Mixed Pollutants Research Articles

The simultaneous promotion of Cr (VI) photoreduction and tetracycline removal over 3D/2D Cu2O/BiOBr S-scheme nanostructures

Although the degradation of hexavalent chromium (Cr (VI)) or tetracycline hydrochloride (TC) in water bodies has been intensively studied, the degradation of mixed pollutants in the liquid phase is still an arduous challenge. In this paper, a series of Cu2O/BiOBr S-scheme composite photocatalysts were successfully prepared by a hydrothermal and subsequent precipitation method to purify the water body where Cr (Ⅵ) and TC coexist. The morphologies and photoelectrochemical characteristics of the prepared samples were characterized by XRD, FTIR, TEM, UV–vis, XPS, PL, EIS, and other methods. The optimal Cu2O/BiOBr with 15 wt% Cu2O (CB-15) provided the best photocatalytic activity. CB-15 exhibited a Cr (Ⅵ) reduction efficiency 21.75 times higher than BiOBr. The TC degradation efficiency of CB-15 was 1.21 times higher than Cu2O. It was interesting that the synergistic photocatalytic activity of CB-15 in the mixed system was improved. The reduction ability of Cr (Ⅵ) and the degradation ability of TC were increased by 1.67 times and 1.18 times, respectively. The enhanced activity of CB-15 was ascribed to the S-scheme heterojunction and 3D/2D structure. The S-scheme transfer mechanism in CB-15 could suppress the recombination of photogenerated carriers and thus prolong the fluorescence lifetime of carriers. While the 3D/2D heterostructure with a large number of contact areas and active sites could further promote the efficiency of the photocatalytic reaction. Notably, the photocatalyst still maintained an excellent degradation ability after four recycles. In general, this paper provided new insights into the design of 3D/2D S-scheme heterojunction photocatalysts and the degradation of mixed wastewater.

A review on synergistic coexisting pollutants for efficient photocatalytic reaction in wastewater remediation

With the tremendous development of the economy and industry, the pollution of water is becoming more serious due to the excessive chemical wastes that need to remove thru reduction or oxidation reactions. Simultaneous removal of dual pollutants via photocatalytic redox reaction has been tremendously explored in the last five years due to effective decontamination of pollutants compared to a single pollutants system. In a photocatalysis mechanism, the holes in the valence band can remarkably promote the oxidation of a pollutant. At the same time, photoexcited electrons are also consumed for the reduction reaction. The synergistic between the reduction and oxidation inhibits the recombination of electron-hole pairs extending their lifetime. In this review, the binary pollutants that selectively removed via photocatalysis reduction or oxidation are classified according to heavy metal-organic pollutant (HM/OP), heavy metal-heavy metal (HM/HM) and organic-organic pollutants (OP/OP). The intrinsic between the pollutants was explained in three different mechanisms including inhibition of electron-hole recombination, ligand to metal charge transfer and electrostatic attraction. Several strategies for the enhancement of this treatment method which are designation of catalysts, pH of mixed pollutants and addition of additive were discussed. This review offers a recent perspective on the development of photocatalysis system for industrial applications.

Enhanced Cr (VI) removal with Pb (II) presence by Fe2+-activated persulfate and zero-valent iron system

ABSTRACT Combined heavy metals such as chromium (Cr (VI)) and lead (Pb (II)) in natural water have globally posed severe environmental and public health risk. Here the removal of Cr (VI) and Pb (II) mixed pollutants using Fe2+-activated persulfate (PS) with extra zero-valent iron (ZVI), which was not only a supplementary Fe2+ source, but also a high-efficiency absorbent, was investigated. During removal, pivotal factors of initial pollutant concentration, dosages of ZVI and PS, initial pH and temperatures were examined. Interestingly, generating a lot of H+ in the process of Fe (II) activating persulfate were helpful to the corrosion of ZVI over a large range of pH (1–9). Under the optimum condition, removal efficiency of Pb (II) and Cr (VI) have reached 100% and 94.26% respectively. The removal mechanism was suggested as a three-step reaction that the Pb (II) boosted the removal of Cr (VI) by co-precipitated in wastewater, and the Pb (II) and Cr (VI) were adsorbed and subsequently reduced to Pb0 and Cr3+ as Cr(OH)3 or Cr3+-Fe3+ hydroxides on ZVI surface. Cr (VI) and Pb (II) adsorption kinetics agreed with the pseudo-second-order reaction rate expression. In addition, we were surprised to found that the contribution effect of chromium and lead co-precipitation for their removal by Fe (II) – PS-ZVI has strong dependence on initial pH and concentration ratio of Cr (VI) and Pb (II). The result indicated that Fe (II)-PS-ZVI system should be a favourable removal technology for Cr (VI) and Pb (II).

