Physiological and biochemical characteristic of Miscanthus × giganteus grown in heavy metal – oil sludge co-contaminated soil

The effect of oil sludge and zinc, present in soil both separately and as a mixture on the physiological and biochemical parameters of Miscanthus × giganteus plant was examined in a pot experiment. The opposite effect of pollutants on the accumulation of plant biomass was established: in comparison with uncontaminated control the oil sludge increased, and Zn reduced the root and shoot biomass. Oil sludge had an inhibitory effect on the plant photosynthetic apparatus, which intensified in the presence of Zn. The specific antioxidant response of M. × giganteus to the presence of both pollutants was a marked increase in the activity of superoxide dismutase (mostly owing to oil sludge) and glutathione-S-transferase (mostly owing to zinc) in the shoots. The participation of glutathione-S-transferase in the detoxification of both the organic and the inorganic pollutants was assumed. Zn inhibited the activity of laccase-like oxidase, whereas oil sludge promoted laccase and ascorbate oxidase activities. This finding suggests that these enzymes play a part in the oxidative detoxification of the organic pollutаnt. With both pollutants used jointly, Zn accumulation in the roots increased 6-fold, leading to increase in the efficiency of soil clean-up from the metal. In turn, Zn did not significantly affect the soil clean-up from oil sludge. This study shows for the first time the effect of co-contamination of soil with oil sludge and Zn on the physiological and biochemical characteristics of the bioenergetic plant M. × giganteus. The data obtained are important for understanding the mechanisms of phytoremediation with this plant.     

A monoclonal antibody against Lates calcarifer vitellogenin and a competitive ELISA to evaluate vitellogenin induction after exposure to xenoestrogen

A monoclonal antibody specific to sea bass(Lates calcarifer) vitellogenin(VTG) was developed,for use as a tool for monitoring endocrine disrupting chemicals(EDCs). VTG was induced in sea bass by intramuscular injection of 17β-estradiol(E_2: 2 mg/kg) every three days. Blood was collected three days after the last injection. Plasma VTG was then purified by chromatography in hydroxyapatite and a sephacryl-S300 column. Characterizations of purified VTG were done by phospholipoglycoprotein staining on a native-PAGE with confirmation by mass spectrometry(LC-MS/MS). Antibody was raised in mice by injection of purified VTG. After monoclonal antibody production, the hybridoma clone No. 41(MAb-sea bass VTG 41)was selected and developed for quantification of VTG by competitive enzyme-linked immunosorbent assay(ELISA). The ELISA method was sensitive with a detection limit of VTG 40 ng/mL. MAb-sea bass VTG 41 was specific to VTG from E_2-treated sea bass and others EDCs(Nonylphenol, Benzo[a]pyrene and CdCl_2). Moreover, cross-reactivity was also found in E_2-treated coral grouper(Epinephelus corallicola). The ELISA method obtained from this work can be further applied for the assessment of EDCs in Thailand and Southeast Asia's aquatic environment.     

Influence of seasonal temperature change on autotrophic nitrogen removal for mature landfill leachate treatment with high-ammonia by partial nitrification-Anammox process

In this study, a denitrification (DN)–partial nitritation (PN)–anaerobic ammonia oxidation (Anammox) system for the efficient nitrogen removal of mature landfill leachate was built with a zone-partitioning self-reflux biological reactor as the core device, and the effects of changes in seasonal temperature on the nitrogen removal in non-temperature-control environment were explored. The results showed that as the seasonal temperature decreased from 34°C to 11.3°C, the total nitrogen removal rate of the DN-PN-Anammox system gradually decreased from the peak value of 1.42 kg/(m³?day) to 0.49 kg/(m³?day). At low temperatures (<20°C), when the nitrogen load (NLR) of the system is not appropriate, the fluctuation of high NH₄⁺-N concentration in the landfill leachate greatly influenced the stability of the nitrogen removal. At temperatures of 11°C–15°C, the NLR of the system is controlled below 0.5 kg/(m³?day), which can achieve stable nitrogen removal and the nitrogen removal efficiency can reach above 96%. The abundance of Candidatus Brocadia gradually increased with the decrease of temperature. Nitrosomonas, Candidatus Brocadia and Candidatus Kuenenia as the main functional microorganisms in the low temperature.     

