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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.

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.

It has been proven that the raw wastewater, secondary effluent and even reclaimed water may have toxic effects on aquatic organisms. In the present study, fractionation procedures combined with bioassays using luminescent bacteria were conducted to identify the fractions that contributed to the acute and long-term toxicity of municipal wastewater. Solid phase extraction was used to divide dissolved organic matter from the wastewater into three fractions, including non-polar, medium-polar and polar fraction. Among these fractions, although the acute toxicity of municipal wastewater was mainly caused by polar and medium-polar chemicals, the acute toxicity induced by the unit mass of the medium-polar fraction was the greatest. Using three kinds of resins, the organic substances in municipal wastewater were classified into six fractions, and the long-term toxicity of these fractions was further identified. The long-term toxicity of the hydrophobic neutrals, which were the primary toxic substances in raw wastewater, decreased after the conventional secondary biological treatment. Hydrophilic neutrals, which accounted for the majority of organic substances in the secondary effluent, were the main substances with long-term toxicity in the secondary effluent. The identification of fractions with acute and long-term toxicity in municipal wastewater is beneficial for further treatment to attenuate the ecotoxicity of wastewater before discharge into the aquatic environment.

Fifteen native luminescent bacteria were isolated from the Gulf of Thailand, and their sensitivity for the detection of toxicity of crude oil and its aromatic components was investigated. Of these isolates, Vibrio campbellii strain FS5 was one of the two most highly inhibited bacteria at all crude oil concentrations. This bacterium showed a decrease in luminescence intensity of between 10.7 and 80.2% after a 15-min exposure to 0.0001–10 mg/L of crude oil. The degree of bioluminescence inhibition increased with increasing concentrations of crude oil. The presence of crude oil at all concentrations had negative effects on the log bioluminescence per log number of viable cells after 15- to 105-min exposure. About 10 to 100 times, lower half maximal effective concentration (EC50) values were observed for polycyclic aromatic hydrocarbons (PAHs) than those for benzene, toluene, ethylbenzene, and xylene (BTEX). In the presence of each individual BTEX and PAH, the bioluminescence inhibition increased with increasing exposure time (1–32 h). This indigenous bacterium can be used as a simple and general indicator of oil contamination and its impact on coastal waters as well as for assessing potential toxicity during oil bioremediation.

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.

This study evaluated the acute effects of nine different production chemicals typically employed in oil exploration on the toxicity of a synthetic produced water (PW). Bioassays with the Microtox® System were performed to monitor changes in the level of light emission of the marine luminescent bacteria Vibrio fischeri during exposure to the samples. The results show that synthetic PW is moderately toxic to these organisms, and the addition of oilfield chemicals significantly increases its toxicity. For most of the additives tested, the toxicity of the aqueous phase following partitioning against crude oil was not strongly altered by the presence of these chemicals. Synergistic effects occurred in the three different mixtures investigated. Among the additives studied, biocide, corrosion inhibitor, H2S scavenger, and surfactant were the most toxic for V. fischeri. Furthermore, the surfactant has been identified as the possible source of the acute toxicity observed.

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.

The aim of the study was ecological risk assessment (ERA) of the agricultural soils located in the vicinity of the highly industrialized area and exposed to different emission sources of polycyclic aromatic hydrocarbons (PAHs). In this study, we demonstrated the combination of generic and site-specific ERA approach for screening assessment and delineation of the area of a high ecological risk. Generic approach was based on a hazard quotient and indicated that 62% of the research area needs further assessment. For site-specific evaluation, the Triad approach was utilized. Information from three lines of evidence (LoE): chemical, ecotoxicological and ecological, was integrated into one environmental risk (EnvRI) index. The chemical risk was derived from toxic pressure coefficients based on the total PAHs concentration. The ecotoxicological LoE included an acute toxicity testing: the luminescent bacteria Aliivibrio fischeri activity in both liquid- and solid-phase samples and the ability of crustacean Thamnocephalus platyurus to food uptake. The ecological LoE comprised microbial parameters related to soil respiration and enzymatic activity. Integrated EnvRI index ranged from 0.44 to 0.94 and was mainly influenced by high values of chemical LoE risk, while the ecotoxicological and ecological LoE indicated no or low risk. Due to the relatively high uncertainty associated with the contradictory information given by LoEs, there is the need to confirm potential risk in a tier 2 analysis.