Natural aging of expanded shale, clay, and slate (ESCS) amendment with heavy metals in stormwater increases its antibacterial properties: Implications on biofilter design

Aging is often expected to decrease the pathogen removal capacity of media because of exhaustion of attachment sites by adsorption of co-contaminants and dissolved organics. In contrast, the adsorption of metals naturally present in stormwater during aging could have a positive impact on pathogen removal. To examine the effect of adsorbed metals on pathogen removal, biofilter media amended with expanded clay, shale, and slate (ESCS) aggregates, a lightweight aggregate, were exposed to metals by intermittently injecting natural stormwater spiked with Cu, Pb, and Zn, and the capacity of aged and unaged media to remove Escherichia coli (E. coli), a pathogen indicator, were compared. Metal adsorption on ESCS media decreased their net negative surface charge and altered the surface properties as confirmed by zeta potential measurement and Fourier-Transform Infrared Spectroscopy (FTIR) analysis. These changes increased the E. coli adsorption capacity of aged media compared with unaged media and decreased overall remobilization of attached E. coli during intermittent infiltration of stormwater. A live-dead analysis confirmed that the adsorbed metals inactivated attached E. coli, thereby replenishing the adsorption capacity. Overall, the results confirmed that natural aging of biofilter media with adsorbed metals could indeed have a net positive effect on E. coli removal in biofilters and therefore should be included in the conceptual model predicting long-term removal of pathogens from stormwater containing mixed pollutants.

Effect of Carbamazepine, Ibuprofen, Triclosan and Sulfamethoxazole on Anaerobic Bioreactor Performance: Combining Cell Damage, Ecotoxicity and Chemical Information.

Pharmaceuticals and personal care products (PPCPs) are partially degraded in wastewater treatment plants (WWTPs), thereby leading to the formation of more toxic metabolites. Bacterial populations in bioreactors operated in WWTPs are sensitive to different toxics such as heavy metals and aromatic compounds, but there is still little information on the effect that pharmaceuticals exert on their metabolism, especially under anaerobic conditions. This work evaluated the effect of selected pharmaceuticals that remain in solution and attached to biosolids on the metabolism of anaerobic biomass. Batch reactors operated in parallel under the pressure of four individual and mixed PPCPs (carbamazepine, ibuprofen, triclosan and sulfametoxazole) allowed us to obtain relevant information on anaerobic digestion performance, toxicological effects and alterations to key enzymes involved in the biodegradation process. Cell viability was quantitatively evaluated using an automatic analysis of confocal microscopy images, and showed that triclosan and mixed pollutants caused higher toxicity and cell death than the other individual compounds. Both individual pollutants and their mixture had a considerable impact on the anaerobic digestion process, favoring carbon dioxide production, lowering organic matter removal and methane production, which also produced microbial stress and irreversible cell damage.

