work provides an optional method for agricultural soil pollution control.

Biotic ligand model (BLM) was extended to predict the toxicity of inorganic arsenate (iAs(V)) to the luminescent bacteria, Aliivibrio fischeri. As the pH increased from 5 to 9, the HAsO42- form predominated more than the H2AsO4- form did, and the EC50[As]T (50% effective iAs(V) concentration) decreased drastically from 3554 ± 393 to 39 ± 6 μM; thus, the HAsO42- form was more toxic to A. fischeri than H2AsO4-. As the HPO42- activity increased from 0 to 0.44 mM, the EC50{HAsO42-} values (50% effective HAsO42- activity) increased from 31 ± 6 to 859 ± 128 μM, indicating that the toxicity of iAs(V) decreased, owing to the competition caused by the structural similarity between iAs(V) and phosphate ions. However, activities of Ca2+, Mg2+, K+, SO42-, NO3-, and HCO3- did not significantly affect the EC50{HAsO42-} values. The BLM was reconstructed to take into account the effects of pH and phosphate, and the conditional binding constants for H2PO4-, HPO42-, H2AsO4-, and HAsO42- to the active binding sites of A. fischeri were obtained; 3.424 for logKXH2PO4, 4.588 for logKXHPO4, 3.067 for logKXH2AsO4, and 4.802 for logKXHAsO4. The fraction of active binding sites occupied by iAs(V) to induce 50% toxicity (fmix50%) was found to be 0.616.

A novel tool, the DAMTA analyzer (Device for Analytical Monitoring and Toxicity Assessment), designed for fully automated toxicity measurements based on luminescent bacteria as well as for concomitant determination of chemical parameters, was developed and field-tested. The instrument is a robotic water analyzer equipped with a luminometer and a spectrophotometer, integrated on a thermostated reaction plate which contains a movable carousel with 80 cuvettes. Acute toxicity is measured on-line using a wild type Photobacterium phosphoreum strain with measurable bioluminescence and unaltered sensitivity to toxicants lasting up to ten days. The EC50 values of reference compounds tested were consistent with A. fischeri and P. phosphoreum international standards and comparable to previously published data. Concurrently, a laboratory trial demonstrated the feasibility of use of the analyzer for the determination of nutrients and metals in parallel to the toxicity measurements. In a prolonged test, the system was installed only in toxicity mode at the premises of the World Fair “Expo Milano-2015″, a high security site to ensure the quality of the supplied drinking water. The monitoring program lasted for six months during which ca. 2400 toxicity tests were carried out; the results indicated a mean non-toxic outcome of −5.5 ± 6.2%. In order to warrant the system's robustness in detecting toxic substances, Zn was measured daily with highly reproducible inhibition results, 70.8 ± 13.6%. These results assure that this novel toxicity monitor can be used as an early warning system for protection of drinking water sources from emergencies involving low probability/high impact contamination events in source water or treated water.

Acute toxicities of anaerobic ammonia oxidation (ANAMMOX) substrates and four antibiotics from pharmaceutical wastewaters on ANAMMOX process were reported. Individual and joint acute toxicity assays were performed using 50% inhibitory concentration (IC50). Results showed that IC50 values and their 95% confidence interval of ammonium chloride (A), sodium nitrite (B), penicillin G-Na (C), polymyxin B sulfate (D), chloramphenicol (E) and kanamycin sulfate (F) were 2708.9 (2247.9–3169.9), 1475.4 (1269.9–1680.9), 5114.4 (4946.4–5282.4), 10.2 (1.8–18.6), 409.9 (333.7–486.1) and 5254.1 (3934.4–6573.8) mg L−1 respectively, suggesting toxicities were in the order of D > E > B > A > C > F. Joint acute toxicities of bicomponent mixtures A and B, C and D, C and F, D and F were independent; D and E, E and F were additive while C and E were synergistic. Joint acute toxicities of multicomponent mixtures were synergistic or additive. Luminescent bacteria test is an easy and robust method for forecasting the feasibility of ANAMMOX process for pharmaceutical wastewater treatment.