Fish carpaccio is a ready-to-eat product with a very limited shelf life. In the present work, the use of high pressure treatment (HP) and/or antimicrobial edible film was studied in order to improve quality and stability of salmon carpaccio. In a preliminary part of the work, a film composed of gelatin plus chitosan incorporating clove essential oil was selected, based on its physicochemical and antimicrobial properties. Eugenol and β-caryophyllene, the main volatile components of the film, migrated to salmon muscle, the release being favored by HP and storage time. Concurrently, reducing power of the muscle increased, resulting in prevention of lipid oxidation derived from either HP or refrigerated storage. HP treatment reduced total microbial counts by 1.5 log cycles from the onset of storage, whereas the film reduced it by 2 log cycles after 3 days. The combination of HP and edible film exerted the most intense antimicrobial effect, total bacterial counts, luminescent bacteria, HS-producing organisms, pseudomonads, enterobacteria, and lactic acid bacteria remaining constant or under detection limit over the whole storage period (11 days). The combined use of HP treatment and gelatin–chitosan–clove essential oil film is an effective way of improving quality and stability of salmon carpaccio., This research was financed by the Spanish Ministry of Economy and Competitiveness (projects I3-200670l141, AGL2014-52825-R). Author López de Lacey was funded by the JAE-CSIC predoc program and Gómez-Estaca by the “Juan de la Cierva” program.

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.

In effect-directed analysis (EDA) with high-performance thin-layer chromatography (HPTLC), the effect is often detected using images. Thus, an approach to create inhibition chromatograms from these images was developed using the example of the HPTLC- bioluminescence inhibition test. A comparison between the cuvette test and the HPTLC test shows that the test on the plate is significantly more sensitive. To describe the strength of the effect, the EC50 value is determined from the dose-response relationship. However, the inhibiting compounds are generally unknown and thus their concentrations are also unknown. Therefore, instead of the concentration, the known application volumes are used. This enables the calculation of the application volume necessary to achieve 50% inhibition. Since the volume is inversely proportional to the concentration, the reciprocal value of the calculated volume is indicated and is referred to as the reciprocal iso-inhibition volume (RIV). Using this RIV-concept, it is now possible to compare inhibition bands within and between plates. The entire evaluation is described by the means of two samples from a contaminated site using the bioluminescence inhibition.

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

Chlorination is essential to the safety of reclaimed water; however, this process leads to concern regarding the formation of disinfection byproducts (DBPs) and toxicity. This study reviewed the formation and control strategies for DBPs and toxicity in reclaimed water during chlorination. Both regulated and emerging DBPs have been frequently detected in reclaimed water during chlorination at a higher level than those in drinking water, indicating they pose a greater risk to humans. Luminescent bacteria and Daphnia magna acute toxicity, anti-estrogenic activity and cytotoxicity generally increased after chlorination because of the formation of DBPs. Genotoxicity by umu-test and estrogenic activity were decreased after chlorination because of destruction of toxic chemicals. During chlorination, water quality significantly impacted changes in toxicity. Ammonium tended to attenuate toxicity changes by reacting with chlorine to form chloramine, while bromide tended to aggravate toxicity changes by forming hypobromous acid. During pretreatment by ozonation and coagulation, disinfection byproduct formation potential (DBPFP) and toxicity formation potential (TFP) occasionally increase, which is accompanied by DOC removal; thus, the decrease of DOC was limited to indicate the decrease of DBPFP and TFP. It is more important to eliminate the key fraction of precursors such as hydrophobic acid and hydrophilic neutrals. During chlorination, toxicities can increase with the increasing chlorine dose and contact time. To control the excessive toxicity formation, a relatively low chlorine dose and short contact time were required. Quenching chlorine residual with reductive reagents also effectively abated the formation of toxic compounds.

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.