Investigation of heterojunction between α-Fe2O3/V2O5 and g-C3N4 ternary nanocomposites for upgraded photo-degradation performance of mixed pollutants: Efficient dual Z-scheme mechanism

In this present work, a g-C3N4 decorated dual Z-scheme α-Fe2O3 and V2O5 heterojunction of magnetically recoverable GFV (g-C3N4/α-Fe2O3/V2O5) composite was rationally synthesized using facile calcination and hydrothermal approach. The crystal structure, surface morphology, chemical composition and optical properties of the as-obtained composite photocatalysts (PCs) were characterized by powder X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectra high-resolution scanning electron microscopy (HR-SEM, high-resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS) measurement, UV-Vis diffuse reflectance spectra (DRS) and photoluminescence (PL) analyses respectively. Benefiting from these structural and compositional features, the optimum GFV heterostructured PCs sample revealed that the superior photo-degradation performance of methyl yellow (MY) and methylene blue (MB) mixed dye under visible-light, while the degradation rates were 93.4% for MY and 87.5% for MB dye at 90 min, respectively. Moreover, the enhanced photo-degradation performance of GFV composite PCs displayed an extended visible-light fascination due to lower bandgap, reduced recombination rates, high charge separation and good charge transfer capacity with the efficient dual Z-scheme heterojunction. Meanwhile, high photo-degradation stability is continued after five successive reusability tests. A possible photo-degradation mechanism of dual Z-scheme charge transfer paths was also been proposed. This study is also capable of emerging visible-light active facile heterojunction photocatalysts for various organic pollutants removal with great efficiency.

Single enrichment systems possibly underestimate both exposures and biological effects of organic pollutants from drinking water

Comprehensive enrichment of contaminants in drinking water is an essential step for accurately determining exposure levels of contaminants and testing their biological effects. Traditional methods using a single absorbent for enriching contaminants in water might not be adequate for complicated matrices with different physical-chemical profiles. To examine this hypothesis, we used an integrated enrichment system that had three sequential stages-XAD-2 resin, poly (styrene–divinylbenzene) and activated charcoal to capture organic pollutants and disinfection by-products (DBPs) from drinking water in Shanghai. Un-adsorbed Organic Compounds in Eluates (UOCEs) named UOCEs-A, -B, and-C following each adsorption stage were determined by gas chromatography-mass spectrometry to evaluate adsorption efficiency of the enrichment system. Meanwhile, biological effects such as cytotoxicity, effects on reactive oxygen species (ROS) generation and glutathione (GSH) depletion were determined in human LO2 cells to identify potential adverse effects on exposure to low dose contaminants. We found that poly-styrene–divinylbenzene (PS-DVB) and activated charcoal (AC) could still partly collect UOCEs-A and-B that the upper adsorption column incompletely captured, and that potential carcinogens like 2-naphthamine were present in all eluates. UOCEs-A at (1–4000), UOCEs-B at (1000–4000), and UOCEs-C at (2400–4000) folds of the actual concentrations had significant cytotoxicity to LO2 cells. Additionally, ROS and GSH change in cells treated with UOCEs indicated the potential for long-term effects of exposure to some mixtures of contaminants such as DBPs at low doses. These results suggested that an enriching system with a single adsorbent would underestimate the exposure level of pollutants and the biological effects of organic pollutants from drinking water. Effective methods for pollutants’ enrichment and capture of drinking water should be given priority in future studies on accurate evaluation of biological effects exposed to mixed pollutants via drinking water.

Combined effect of tetracycline and copper ion on catalase activity of microorganisms during the biological phosphorus removal

Microbial catalase is a key enzyme that affects the activities of microorganisms, and the catalase activity is affected by pollutants in wastewater. However, the effects of mixed pollutants on catalase activity are rather complex. To reveal the effect of the mixed pollutants on catalase activity of microorganisms, the present study investigated tetracycline and copper ion as pollutants during the biological phosphorus removal. Three concentration ratios of tetracycline and copper ion and 27 different concentration gradients were designed through the direct equipartition ray and the dilution factor method. The effects of mixed pollutants on the catalase activity of microorganisms were analyzed by the nonlinear regression equation and concentration-addition model. The results showed that, with the increase of actuation duration and the pollutant concentration, the inhibitory effects on the catalase activity of microorganisms obviously increased, which indicated that the inhibitory effects are concentration-dependent and time-dependent. The concentration-addition model suggested that when the ratio was 0.297, the combined effect of mixed pollutants on the activity of microbial catalase was mainly antagonism. When the ratio is 0.894, the combined effect was mainly additivity. When the ratio was 2.676, the combined effect transformed from synergism to additivity and antagonism. The study of the combined effects of tetracycline and copper ion on the catalase activity is helpful to further study their ecotoxicological mechanisms in wastewater treatment.