Assessing the anti-estrogenic activity of sodium pentachlorophenol in primary cultures of juvenile goldfish (Carassius auratus) hepatocytes using vitellogenin as a biomarker

Both pentachlorophenol and 2,3,7,8-tetrachlorodibenzo-p-dioxin （TCDD） had been studied widely because of their probable anti-estrogenic activity. Sodium pentachlorophenol （PCP-Na）, as a industrial product used in many fields, usually contains a trace of TCDD. The aim of this study was to assess the anti-estrogenic effect of PCP-Na in juvenile goldfish （Gurassius auratus） hepatocyte cultures using vitellogenin （VTG） as the biomarker. The ID50 of PCP-Na was investigated and then a series of concentrations （0.001 0.5 μg/ml） of PCP-Na were evaluated to estimate the anti-estrogenic activity. Results showed that PCP-Na was cytotoxic for hepatocytes even at very low concentration 〈1.21 μg/ml, and it could not induce VTG at any concentrations tested. Since it failed to stimulate VTG production, the possibility of its anti-estrogenic effect was tested, and a well-known anti-estrogenic compound-tamoxifen was used as positive control. PCP-Na caused a reduction in VTG synthesis in juvenile goldfish （Carassius auratus） hepatocytes at concentrations 〉0.1μg/ml when co-exposure with 1μg/ml 17β-estradiol （E2）, making its anti-estrogenic activity approximately as potent as tamoxifen. Our results indicate that PCP-Na can act as negative modulators of estrogenic function in juvenile goldfish （Carassius auratus） hepatocytes.     

Reproductive toxicity and underlying mechanisms of di(2-ethylhexyl) phthalate in nematode Caenorhabditis elegans

DEHP (di(2-ethylhexyl) phthalate) is an endocrine disruptor commonly found in plastic products that has been associated with reproduction alterations, but the effect of DEHP on toxicity is still widely unknown. Using DEHP concentrations of 10, 1, and 0.1 mg/L, we showed that DEHP reduced the reproductive capacity of Caenorhabditis elegans after 72 hr. of exposure. DEHP exposure reduced the reproductive capacity in terms of decreased brood sizes, egg hatchability (0.1, 1 and 10 mg/L), and egg-laying rate (1 and 10 mg/L), and increased numbers of fertilized eggs in the uterus (1 and 10 mg/L). DEHP also caused damage to gonad development. DEHP decreased the total number of germline cells, and decreased the relative area of the gonad arm of all exposure groups, with worms in the 1 mg/L DEHP exposure group having the minimum gonad arm area. Additionally, DEHP caused a significant concentration‐dependent increase in the expression of unc-86. Autophagy and ROS contributed to the enhancement of DEHP toxicity in reducing reproductive capacity, and glutathione peroxidase and superoxide dismutase were activated as the antioxidant defense in this study. Hence, we found that DEHP has a dual effect on nematodes. Higher concentration (10 mg/L) DEHP can inhibit the expression of autophagy genes (atg-18, atg-7, bec-1, lgg-1 and unc-51), and lower concentrations (0.1 and 1 mg/L) can promote the expression of autophagy genes. Our data highlight the potential environmental risk of DEHP in inducing reproductive toxicity toward the gonad development and reproductive capacity of environmental organisms.     

Effects of a municipal effluent on the freshwater mussel Elliptio complanata following challenge with Vibrio anguillarum

The purpose of this study was to examine the cumulative effects of exposure to a pathogenic bacteria and municipal effluent in the freshwater mussel Elliptio complanata. Mussels were exposed to increasing concentrations of an ozone-treated effluent at 15°C for 7 days. A sub-group of mussels was inoculated with Vibrio anguillarum and exposed to the same conditions as above.After the exposure period, mussels were collected to assess hemocyte count and viability,immunocompetence(phagocytosis and nitrite production), oxidative stress/inflammation(cyclooxygenase and lipid peroxidation) and oxygen radical/xenobiotic scavenging activity(metallothioniens, glutathione S-transferase). The results showed that mussels exposed to municipal effluent had increased hemocyte counts, phagocytosis, nitrites, lipid peroxidation and metallothioneins. In the inoculated mussels, the same responses were observed, in addition to cyclooxygenase and glutathione S-transferase activities. Multivariate analyses revealed that(1)the response pattern changed with effluent concentration, where increased responses observed at low effluent concentrations(10%, V/V) were attenuated at higher effluent concentrations,(2)the effluent produced more pronounced changes in lipid peroxidation, metallothionein and hemocyte viability, and(3) the simultaneous presence of V. anguillarum led to more important changes in hemocyte count and viability and nitrite levels. In conclusion, the presence of V.anguillarum could alter the response of mussels to municipal effluent, which could lead to increased inflammation in mussels.     