One of the major problems of airport operation is the impact of pollution caused by runoff waters. Runoff waters at an airport may contain high concentrations of different contaminants resulting from various activities of its operation. High quantities of aircraft de-icing/anti-icing fluids are used annually at airports worldwide. Aircraft de-icers and anti-icers may have negative environmental impacts, but their effects on aquatic organisms are virtually unknown. In order to address this issue, aircraft de-icers, pavement de-icers and wastewater samples were obtained from a regional airport. To evaluate the toxicity of wastewater samples and aircraft de-icing/anti-icing fluids (ADAFs), two bio-tests were performed: the Lemna growth inhibition test according to OECD guideline 221 and the luminescent bacteria test according to ISO guideline 11348-2. In the Lemna growth inhibition test, phytotoxicity was assessed using the endpoints frond number and frond area. The luminescent bacteria test involved the marine bacterium Vibrio fischeri. The estimates of effective concentrations (EC50) values were determined using the free software R and the "drc" library. Aquatic plants and marine bacteria showed a higher sensitivity towards ADAFs than to wastewater samples. Experiments showed that aircraft de-icing/anti-icing fluids and wastewater samples were relatively more toxic towards Lemna gibba L. in comparison to V. fischeri.

The increasing application of nanoparticles (NPs) to a variety of new technologies has become a matter ofconcern due to the potential toxicity of these materials. Many questions about the fate of NPs in the environmentand the subsequent impact on ecosystems need to be answered. The aim of this work was to evaluate theecotoxicity of two alumina-based nanoceramics, γ-Al2O3 (NC) and Ni/ γ-Al2O3 (NiNC) by means of three differentstandardized tests: Biochemical Oxygen Demand (BOD5), bioassay with luminescent bacteria (Vibrio fischeri;Microtox), and bioassay on amphibian larvae (Rhinella arenarum) (AMPHITOX). BOD5 values of a verybiodegradable mixture (glucose/glutamic acid) decreased with the addition of NiNC(43.8%) and NC (31.6%)with respect to control samples (52.9%). Microtox test results indicated that NiNC presents higher toxicity thanNC, with EC50s values of 16.1% and 29.9% respectively; a reduced toxicity was observed, however, in presenceof organic matter, thus obtaining EC50s of 37.8% and 19.4%. The results of AMPHITOX test showed a significantincrease in the toxicity of both substances over time, the NiNC toxicity being greater than that of NC. The valuesof 96 h-LC50 and 504 h-LC50 determined for NiNC were 1.58 and 0.83 mg/L, respectively, and 14.5 and10.5 mg/L for NC samples. Amphibian larvae exhibited collapsed cavities, edema, axial flexures, and behavioralalterations as hyperkinesia and reduced movements. These results evidence the vulnerability of wildlife to xenobioticsand the need to develop specific standardized ecotoxicity tests in order to help environmental sustainabilityand natural species conservation. Fil: Svartz, Gabriela Veronica. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de San Martín. Instituto de Investigación e Ingeniería Ambiental; Argentina Fil: Papa, Mariana Inés. Instituto Nacional de Tecnología Industrial; Argentina Fil: Gosatti, Marina. Comisión Nacional de Energía Atómica. Gerencia Complejo Tecnológico Pilcaniyeu; Argentina Fil: Jordán, Marianela Paula. Instituto Nacional de Tecnología Industrial; Argentina Fil: Soldati, Analía Leticia. Comisión Nacional de Energía Atómica. Gerencia Complejo Tecnológico Pilcaniyeu; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Samter, Paula. Instituto Nacional de Tecnología Industrial; Argentina Fil: Guraya, María M.. Comisión Nacional de Energía Atómica. Gerencia Complejo Tecnológico Pilcaniyeu; Argentina. Universidad Tecnológica Nacional. Facultad Regional Buenos Aires; Argentina Fil: Perez Coll, Cristina Silvia. Universidad Nacional de San Martín. Instituto de Investigación e Ingeniería Ambiental; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Perez Catán, Soledad. Comisión Nacional de Energía Atómica. Gerencia Complejo Tecnológico Pilcaniyeu; Argentina