As the application of nanoparticles (NPs) and their release to the environment has increased, it is important to verify their toxicity, with a special emphasis on particle solubilization and the interaction of NP mixtures. In the current study, a model luminescent bacteria, Vibrio fischeri, was employed to test the acute toxicity of individual NPs and their binary mixtures, including metal NPs (ZnNPs, CuNPs) and metal oxide NPs (ZnONPs, CuONPs). The independent action model was used to reflect the synergistic, additive, or antagonistic interactions of binary mixtures of these NPs. The results showed that the median effective concentration (EC50) inhibited the luminescence of V. fischeri were 20.5, 4.1, 11.6, and 118.7 mg L−1 for ZnNPs, CuNPs, ZnONPs, and CuONPs, respectively, suggesting that the toxicity of these NPs to V. fischeri were as the following order: CuNPs > ZnONPs > ZnNPs > CuONPs. The combined effect of NPs were found to be antagonistic for CuNPs-ZnONPs and CuNPs-CuONPs, synergistic for CuONPs-ZnNPs, CuNPs-ZnNPs, and ZnONPs-CuONPs, and additive for ZnNPs-ZnONPs, revealing a complex pattern of possible interactions. The differences of dissolved metal ions partly accounted for the different combined toxicity of binary mixtures of NPs. The findings have important implications for better understanding the true environmental risk of NP mixtures.

A biosensitive element in the form of bacterial Photobacterium phosphoreum cells immobilized in poly(vinyl alcohol) cryogel was tested for the determination of different mycotoxins under discrete and flow-through analysis conditions. The immobilized bioluminescent cells made it possible to quantify the presence of Ochratoxin A, Sterigmatocystin, Zearalenone, and Deoxynivalenon in aqueous media in a wide range of their concentrations (0.017&ndash, 56 mg/L, 0.010&ndash, 33 mg/L, 0.009&ndash, 14 mg/L, and 0.026&ndash, 177 mg/L, respectively) via measuring the quenching of cell luminescence. The flow conditions allowed the analysis sensitivity to be improved by an order of magnitude in terms of detected concentrations. Using the immobilized luminescent bacterial cells, we have shown the possibility of evaluating the efficiency of the mycotoxins&rsquo, hydrolysis under the action of enzymes. In this way, a 94 &plusmn, 4.5% efficiency of Zearalenone hydrolysis with hexahistidine-containing organophosphorus hydrolase for 1h-long treatment of the mycotoxin solution (100 mg/L) was shown.

The development of real-time online warning system for toxicity materials is important to ensure the safety of water supply. This study for the first time constructs luminescent bacteria (Vibrio fischeri) biofilm to deliver both electrical and optical real-time response for Cu(II) toxic shock in a bioelectrochemical system (BES) sensor. Compared to biocathode, bioanode was more suitable as sensitive elements. With three tested concentrations of Cu(II), i.e., 1 mg/L, 3 mg/L and 6 mg/L, electrical signals were raised. But optical signal failed to respond to the lowest concentration, suggesting that electrical signal then was produced by chemical reaction of Cu(II) on the electrode surface. For 3 mg/L and 6 mg/L Cu(II) shock, more rapid optical signals were observed than electrical signal, indicating that both the biofilm's surface and inner was affected. In addition, high concentration of Cu(II) toxic as 6 mg/L caused irreversible damage in the biosensor as there were great fluctuation in the recovery curve and large recovery ratio up to -10.39% for optical signal. These results provided a comparison between optical and electrical signals simultaneously produced by a biosensor and visual evidences for better understanding of the toxicity process in the biosensor.

This study presented a HPTLC platformed luminescent biosensor system for screening captan residue. First, the potential bio-effects of layers materials on the detectability of a luminescent bacteria Photobacterium phosphoreum (ATCC 11040) as the sensor cell were assessed. From comparison, it was noteworthy that the combination of sensor cells with normal silica gel layer exclusively gave outstanding detectability (10 ng/zone). On this basis, HPTLC mediated separation and biosensing was further optimized. Then, the obtained graphic results were digitally quantified via software processing, offering satisfactory selectivity, linearity (R

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.