In situ combined chemical and biological assessment of estrogenic pollution in a water recycling system

Estrogenic pollution and its control in aquatic systems have drawn substantial attention around the world. The chemical and biological assessment approaches currently utilized in the laboratory or field cannot give an integrated assessment of the pollution when used separately. In this study, in situ chemical and biological methods were combined to detect pollution in a water recycling system. Data for the water quality index(WQI) demonstrated that the water treatment resulted in the decline of pollution from upstream to downstream.Wild male Nile tilapia, Oreochromis niloticus, was sampled in June and September. The concentrations of four common endocrine disrupting chemicals(EDCs) were determined in the tilapia liver by chromatographic analysis methods. The level of 17β-estradiol(E2) declined from upstream to downstream in both months. In contrast, the levels of bisphenol A(BPA),di-(2-ethylhcxyl) phthalate(DEHP), and perfluorooctane sulfonate(PFOS) did not display this declining tendency. The highest relative expression of vitellogenin 1(VTG1) was observed in tilapia from upstream, then the level significantly decreased along the water system. The relative expression levels of CYP1A1 in the water system were also significantly higher than that of the control. However, no declining trend could be observed along the water system. The change of VTG1 expression corresponded well with that of E2 levels in the tilapia liver. Overall,our study assessed the pollution by endocrine disruptors using chemical and biological data with good correspondence. This study also demonstrated the effectiveness of the water recycling system in eliminating estrogen pollution in municipal sewage.     

Investigation of UV-TiO2 photocatalysis and its mechanism in Bacillus subtilis spore inactivation

The inactivation levels of Bacillus subtilis spores for various disinfection processes （ultraviolet （UV）, TiO2 and UV-TiO2） were compared. The results showed that the inactivation effect of B. subtilis spores by UV treatment alone was far below that for bacteria without endospores. TiO2 alone in the dark, as a control experiment, exhibited almost no inactivation effect. Compared with UV treatment alone, the inactivation effect increased significantly with the addition of TiO2. Increases of the UV irradiance and Ti02 concentration both contributed to the increase of the inactivation effect. Lipid peroxidation was found to be the underlying mechanism of inactivation. Malondialdehyde （MDA）, the degradation product of lipid peroxidation, was used as an index to determine the extent of the reaction. The MDA concentration surged surprisingly to 3.24 nmol/mg dry cell with the combination disinfection for 600 see （0.10 mW/cm2 irradiance and 10 mg/L TiO2）. In contrast, for UV alone or TiO2 in the dark, the MDA concentration was 0.38 and 0.25 nmol/mg dry cell, respectively, under the same conditions. This indicated that both UV and TiO2 were essential for lipid peroxidation. Changes in cell ultrastructure were observed by transmission electron microscopy. The cell membrane was heavily damaged and cellular contents were completely lysed with the UV-TiO2 process, suggesting that lipid peroxidation was the root of the enhancement in inactivation efficiency.     

Sex‐specific and dose‐response relationships of urinary cobalt and molybdenum levels with glucose levels and insulin resistance in U.S. adults