Since aminophosphonate-based herbicides like glyphosate are currently one of the most popular and widely applied active agent in agrochemistry, there is an urgent need for searching new compounds among this family with potential herbicidal activity, but exhibiting low toxicity against surrounding environment. Six new (5-nitrofurfuryl)-derived aminophosphonates were synthesized for the first time and apart from the only one example of N-benzylamino(5-nitrofuryl)-methylphosphonic acid, it was the first time in the history, when this class of compounds was prepared. Their prospective and real biological properties have been followed up by evaluation of their preliminary ecotoxicology. They have been then investigated in aspect of their phytotoxicity against oat (A. sativa) and common radish (R. sativus) exhibiting moderate-to-severe toxicity for these plants. The significant selectivity towards radish (up to 3 times greater toxicity against radish) was observed in some cases. Title compounds were also tested in terms of their toxicity for freshwater crustaceans H. incongruens (ostracods) and marine luminescent bacteria A. fischeri. Although their harmful action on ostracods was not too much elevated, they were found to be highly toxic for bacteria. Various aspects of their ecotoxicity are discussed in this paper.

Monitoring and assessing toxic materials which are being released into the environment along with wastewater is a growing concern in many industries. The current research describes a highly sensitive and rapid method for the detection of toxic concentrations of heavy metals in aquatic environments. Water samples were collected from southern coasts of the Caspian Sea followed by screening of luminescent bacteria. Phylogenetic analysis, including gene sequence of 16S rRNA, and biochemical tests were performed for identification of the isolate. Luminescence activity was tested and measured after treatment of the isolate with different concentrations of heavy metals and reported as EC50 value for each metal. A luminous, gram negative bacterium with the shape of a curved rod was isolated from the Caspian Sea. Biochemical tests and 16S rRNA gene sequence analysis indicated that the isolate MM1 had more than 99% similarity to Vibrio campbellii. The novel isolate is able to emit high levels of light. Bioluminescence inhibitory assay showed that the Vibrio sp. MM1 had the highest sensitivity to zinc and the lowest sensitivity to cadmium; EC50 values were 0.97mgl-1 and 14.54mgl-1, respectively. The current research shows that even low concentrations of heavy metals can cause a detectable decline in luminescence activity of the novel bacterium Vibrio sp. MM1; hence, it makes a good choice for commercial kits for the purpose of monitoring toxic materials.

A European round robin test according to ISO 5725-2 was conceptually prepared, realised, and evaluated. The aim was to determine the inter-laboratory variability of the overall process for the ecotoxicological characterization of construction products in eluates and bioassays. To this end, two construction products BAM-G1 (granulate) and HSR-2 (roof sealing sheet), both made of EPDM polymers (rubber), were selected. The granular construction product was eluted in a one stage batch test, the planar product in the Dynamic Surface Leaching test (DSLT). A total of 17 laboratories from 5 countries participated in the round robin test: Germany (12), Austria (2), Belgium (1), Czech Republic (1) and France (1). A test battery of four standardised ecotoxicity tests with algae, daphnia, luminescent bacteria and zebrafish eggs was used. As toxicity measures, EC50 and LID values were calculated. All tests, except the fish egg test, were basically able to demonstrate toxic effects and the level of toxicity. The reproducibility of test results depended on the test specimens and the test organisms. Generally, the variability of the EC50 or LID values increased with the overall level of toxicity. For the very toxic BAM-G1 eluate a relative high variability of CV = 73%-110% was observed for EC50 in all biotests, while for the less toxic HSR-2 eluate the reproducibility of EC50 varied with sensitivity: it was very good (CV = 9.3%) for the daphnia test with the lowest sensitivity, followed by the algae test (CV = 36.4%). The luminescent bacteria test, being the most sensitive bioassay for HSR-2 Eluate, showed the highest variability (CV = 74.8%). When considering the complex overall process the reproducibility of bioassays with eluates from construction products was acceptable.