Today, nanomaterials have significant potential for practical application in a variety of research areas, in industrial production, the agrarian sector and in everyday life. Nanomaterials have received considerable attention due to the complex of their special properties, including taking into account the large specific surface area and high biological activity [1, р. 97-114; 2 р. 5728-5743]. In connection with the rapid development of nanotechnologies, nanomaterials of various shapes and diameters were obtained, which were then used in the production of products and products [3, р. 2064-2110; 4, р. 1504-1534]. On the one hand, skilled application of nanoparticles opens up new opportunities in many areas of human activity, and on the other hand due to its small size and the ability to penetrate through tissues can cause toxic effects in relation to living organisms. Therefore, scientific research must be aimed at studying the influence of nanomaterials on biological objects of different levels of organization, in particular on the analysis of the state of subcellular, cellular, organ levels and the whole organism [5, p. 51-56]. The aim was to investigate the effect of nanocomposites and their component nanosized SiO 2 on different types of microorganisms. Materials and methods. Influence of nanomaterials was studied using beer yeast, bioluminescent bacteria and associative culture of aerobic bacteria. Nanomaterials were provided by the Research Institute of Molecular Technologies in Milan, Italy. An associative culture was used ( Pseudomonas pseudo alcaligenes 102 , Bacillus subtilis 138 , Stenotrophomonas maltophilia 5246 UKM) from the collection of the Institute of Microbiology and Virology. D.K. Zabolotnoy National Academy of Sciences of Ukraine. The associative culture in the ratio 1: 1: 1 was cultivated on a nutrient medium (Himedia, India) during the day. After incubation, the suspension was applied to an agarified nutrient medium. In the center of the Petri dish, with a lawn crop, the agar blocks (hungry 4% agar with concentrations of nanomaterials) were sterilized. The culture was incubated for 2 days at a temperature of 28 0 C and the analysis was performed taking into account the fact and size of the growth retardation of the colonies (mm) [6, р. 273]. The biological effects of the NPs and NC were studied in form colloidal water mixtures obtained in appropriate volumes of 3% of sodium chloride. Three strains of luminescent bacteria ( V. fischeri F1, P. leiognathi Sh1) from collection of Crimean State Medical University (Simferopol, Ukraine) To determine the acute (toxicity) of samples, in blisters of a luminometer BLM 8801, a mixture of 0.8-0.9 ml of the test solution in a 2.5-3% solution of NaCl, 100 μl of a buffer solution with pH = 7.0 (phosphate) and 50 μl of bacterial suspension. The change in the intensity of the bioluminescence was recorded for 30-120 minutes using a recorder (LKB Bromma, Sweden). The analyzes were carried out at a temperature of 28-30 ° C. The biological effect of the samples was evaluated qualitatively by the nature of the graphic dependences of the intensity of the bioluminescence on the sample concentration. The presence of pronounced concentration inhibition of bioluminescence, reduction of bioluminescence to 50% and lower were treated as toxic [7, р. 93-97]. To study the influence of nanomaterials on beer yeast, they took a pure culture of Saccaromyces cerevisiae strain U-517 from the collection of the Institute of Microbiology and Virology. D.K. Zabolotny. Cultivated on a medium of YPD (yeast extract - 1%, peptone - 2%, glucose / dextrose - 2%, agar - 2.5%) during the day at 28 0 C. The daily subplanted culture at a concentration of 105 cells / ml in 25 ml of YPD medium with certain concentrations of nanomaterials: 150 mg / L, 300 mg / L, 450 mg / L, 600 mg / l and incubated for 1 day. Cultivate the day statically in falcons of 50 ml. The number of cells was calculated by the method of counting in the camera Goryaevа. Cell counting occurred in a heterogeneous population of Saccaromyces cerevisiae in a stationary phase of growth. MTT test was performed as follows. After daily processing with nanomaterials, 100 μl of yeast culture was incubated in the presence of 20 μl of 5 mg / ml MTT for 3.5 hours at 37 ° C in a 96-well plate in three replicates. After incubation, the culture medium was removed and the formazan crystals were dissolved in 150 μl DMSO. Incubated in the presence of DMSO in dark 15 minutes and measured the performance of the optical density (CO) formazan at a wavelength of 620 nm with a Multiskan FC device with version 1.00.94 and serial number 357-902509 [8, р. 383-393]. Research results. Having