Growing studies have linked metal exposure to diabetes risk. However, these studies had inconsistent results. We used a multiple linear regression model to investigate the sex-specific and dose-response associations between urinary metals (cobalt (Co) and molybdenum (Mo)) and diabetes-related indicators (fasting plasma glucose (FPG), hemoglobin A1c (HbA1c), homeostasis model assessment for insulin resistance (HOMA-IR), and insulin) in a cross-sectional study based on the United States National Health and Nutrition Examination Survey. The urinary metal concentrations of 1423 eligible individuals were stratified on the basis of the quartile distribution. Our results showed that the urinary Co level in males at the fourth quartile (Q4) was strongly correlated with increased FPG (β = 0.61, 95% CI: 0.17–1.04), HbA1c (β = 0.31, 95% CI: 0.09–0.54), insulin (β = 8.18, 95% CI: 2.84–13.52), and HOMA–IR (β = 3.42, 95% CI: 1.40–5.44) when compared with first quartile (Q1). High urinary Mo levels (Q4 vs. Q1) were associated with elevated FPG (β = 0.46, 95% CI: 0.17–0.75) and HbA1c (β = 0.27, 95% CI: 0.11–0.42) in the overall population. Positive linear dose-response associations were observed between urinary Co and insulin (P_nonlinear = 0.513) and HOMA–IR (P_nonlinear = 0.736) in males, as well as a positive linear dose-response relationship between urinary Mo and FPG (P_nonlinear = 0.826) and HbA1c (P_nonlinear = 0.376) in the overall population. Significant sex-specific and dose-response relationships were observed between urinary metals (Co and Mo) and diabetes-related indicators, and the potential mechanisms should be further investigated.     

Cobalt and manganese stress in the microalga Pavlova viridis （Prymnesiophyceae）： Effects on lipid peroxidation and antioxidant enzymes

Pollution of marine environment has become an issue of major concern in recent years.Serious environmental pollution by heavy metals results from their increasing utilization in industrial processes and because most heavy metals are transported into the marine environment and accumulated without decomposition.The aim of the present study is to investigate the effects on growth,pigments, lipid peroxidation,and some antioxidant enzyme activities of marine microalga Pavlova viridis,in response to elevated concentrations of cobalt(Co)and manganese(Mn),especially with regard to the involvement of antioxidative defences against heavy metal-induced oxidative stress.In response to Co~(2 ),lipid peroxidation was enhanced compared to the control,as an indication of the oxidative damage caused by metal concentration assayed in the microalgal cells but not Mn~(2 ).Exposure of Pavlova viridis to the two metals caused changes in enzyme activities in a different manner,depending on the metal assayed:after Co~(2 )treatments,total superoxide dismutase(SOD)activity was irregular,although it was not significantly affected by Mn~(2 )exposure.Co~(2 )and Mn~(2 )stimulated the activities of catalase(CAT)and glutathione(GSH),whereas,ghitathione peroxidase(GPX)showed a remarkable increase in activity in response to Co~(2 )treatments and decreased gradually with Mn~(2 )concentration,up to 50μmol/L,and then rose very rapidly,reaching to about 38.98% at 200μmol/L Mn~(2 ).These results suggest that an activation of some antioxidant enzymes was enhanced,to counteract the oxidative stress induced by the two metals at higher concentration.     

A survey on heavy metal concentrations in residential neighborhoods: The influence of secondary water supply systems

Water quality deterioration often occurs in secondary water supply systems (SWSSs), and increased heavy metal concentrations can be a serious problem. In this survey, twelve residential neighborhoods were selected to investigate the influence of SWSSs on the seasonal changes in heavy metal concentrations from input water to tank and tap water. The concentrations of nine evaluated heavy metals in all groups of water samples were found to be far below the specified standard levels in China. The concentrations of Fe, Mn, and Zn increased significantly from the input water samples to the tank and tap water samples in spring and summer (p < 0.05), especially for the water samples that had been stagnant for a long time. Negative correlations were found between most of the heavy metals and residual chlorine (Fe, Cu, Zn, and As, r = -0.186 to -0.519, p < 0.05). In particular, a high negative correlation was observed between Fe and residual chlorine (r = -0.489 to -0.519, p < 0.01) in spring and summer. Fe and Mn displayed positive correlations with turbidity (r = 0.672 and 0.328, respectively; p < 0.05). In addition, Cr and As were found to be positively associated with some nutrients (NO₃⁻, TN, and SO₄²⁻; r = 0.420-0.786, p < 0.01). The material of the storage tanks had little influence on the difference in heavy metal concentrations. Overall, this survey illustrated that SWSSs may pose a chronic threat to water quality and could provide useful information for practitioners.     