Following urbanization, a large number of urban rivers were contaminated and turned to black-odor rivers. The traditional approach for detecting water quality is based on chemical or physical analysis. However, biological toxicity of black-odor water has been less addressed. As two typical black-odor rivers, Jiushanwai River (JS) and Shanxia River (SX) are tributaries of Wen-Rui Tang River in Wenzhou (south of China). The eco-safety of the urban rivers was evaluated by bioassay for water toxicity in this study. Ten and 5 sampling sites were respectively set along JS and SX. Water samples were collected monthly from October 2010 to October 2011. The general physical and chemical parameters of river water were monitored. In order to investigate the ecotoxicological effects of black-odor water, the following bioassays were used: (1) Fish acute toxicity test (Danio rerio, comprehensive toxicity), (2) luminescent bacteria bioassay (Qinghaiensis vibrio, toxicity to bacteria), and (3) tropical claw embryo assay (Xenopus tropicalis, embryo toxicity). Biotoxicity of black-odor rivers water was demonstrated by D. rerio, Q. vibrio, and X. tropicalis embryos. Toxicological effects of black-odor water were respectively shown by mortality of zebrafish, and by the relative inhibitory light rate of luminescent bacteria. However, luminescent bacteria were more sensitive to inspect biotoxicity than zebrafish. In X. tropicalis embryos test, toxicological effects of black-odor water were mostly shown by embryos’ survival rate and teratogenic rate. Bioassay results showed that toxicity of SX water was higher than that of JS water, especially in summer. Statistical analysis of luminescent bacteria toxicity test showed that biotoxicity of SX and JS was high in summer, but low in winter and spring. The seasonal changes of water toxicity of the black-odor river were positively correlative with changes of water temperature (p

A photodegradation technology based on the combination of ultraviolet radiation with H2O2 (UV/H2O2) for degrading tri(chloroisopropyl) phosphate (TCPP) was developed. In ultrapure water, a pseudo-first order reaction was observed, and the degradation rate constant reached 0.0035 min−1 (R2 = 0.9871) for 5 mg L−1 TCPP using 250 W UV light irradiation with 50 mg L−1 H2O2. In detail, the yield rates of Cl− and PO43− reached 0.19 mg L−1 and 0.58 mg L−1, respectively. The total organic carbon (TOC) removal rate was 43.02%. The pH value of the TCPP solution after the reaction was 3.46. The mass spectrometric detection data showed a partial transformation of TCPP into a series of hydroxylated and dechlorinated products. Based on the luminescent bacteria experimental data, the toxicity of TCPP products increased obviously as the reaction proceeded. In conclusion, degradation of high concentration TCPP in UV/H2O2 systems may result in more toxic substances, but its potential application for real wastewater is promising in the future after appropriate optimization, domestication and evaluation.

Luminescent bacterial test is a fast and sensitive method for acute toxicity assessment of water and wastewater. In this study, an improved toxicity testing method was developed using the freshwater luminescent bacteria Vibrio qinghaiensis sp.-Q67 that involved pretreatment of water samples with reverse osmosis (RO) to eliminate the interferences caused by nutrients in concentrated samples and to improve the reliability and sensitivity of the analysis. Because water samples contain low concentrations of several target toxic substances, rapid acute toxicity testing method that is commonly employed does not achieve enough sensitivity. The proposed RO pretreatment could effectively enrich organic and inorganic substances in water samples to enable a more effective and sensitive toxicity evaluation. The kinetic characteristics of toxicity of raw sewage and secondary effluent were evaluated based on the relative luminescence unit (RLU) curves and time-concentration-effect surfaces. It was observed that when the exposure time was prolonged to 8-h or longer, the bacteria reached the logarithmic growth stage. Hence, the stimulating effects of the coexisting ions (such as Na+, K+, NO3-) in the concentrated samples could be well eliminated. A 10-h exposure time in proposed Q67 test was found to quantitatively evaluate the toxicity of the organic and inorganic pollutants in the RO-concentrated samples. © 2013 Elsevier Inc.