studied the influence of nanomaterials on the associative culture of aerobic bacteria, no toxic effects were found. The results of the experiment indicate the absence of antibacterial action of newly synthesized nanocomposites based on saponites on aerobic soil bacteria. For the action of nanosized SiO 2 material at a concentration of 600 mg / l around the agar block, there was no significant growth retardation of the colonies of aerobic bacteria. Thus it can be argued that the antibacterial activity of this material is weak in the associative culture of soil bacteria at a concentration of 600 mg / l. In the study of the acute effects of nanomaterials on bioluminescent bacteria, in 10 and 30 minutes, the newly synthesized nanocosities did not exhibit inhibitory activity, depending on the time and concentrations. The study of acute toxicity of samples showed that SiO 2 nanomaterial suppressed bacterial bioluminescence. During the 10-minute incubation of bacteria in solutions of nanomaterials 150 mg / l, 300 mg / l, 450 mg / l and 600 mg / l, the intensity of the luminescence of bacteria decreased by 18.5%, 54.5%, 61.5% and 59 , 5% respectively. During the 30-minute incubation, the light concentrations decreased by 20.61%, 56.2%, 61.3%, 62.5%, respectively. Accordingly, one can conclude that the inhibitory effect of the nanomaterial depends on the concentrations, and by increasing the incubation time, the change in the inhibitory effect was not significant. Accordingly, the curvature of the bioluminescence of bacteria V. Fischeri , similarly to the previous results, was not detected in the bacteria Р. leiognathi , the inhibitory effect of nanocomposites on the basis of saponites. The nanosized SiO 2 material reduced the intensity of the glow of bacteria. Thus, with a 10-minute incubation in solutions of nanomaterials of 150 mg / l, 300 mg / l, 450 mg / l and 600 mg / l, the intensity of bioluminescence decreased by 13.3%, 35.2%, 41.4% and 42.3%. During incubation for 30 minutes the indices did not change significantly. Having studied the influence of nanomaterials on bacteria, the next step was to investigate the effect of nanomaterials on the growth of yeast cells. It has been established that under the influence of saponite-based nb-containing nanocomposites, the number of S. cerevisiae cells is significantly increased. The nanosized SiO 2 material in the range of 450-600 mg / L showed an inhibitory effect, the number of cells in the samples at concentrations of 450 mg / l and 600 mg / l was 1.96 ∙ 10 8 cells / ml and 1.87 ∙ 10 8 cells / ml, respectively , whereas in the control the given index was 2.06 ∙ 10 8 кл / ml. S. cerevisiae cells are susceptible to the effect of nanomaterials on them. To confirm the preliminary results and obtain more detailed information on the influence of nanomaterials on the intensity of biochemical processes in cells, an MTT test was performed. According to the MTT test, the most pronounced effect compared with the control was found for nanocomposites Nb-Saponite (Cl) and Nb-Saponite (Et) at concentrations of 300-600 mg / l. On average, for optical nanocomposites, the optical density was 0.547 y.o. and 0.645 y.o., while in control it was 0.32 y.o. As in previous experiments on counting the number of cells, we obtain the reproducibility of the results in determining the cytotoxicity of niobium-containing nanocomposites. The growth of optical density speaks of the properties of nanocomposites, in relation to the activation of biochemical processes in cells of S. cerevisiae . Nanomaterial SiO 2 did not exhibit cytotoxic action against S. cerevisiae cells. An insignificant decrease in this indicator for the effects of SiO 2 was observed at concentrations of 450 mg / l and 600 mg / l, it decreased by 9.37% and 12.5% respectively, compared with the control. Conclusion. The influence of Nb-containing nanocomposites based on saponites and their component - nanosized SiO 2 is studied in this work. It was noted that nanocomposites did not exhibit a toxic effect in the concentration range of 150-600 mg / l in relation to bioluminescent, aerobic bacteria and S. cerevisiae . For the action of nanosized SiO 2 , an inhibitory effect was observed to the listed microorganisms. Such results can be justified by the fact that the nanosize SiO 2 material caused inhibition of the parameters, since it is about 20 nm in size so the nanomaterial can penetrate the cell wall of microorganisms and cause a negative effect. In composite materials, SiO 2 during synthesis was agglomerated into large structures, ranging in size from 40-100 nm, thus losing its toxic properties. Keywords: nanomaterials, microorganisms, bacteria, brewer's yeast, nanocomposites