Effects of amine (APTES) and thiol (MPTMS) silanes-functionalized ZnO NPs on the structural, morphological and, selective sonophotocatalysis of mixed pollutants: Box–Behnken design (BBD)

The lack of selectivity of Zinc oxide nanoparticles (ZnO NPs) in the wastewater purification process is considered a severe limitation. This research aims to use surface-modified ZnO NPs with different surface charges for selective removal of methyl orange (MO) and methylene blue (MB) dyes from an aqueous mixture solution. The sonophotocatalyst process was investigated to improve the selective oxidation of the aqueous mixture. The surface of the ZnO NPs has been modified with a silane coupling agent (APTES and MPTMS) to get active surface functional groups. The synthesized modified ZnO NPs were characterized by XRD, FE-SEM, TEM and FTIR analysis. The surface charge and absorption spectrum were investigated using Zeta potential and UV-Vis spectrophotometer approaches, respectively. The selective sonophotocatalytic of anionic MO and cationic MB dyes was performed via APTES-ZnO and MPTMS-ZnO NPs, respectively. The selective removal was optimized using Response Surface Methodology (RSM) based on the Box–Behnken Design (BBD). To this end, the effects of catalyst dosage, dye concentration, and reaction time on selective removal were investigated under various experimental conditions. The results revealed that unmodified ZnO NPs have no selectivity in the decomposition of an MO and MB mixed, whiles the change in surface charges of ZnO NPs has been shown to change significantly the selectivity efficiency of ZnO NPs.

Design a novel g-C3N4 based Ce2O3/CuO ternary photocatalysts for superior photo-degradation performance of organic mixed pollutants: Insights of Z-scheme charge transfer mechanism

In this work, a novel ternary g-C3N4/Ce2O3/CuO (GCC) composite photocatalyst was effectively synthesized by facile calcination and dynamic hydrothermal technique. The as-obtained photocatalysts (PCs) samples were characterized using several techniques such as XRD, FT-IR, FESEM-EDAX with mapping, HR-TEM, high-resolution XPS, UV-DRS absorption and PL spectra respectively. The photo-degradation outcomes specified that the ternary GCC composite PCs possessed the better photocatalytic efficiency by degrading for the aqueous MY (94.5%) and MB (90.3%) mixed dye compared to other as-obtained PCs samples within 150 min under visible-light exposure. Moreover, after the fifth recycles of the superior GCC composite PCs, the photo-degradation rate of MB and MY mixed dyes still could be reached to 81% and 86.5%, respectively, which revealed the excellent reusability and photostability after the five successive recycles. Hence, the improved photo-degradation activity could be ascribed to a lower bandgap, superior visible-light absorption capacity and reduced the recombination rate of photo-excited electron-hole (e−/h+) pairs among the synergistic effects of unique g-C3N4, Ce2O3 and CuO heterointerface in the efficient three-level e−/h+ transfer. Based on the various scavenger's tests, a probable charge transfer pathway with the strong reduction ability process was also proposed. The superior photo-degradation efficiency and their probability, which make reusable PCs and a potential aspirant for environmental wastewater purification and energy conversion.

Gas-to-aqueous Phase Transfer for Three Paint Solvents Injected into an Abiotic, Industrial Biotrickling Filter Measured with a Flame Ionization Detector