Triclosan, one of the most widely used disinfectants, has been found to be toxic to animals and human beings. In this paper, triclosan was degraded on TiO 2 nanotube arrays, using a photoelectrocatalytic (PEC) process under UV illumination, with Na 2 SO 4 as the supporting electrolyte. The effect of bias potential was investigated and the results showed that 0 V was the most appropriate potential for the degradation of triclosan. In 30 min, 78.7% of triclosan had degraded during the PEC process. Intermediate analysis showed that 2,7-dichlorodibenzodioxin (DCDD) had formed during the degradation. The toxicity change during the PEC process was investigated using a luminescent bacteria test, with the results demonstrating that the toxicity of the reaction liquid decreased at the beginning and subsequently increased to a stable level. The indications were that some intermediates such as 2,7-dichlorodibenzodioxin was more toxic and stable than triclosan in the solution.

Crude oil is a complex mixture of petroleum hydrocarbons (PHC) with distinct chemical, physical and toxicological properties relevant for contaminated site risk assessment. Ecotoxicological effects of crude oil distillation fractions on luminescent bacteria (Vibrio fischeri), earthworms (Dendrobaena hortensis) and invertebrates (Heterocypris incongruens) were tested using two spiked soils and their elutriates. Fraction 2 (F2) had an equivalent carbon number (ECN) range of >10 to 16, and F3 from >16 to 39. F2 showed a substantially higher ecotoxicological effect than F3 for Vibrio and Dendrobaena. In contrast, severe inhibition of Heterocypris by the poorly soluble F3 is attributed to mechanical organ blockage. Immediate sequestration of PHC to the organic matter-rich soil effected reduced toxicity for all organisms. This study indicates that a more differentiated consideration (i) of PHC mixtures based on ECN range and (ii) of model soil properties employed for ecotoxicity testing should be included into PHC-contaminated site risk assessment.

Ethyl-4-aminobenzoate (Et-PABA) is currently used as a substitute for 4-aminobenzoate (PABA) in sunscreens and anesthetic ointments. Despite its widespread use and hydrophilicity, Et-PABA has never been found in environmental waters. This study, probed the occurrence of Et-PABA in both seawater and drinking water sources in Hong Kong, and evaluated its transformation products (TPs) and environmental fate via cumulative potency and photocatalytic profile analyses. Another 11 UV filters used in skin-care products were also studied. Et-PABA was not detected in any water sample. Four other UV filters were dominant at ng/L level in both seawater and drinking water sources. UHPLC-QTOF-MS was used to elucidate the structure of TPs. With high resolution accurate mass data and fragment rationalization, 11 Et-PABA TPs were characterized, including seven intermediates firstly proposed as TPs; two compounds were reported for the first time. It is proposed that photocatalysis induces transformation pathways of (de)hydroxylation, demethylation and molecular rearrangement. Luminescent bacteria tests showed decreasing toxicity with increasing irradiation of Et-PABA, suggesting that irradiation TPs are less toxic than the parent compound. Transformation of Et-PABA appears to explain why Et-PABA has not been detected in the natural environment.

Fenamic acids, one important type of non-steroidal anti-inflammatory drugs, are ubiquitous in environmental matrices. Thus it is of high significance to know the fate of them during chlorination disinfection considering their potential toxicity to the environment and humans. In the present study, the chlorination kinetics of three fenamic acids, i.e. mefenamic acid (MEF), tolfenamic acid (TOL) and clofenamic acid (CLO), were examined at different pHs, which followed second-order reaction under studied conditions. The studied fenamic acids degraded fast, with the largest apparent second-order rate coefficient ( k app ) values of 446.7 M −1 s −1 (pH 7), 393.3 M −1 s −1 (pH 8) and 360.0 M −1 s −1 (pH 6) for MEF, TOL and CLO, respectively. The transformation products (TPs) were identified by solid-phase extraction-liquid chromatography-mass spectrometer and ion-pair liquid-liquid extraction and injection port derivatization-gas chromatography-mass spectrometer. Despite different numbers of TPs were detected for each studied fenamic acid through these two analytical methods, the types of TPs were almost the same; chlorine substitution, oxidation and the joint oxidation with chlorine substitution are transformation reactions involved in chlorination. Moreover, the total toxicity of the TPs was assayed based on luminescent bacteria. Under different pHs, the different types of TPs might form, resulting in the varied total toxicity. The toxicity of all three fenamic acids chlorinated at pH of 8 was greater than those at pHs of 6 and 7. This study provided the information about the kinetics, transformation and toxicity of three fenamic acids during water chlorination, which is important to the drinking water safety.