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.

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.

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.

The paper examines the influence of changes in structural and physical state of water on biological activity of test organisms (luminescent bacteria of the transgenic strain Escherichia coli Z905/pPHL7). The preliminary informational effect of UHF radiation on water shifts the energy distribution in water associates, which causes a growth spurt of microorganism activity by more than a decimal exponent. The paper also shows that the energy source for ATP synthesis, produced by proton ATP synthase (F0F1-ATP synthase, where F1 and F0 are protein complexes), is connected with a nonlocal electron transfer from water to the hydrate structures of the F0-complex, which, by way of rotation, transfers protons for ATP synthesis.

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.

Mercury and its organic compounds have been of severe concern worldwide due to their damage to the ecosystem and human health. The development of effective and affordable technology to monitor and signal the presence of bioavailable mercury is an urgent need. The Mer gene is a mercury-responsive resistant gene, and a mercury-sensing recombinant luminescent bacterium using the Mer gene was constructed in this study. The mer operon from marine Pseudomonas putida strain SP1 was amplified and fused with prompterless luxCDABE in the pUCD615 plasmid within Escherichia coli cells, resulting in pTHE30-E. coli. The recombinant strain showed high sensitivity and specificity. The detection limit of Hg(2+) was 5nmol/L, and distinct luminescence could be detected in 30min. Cd(2+), Cu(2+), Zn(2+), Ca(2+), Pb(2+), Mg(2+), Mn(2+), and Al(3+) did not interfere with the detection over a range of 10(-5)-1mM. Application of recombinant luminescent bacteria testing in environmental samples has been a controversial issue: especially for metal-sensing recombinant strains, false negatives caused by high cytotoxicity are one of the most important issues when applying recombinant luminescent bacteria in biomonitoring of heavy metals. In this study, by establishing an internal standard approach, the false negative problem was overcome; furthermore, the method can also help to estimate the suspected mercury concentration, which ensures high detection sensitivity of bioavailable Hg(2+).

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.

Slaughterhouse industry produces large volumes of polluted wastewater, which cause negative impacts on the environment. The objective of this study was to assess the effect of electron-beam irradiation on the ecotoxicity of slaughterhouse effluents with absorbed doses up to 35 kGy. Two acute toxicity assays were applied to evaluate the efficiency of irradiation onto toxicity of wastewater. The exposed living-organisms were a luminescent bacteria Vibrio fischeri, and a freshwater microcrustacean Daphnia similis. Also, the total organic carbon was analysed in order to determine any possible organic carbon removal after irradiation. The ecotoxicological results evidenced that both living-organisms were suitable for the measurements. Therefore, the results demonstrated the toxicity of the effluent and its similarity for both organisms as well as the potential of radiation to reduce these effects. The 35 kGy dose was very effective for reducing toxic effects of slaughterhouse wastewater for daphnids suggesting that ionizing radiation could be used as a tool for removing toxic charge of such effluents. The type of contamination presented by the effluent justify the needs for alternatives of treatment.

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.

In this research, the effect of modified bentonite on removing harmful organisms in ballast water was discussed using HDTMA+ modified bentonite as flocculating material, and Alexandrium tamarense, Nitzchia closterium, and Photobacterium phosphoreum as the objects of harmful organisms, and also through an observation of the reaction mechanism between HDTMA+ and bentonite with Fourier transform infrared spectroscopy (FTIR). The result showed that there was an effective combination of HDTMA+ with bentonite, and the modified organic bentonite possessed a powerful ability to remove harmful organisms. The removal rate against Alexandrium tamarense within 24h was greater than 85% if the dosage of the organic bentonite was 0.03 g/L; the removal rate against Nitzchia closterium was approximate to 80% if the dosage was 0.06 g/L; the luminous intensity could not be displayed by luminescent bacteria under the condition of concentration 0.30 g/L, and also the original soil with modification did not shown a significant removal effect under the same dosage. Therefore, it was concluded that the conditions such as aging time, organic bentonite’s particle size, and HDTMA+ dosage were the important factors affecting the harmful biological removal efficiency.

The effect of different genetically engineered bacteria, Pseudomonas syringae, Pseudomonas savastanoi, and Ralostonia solanacerum and also a natural marine bacterial species, Vibrio fischeri NRRL B-11177, is studied in producing gold nanoparticles. This is the first report about the biosynthesis of gold nanoparticles by natural and genetically engineered luminescent bacteria. These microorganisms reduced gold ions and produced fairly monodisperse nanoparticles. TEM analysis indicated that spherical nano gold particles in the different diameters and shapes were obtained at pH values of 6.64. In this biosynthesis protocol, the gold nanoparticles with desired shape and size can be prepared.

Twelve kinds of lignite from different areas of China were used for the study of solid-phase biodenitrification. The amount of released carbon, rate of nitrate removal and acute toxicity were examined for all the lignite samples. The results showed that the averaged nitrate removal rates of lignite from Wangniutan and Zhangjiakou were higher than the others, which can reach above 30%. The averaged removal rates of lignite from Zhaotong, Aksu and Faku were more than 20%, and others were less than 10%. Lignite from Wangniutan, Zhangjiakou, Aksu and Faku were more suitable fillers as biodenitrification carbon for its less luminescent bacteria acute toxicity.

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.