Combined effect of tributyltin and benzo[a] pyrene on the levels of sex hormone and vitellogenin in female Sebastiscus marmoratus

Tributyltin（TBT）, an organometal used as an antifouling biocide, has been reported to induce masculinization of fish. Benzo [a]pyrene （BaP）, a widespread carcinogenic polycyclic aromatic hydrocarbon, has been reported that its microsomal metabolites can produce an estrogenic response when tested in vitro. This study was therefore designed to examine the potential in vivo influence of TBT, BaP and their mixture on sex hormone levels in serum of Sebastiscus marmoratus, which were given 2 separate intraperitoneally （ip） injections（a single injection every 7 d） of TBT（0.5, 1, 5 and 10 mg/kg）, BaP（0.5, 1, 5 and 10 mg/kg）, or both in combination（0.5, 1, 5 and 10 mg/kg）; control fish received olive oil vehicle only. Six days after the 2nd injection, serum samples were collected and analyzed for sex hormone levels and alkali labile protein phosphorus （ALPP）, which is related to the yolk precursor protein vitellogenin. The pollutants at all doses significantly reduced serum testosterone, estradiol and ALPP content after 2 injections compared with the corresponding controls. The reduction of the estradiol levels should be response for the decrease of the vitellogenin levels. The results in the present study suggested that aromatase seems not the major target acted by TBT and BaP in fish. This study demonstrated that TBT or BaP exposure both inhibit the reproductive potential in female Sebastiscus marmoratus. Combined effect of TBT and BaP on the serum testosterone, estradiol and ALPP was not antagonism from the anticipation.     

2,3,7,8-Tetrachlorodibenzo-p-dioxin promotes migration ability of primary cultured rat astrocytes via aryl hydrocarbon receptor

Emerging evidence showed that 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) could induce expression of certain reactivation-associated genes in astrocytes, however, the consequent cellular effects and molecular mechanisms are still unclear. During the process of astrocyte reactivation, migration is a critical cellular event. In the present study, we employed wound-healing assay and Transwell® motility assay to explore the effects of TCDD on cell migration in primary cultured rat cortical astrocytes. We found that upon TCDD treatments at relative low concentrations (10^? 10 and/or 10^? 9?mol/L), the ability of primary astrocytes to migrate horizontally and vertically was promoted. In line with this cellular effect, the mRNA expression of two pro-migratory genes, including cell division cycle 42 (CDC42) and matrix metalloproteinase 2 (MMP2) was induced by TCDD treatment. Dioxin exerts its toxic effects mainly through aryl hydrocarbon receptor (AhR) pathway. So the role of AhR pathway in the pro-migratory effects of TCDD was examined using an AhR antagonist, CH223191. We found that application of CH223191 significantly reversed the pro-migratory effects of TCDD. Interestingly, the basal ability of horizontal migration as well as basal levels of CDC42 and MMP2 expression were dramatically reduced suggesting a possible physiological role of AhR in maintaining the endogenous migration ability of the primary astrocytes. These findings support the notion that dioxin promotes astrocyte reactivation at molecular and cellular levels.     

Coking wastewater increases micronucleus frequency in mouse in vivo via oxidative stress

Coking wastewater has caused serious health risk in coal-producing areas of China, however its toxic effects have not been well understood. The genotoxicity induced by coking wastewater on mice in vivo and its possible oxidative mechanisms were investigated via observing the induction of micronuclei in polychromatic erythrocytes of mouse bone marrow, and subsequently determining the antioxidative enzyme activities （superoxide dismutase Cu, Zn-SOD, Se-dependent glutathione peroxidase, and catalase）, thiobarbituric acid reactive substance contents and protein carbonyl levels in brains and livers of mice. Results showed that the tested coking wastewater caused a significant increase of micronucleus frequencies in a concentration-dependent manner. Also, the sample increased lipid peroxidation and protein oxidation levels, which was accompanied by changes in antioxidative status. Interestingly, pre-treatment with an antioxidant （vitamin C） led to a statistical reduction in the micronucleus frequency caused by coking wastewater. This implies that coking wastewater induces evident genetic damage in mammalian cells, and exposure to polluted areas might pose a potential genotoxic risk to human beings; in the process, oxidative stress played a crucial role.     