The European Construction Products Regulation allows Member States to adopt rules for evaluating the environmental impact of their buildings. The aim of the project was to develop recommendations for a test battery for the ecotoxicological assessment of the environmental impact of construction products for outdoor use and contribute to the European harmonization of test methods. From a shortlist of 39 products 20 products were included in the ecotoxicological testing program. Monolithic and plate-like construction products were eluted in the Dynamic Surface Leaching test (DSLT) in accordance with CEN/TS 16637-2, granular products were eluted in a one stage batch test in accordance with DIN EN 12457-1. The eluates were examined in four aquatic toxicity tests (algae, daphnia, luminescent bacteria, fish eggs), a genotoxicity test (umu test) and in the respirometer test (OECD 301 F). Here, low to very high ecotoxicity was observed (up to a dilution factor of 1536). Six out of 8 eluates, whose TOC exceeded 10 mg L −1 showed a good biodegradability above 75%. The intra-laboratory repeatability of the Lowest Ineffective Dilution (LID) usually was within ±1 dilution steps (ecotoxicity tests) and ±2 dilution steps (leaching and ecotoxicity tests). This is acceptable, when considering that the overall variability of sample preparation, leaching test, and bioassays add up. The conclusions lead to practical recommendations for a suitable combination of leaching and ecotoxicity tests.

Traditionally, the toxicity of river contaminants is analyzed chemically or physically through river bed sediments. The biotoxicity of polluted sediment leachates has not caught our attention. This study aims to overcome this deficiency through a battery of biotests which were conducted to monitor comprehensive toxicity of sediment leachates for the Yaogang River in East Jiangsu Province of China, which is in close proximity to former pesticide plants. The general physical and chemical parameters of major pollutants were analyzed from river bed sediments collected at five strategic locations. The ecotoxicity analyses undertaken include overall fish (adult zebrafish) acute toxicity, luminescent bacteria (Vibrio fischeri) bioassay, and zebrafish embryo toxicity assay. Compared with the control group, sediment leachates increased the lethality, inhibited the embryos hatching and induced development abnormalities of zebrafish embryos, and inhibited the luminescence of V. fischeri. The results show that sediment leachates may assume various toxic effects, depending on the test organism. This diverse toxicity to aquatic organisms reflects their different sensitivity to sediment leachates. It is found clearly that V. fischeri was the organism which was characterized by the highest sensitivity to the sediment leachates. The complicated toxicity of leachates was not caused by one single factor but by multiple pollutants together. This indicates the need of estimations of sediment leachate not only taking into account chemical detection but also of applying the biotests to the problem. Thus, multigroup bioassays are necessary to realistically evaluate river ecological risks imposed by leachates.

The present study demonstrates development of a rapid testing protocol based on a small portable luminometer using flash kinetic assessment of bacterial bioluminescence. The laboratory comparisons based on six model organic toxicants and two metals showed significant correlations between responses of freshwater bacteria Photorhabdus luminescens and standard marine bacterial species Vibrio fisheri. While P. luminescens was less sensitive in standard arrangements, the responses of both organisms were comparable in the newly introduced portable luminometer setup. The applicability and reproducibility of the portable luminometer protocol was further demonstrated in the assessment of 43 European wastewater effluents that were simultaneously tested for toxicity and analysed for 150 organic and 20 inorganic contaminants grouped into 13 major chemical classes. Clear association between the toxic responses in both compared bacterial species and the elevated levels of inorganic compounds (toxic metals), chlorophenols and benzotriazole anticorrosives was observed. The new protocol with a portable luminometer provides a fast (30 s) response and may be used as a tool for rapid in situ toxicity evaluation of freshwater environmental samples such as effluents.

The environmental impact of two biocide-free antifouling paints, fluoropolymer and silicone types, painted on a test cylinder was assessed using a battery of ecotoxicity test and chemical analyses for organic micro-pollutants such as perfluoroalkyl substances (PFAS). A biocide paint containing zinc pyrithione (ZnPT2) and cuprous oxide was assessed as a positive control. A standardized laboratory rotating-cylinder method using each test cylinder with artificial seawater was performed for 45 days. After 1 h rotation, the leaked seawater was subjected for bioassay and chemical analyses twice weekly. The seawater extracts from the biocide paint showed adverse effects on bacteria, algae, and crustaceans, but those from the biocide-free paints did not. The leakage seawater from biocide-free paints, after 7-day continuous rotation, contained the same concentration levels of PFAS as blank seawater used to conduct the tests. Thus, no significant toxicities of the biocide-free paints were found under the conditions...

Degradation and toxicity reduction of perfluorooctanoic acid (PFOA) were investigated using TiO2 adsorption, vacuum ultraviolet (VUV) photolysis, and VUV/TiO2 photocatalysis in acidic and basic aqueous solutions. Chemical analyses of PFOA and its selected by-products and an acute toxicity assessment using the luminescent bacteria Vibrio fischeri (Microtox®) were conducted during and after the various treatment methods. PFOA was found to be best treated by VUV/TiO2 at pH 4 with HClO4, as illustrated by the almost complete degradation of PFOA within 360 min and rapid removal of acute microbial toxicity within 60 min. This difference in the efficiency may be attributed to the strong oxidation effectiveness of the radical species generated in acidic media and the electron scavenger effect of the addition of HClO4 in VUV/TiO2 photocatalysis. In addition, the proposed method could effectively decompose other perfluorocarboxylic acid (PFCA) species (C3–C7 perfluoroalkyl groups) if the initial intermediates forme...

The compositions of explosive wastewater generated from TNT (2,4,6-trinitrotoluene) purification stage were characterized by using UV–vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), high performance liquid chromatograph (HPLC) and gas chromatograph/mass spectroscopy (GC/MS). The acute toxicity was evaluated by bacterium bioluminescence assay using a freshwater luminescent bacterium (Vibrio qinghaiensis sp. Nov.) and a marine luminescent bacterium (Photobacterium phosphoreum). The results showed that the wastewater's biodegradability was poor due to the high amount of chemical oxygen demand (COD). The main organic components were dinitrotoluene sulfonates (DNTS) with small amount of TNT, dinitrotoluene (DNT), mononitrotoluene (MNT) and other derivatives of nitrobenzene. It was highly toxic to luminescent bacteria P. phosphoreum and V. qinghaiensis sp. Nov. After reaction time of 15 min, the relative concentration of toxic pollutants (expressed as reciprocal of dilution ratio of wastewater) at 50% of luminescence inhibition ratio was 5.32 × 10−4 for P. phosphoreu, while that was 4.34 × 10−4 for V. qinghaiensis. V. qinghaiensis is more sensitive and suitable for evaluating the wastewater's acute toxicity than P. phosphoreum. After adsorption by resin, the acute toxicity can be greatly reduced, which is helpful for further treatment by biological methods.

The present study presents the toxicity data of benzoic acid and its derivatives on Pseudokirchneriella subcapitata, in terms of EC50 and NOEC values. Median effective concentrations (EC50) range from 0.55 to 270.7 mg/L (based on final yield) and 1.93 to 726.3mg/L (based on algal growth rate). No-observed-effect concentration (NOEC) is within the range of

In Europe hazardous wastes are classified by 14 criteria including ecotoxicity (H 14). Standardized methods originally developed for chemical and soil testing were adapted for the ecotoxicological characterization of wastes including leachate and solid phase tests. A consensus on which tests should be recommended as mandatory is still missing. Up to now, only a guidance on how to proceed with the preparation of waste materials has been standardized by CEN as EN 14735. In this study, tests including higher plants, earthworms, collembolans, microorganisms, duckweed and luminescent bacteria were selected to characterize the ecotoxicological potential of a boiler slag, a dried sewage sludge, a thin sludge and a waste petrol. In general, the instructions given in EN 14735 were suitable for all wastes used. The evaluation of the different test systems by determining the LC/EC50 or NOEC-values revealed that the collembolan reproduction and the duckweed frond numbers were the most sensitive endpoints. For a final classification and ranking of wastes the Toxicity Classification System (TCS) using EC/LC50 values seems to be appropriate.