Simultaneous removal of Congo red and cadmium(II) from aqueous solutions using graphene oxide–silica composite as a multifunctional adsorbent

Graphene oxide is a very high capacity adsorbent due to its functional groups and π?π interactions with other compounds. Adsorption capacity of graphene oxide, however, can be further enhanced by having synergistic effects through the use of mixed-matrix composite. In this study, silica-decorated graphene oxide (SGO) was used as a high-efficiency adsorbent to remove Congo red (CR) and Cadmium (II) from aqueous solutions. The effects of solution initial concentration (20 to 120 mg/l), solution pH (pH 2 to 7), adsorption duration (0 to 140 min) and temperature (298 to 323 K) were measured in order to optimize the adsorption conditions using the SGO adsorbent. Morphological analysis indicated that the silica nanoparticles could be dispersed uniformly on the graphene oxide surfaces. The maximum capacities of adsorbent for effective removal of Cd (II) and CR were 43.45 and 333.33 mg/g based on Freundlich and Langmuir isotherms, respectively. Langmuir and Freundlich isotherms displayed the highest values of Q_max for CR and Cd (II) adsorption in this study, which indicated monolayer adsorption of CR and multilayer adsorption of Cd (II) onto the SGO, respectively. Thermodynamic study showed that the enthalpy (ΔH) and Gibbs free energy(ΔG) values of the adsorption process for both pollutants were negative, suggesting that the process was spontaneous and exothermic in nature. This study showed active sites of SGO (π-π, hydroxyl, carboxyl, ketone, silane-based functional groups) contributed to an enormous enhancement in simultaneous removal of CR and Cd (II) from an aqueous solution, Therefore, SGO can be considered as a promising adsorbent for future water pollution control and removal of hazardous materials from aqueous solutions.     

Use of sub-micron sized resin particles for removal of endocrine disrupting compounds and pharmaceuticals from water and wastewater

Endocrine disrupting compounds(EDCs) and pharmaceuticals pose a challenge for water and wastewater treatment because they exist at very low concentrations in the presence of substances at much higher concentrations competing for adsorption sites.Sub-micron sized resin particles(approximately 300 nm in diameter)(SMR) were tested to evaluate their potential as a treatment for EDCs including:17-β estradiol(E2),17-α ethinylestradiol(EE2),estrone(E1),bisphenol A(BPA),and diethylstilbestrol(DES) as well as 12 pharmaceuticals.SMR were able to remove 98%of spiked E2,80%of EE2,87%of BPA,and up to 97%of DES from water.For a 0.5 ppm mixture of E2,EE2,E1,BPA and DES,the minimum removal was24%(E2) and the maximum was 49%(DES).They were also able to remove the pharmaceuticals from deionized water and wastewater.Overall,SMR are a promising advanced treatment for removal of both EDCs and pharmaceuticals.     

Electrokinetic movement of multiple chlorobenzenes in contaminated soils in the presence of β-cyclodextrin

This study investigated the electrokinetic (EK) behavior of multiple chlorobenzenes, including 1,2,3,4-tetrachlorobenzene (TeCB), 1,2,4,5-tetrachlorobenzene (i-TeCB), and 1,2,3-trichlorobenzene (TCB) in contaminated clayed soils. The effect of β-cyclodextrin (β-CD) on the EK removal of the chlorobenzenes was studied. The largest removal was obtained when Na2CO3/NaHCO3 buffer was used as anodic purging solution without β-CD. The removal efficiencies were related to the aqueous solubilities of chlorobenzenes. With the same cumulative electroosmotic flow, greater solubility led to higher removal efficiency. The addition of β-CD inhibited the EK removal efficiency of all chlorobenzenes. The inhibition increased with the increase of β-CD concentration. With the same β-CD concentration, the inhibition increased with the rise of electric potential. It was found that the inclusion compounds between β-CD and chlorobenzenzes were less soluble than chlorobenzenes. The formation of the less soluble inclusion compounds reduced the aqueous solubility of chlorobenzenes and led to the partial immobilization of the chlorobenzenes that desorbed from soil. It was feasible to use the EK technology to remove chlorobenzenes in contaminated soils using water as the anodic flushing solution. The addition of β-CD was not recommended for the EK removal of chlorobenzenes.     

Electrokinetic movement of multiple chlorobenzenes in contaminated soils in the presence of β-cyclodextrin

This study investigated the electrokinetic(EK)behavior of multiple chlorobenzenes,including 1,2,3,4-tetrachlorobenzene(TeCB), 1,2,4,5-tetrachlorobenzene(i-TeCB),and 1,2,3-trichlorobenzene(TCB)in contaminated clayed soils.The effect ofβ-cyclodextrin(β- CD)on the EK removal of the chlorobenzenes was studied.The largest removal was obtained when Na_2CO_3/NaHCO_3 buffer was used as anodic purging solution withoutβ-CD.The removal efficiencies were related to the aqueous solubilities of chlorobenzenes. With the same cumulative electroosmotic flow,greater solubility led to higher removal efficiency.The addition ofβ-CD inhibited the EK removal efficiency of all chlorobenzenes.The inhibition increased with the increase ofβ-CD concentration.With the sameβ-CD concentration,the inhibition increased with the rise of electric potential.It was found that the inclusion compounds betweenβ-CD and chlorobenzenzes were less soluble than chlorobenzenes.The formation of the less soluble inclusion compounds reduced the aqueous solubility of chlorobenzenes and led to the partial immobilization of the chlorobenzenes that desorbed from soil.It was feasible to use the EK technology to remove ehlorobenzenes in contaminated soils using water as the anodic flushing solution.The addition ofβ-CD was not recommended for the EK removal of chlorobenzenes.     

Electrokinetic removal of chromium and copper from contaminated soils by lactic acid enhancement in the catholyte

The electrokinetic removal of chromium and copper from contaminated soils by adding lactic acid in cathode chamber as an enhancing reagent was evaluated. Two sets of duplicate experiments with chromium contaminated kaolinite and with a silty soil sampled from a supeffund site in Califomia of USA and polluted by Cr and Cu, were carried out in a constant current mode. Changes of soil water content and soil pH before and after the electrokinetic experiments, and variations of voltage drop and electroosmosis flow during the treatments were examined. The results indicated that Cr, spiked as Cr(Ⅵ) in the kaolinite, was accumulated mainly in the anode chamber, and some of Cr and metal hydroxides precipitated in the soil sections in contact with the cathode, which significantly increased electrical energy consumption. Treatment of the soil collected from the site showed accumulation of large amounts of Cr and Cu in the anode chamber while none was detected in the cathode one. The results suggested that the two metals either complexed with the injected lactic acid at the cathode or existed as negatively charged complex, and electromigrated toward the anode under a voltage gradient.     

The study of biological activity of transformation products of diclofenac and its interaction with chlorogenic acid

In the present work we compared the biological activity of DCF, 4′-OHDCF and 5-OHDCF as molecules of most biodegradation pathways of DCF and selected transformation products (2-hydroxyphenylacetic acid; 2,5-dihydroxyphenylacetic acid and 2,6-dichloroaniline) which are produced during AOPs, such as ozonation and UV/H₂O₂. We also examined the interaction of DCF with chlorogenic acid (CGA). CGA is commonly used in human diet and entering the environment along with waste mainly from the processing and brewing of coffee and it can be toxic for microorganisms included in activated sludge. In the present experiment the evaluation of following parameters was performed: E. coli K-12 cells viability, growth inhibition of E. coli K-12 culture, LC₅₀ and mortality of Chironomus aprilinus, genotoxicity, sodA promoter induction and ROS generation. In addition the reactivity of E. coli SM recA:luxCDABE biosensor strain in wastewater matrices was measured. The results showed the influence of DCF, 4′-OHDCF and 5-OHDCF on E. coli K-12 cells viability and bacteria growth, comparable to AOPs by-products. The highest toxicity was observed for selected, tested AOPs by-products, in comparison to the DCF, 4′-OHDCF and 5-OHDCF. Genotoxicity assay indicated that 2,6-dichloroaniline (AOPs by-product) had the highest toxic effect. The oxidative stress assays revealed that the highest level of ROS generation and sodA promoter induction were obtained for DCF, 4′-OHDCF and 5-OHDCF, compared to other tested compounds. We have also found that there is an interaction between chlorogenic acid and DCF, which resulted in increased toxicity of the mixture of the both compounds to E. coli K-12, comparable to parent chemicals. The strongest response of E. coli SM biosensor strain with recA:luxCDABE genetic construct in filtered treated wastewaters, comparable to control sample was noticed. It indicates, that E. coli SM recA:luxCDABE biosensor strains is a good tool for bacteria monitoring in wastewater environment. Due to toxicity and biological activity of tested DCF transformation products, there is a need to use additional wastewater treatment systems for wastewater contaminated with pharmaceutical residues.