This is a knowledge contribution to the unsatisfactory biodegradation problem, when biotrickling filters are purifying mixed paint solvents. A biotrickling filter manufacturer reported low biodegradation rates during the purification of a hydrocarbon pollutant mix from an industrial paint spraying floor. From a gas chromatograph/mass spectrometer analysis both hydrophilic and hydrophobic solvents were found in the polluted air. It is known that biodegradation is retarded, if the pollutant does not transfer from gas to liquid into the biofilm and it was therefore suspected that hydrophobic pollutants do not sufficiently migrate into the water/biofilm. To test this hypothesis, pure, rather than mixed pollutants, were injected into the abiotic biotrickling filter. When hydrophobic paint solvent (xylene) was sprayed into the biotrickling filter, the solvent load at the outlet of the filter was almost as high as at the inlet. But when pure, hydrophilic paint solvent (PGME) was sprayed into the abiotic biotrickling filter, the solvent load measured at the outlet of the filter was zero, indicating complete dissolution into the circulation water. Carbon/solvent loads at the filter outlet and inlet were measured with a portable flame ionization detector instrument. The experiment confirms that the hydrophobic solvent does not migrate into the liquid phase. This poor mass transfer of hydrophobic solvents is likely to be the reason for the low biodegradation rate. The result is highly relevant to the paint spraying industry and manufacturers of exhaust gas treatment equipment alike, who spend millions in non-sustainable incineration of exhaust gases.

Facile fabrication of magnetically recyclable Fe3O4/BiVO4/CuS heterojunction photocatalyst for boosting simultaneous Cr(VI) reduction and methylene blue degradation under visible light

It is a challenging problem that develops a low-cost, efficient and sustainable technology in order to remove heavy metals and organic contaminants in the practical wastewater. Herein, a novel recyclable Fe3O4/BiVO4/CuS (FBCu) heterojunction photocatalyst was facilely fabricated by a method, coating CuS nanoparticles on the surface of Fe3O4 and BiVO4 simultaneously. FBCu composite not only has the ability to degrade Cr(VI) or methylene blue (MB) alone under visible light irradiation, but also exhibits higher photocatalytic ability in simultaneously removing Cr(VI) and MB mixed pollutants. The superior photocatalytic performance of FBCu is related to the formation of p-n heterojunction, which extends the spectral response and facilitates the efficiency of charge carriers separation and utilization. Moreover, FBCu exhibits satisfactory properties of reusability and stability after five cycling experiments in the Cr(VI)-MB coexistence system. Furthermore, the detailed mechanism for simultaneous removal of mixed pollutants was proposed and verified by DRS results, photoelectrochemical analysis, scavenger experiments and electron spin resonance determination. This work provides a recyclable photocatalyst with eco-friendliness and multifunctional applications in water pollution.

Response of antimony and arsenic in karst aquifers and groundwater geochemistry to the influence of mine activities at the world’s largest antimony mine, central China

The elevated levels of antimony (Sb) and arsenic (As) in groundwater caused by mine activities is of particular global concern. Understanding pollution mechanism of Sb and As related to mine activities and their influence on karst groundwater geochemistry is of great significance. However, it is still unclear. To address such questions, Sb and As and major ions, δ34S and δ18O of dissolved sulfate as well as δD and δ18O of water were analyzed for groundwater sampled from three main karst aquifers at the Xikuangshan (XKS) antimony mine from 2013 to 2017. Spatial and temporal variations of Sb and As of the three main karst aquifers were characterized as that, (1) Sb concentrations, rather than As, varied with aquifers, with high Sb (1–50 mg/L) of the D3s2 and C1y3 aquifers and low Sb (0.01–1.0 mg/L) of the D3x4 aquifer; (2) As concentrations had significant seasonal effect that was higher in winter and lower in summer, whereas Sb concentrations did not differ seasonally. Here we applied a recently developed cluster analysis method as well as geochemical indicators to identify pollution types of Sb and As in groundwater related to complex mine activities, and further to reveal main effects on karst groundwater geochemistry. The cluster analysis yielded a classification of four clusters, which was confirmed by principal component analysis. The groundwater of cluster 3 is of weakly alkaline HCO3-Ca type with low Sb (<0.015 mg/L) and low As (<0.005 mg/L), which is typical karst groundwater controlled by limestone dissolution. Whereas the other three clusters with high concentrations of Sb and As were identified to represent three pollution patterns dominated by oxidative dissolution of stibnite, leaching of mine wastes, and mixed pollution, respectively. Moreover, the effects of long-term mine activities on karst groundwater geochemistry are revealed, including: (1) Hydrogeochemical compositions of groundwater changed from HCO3-Ca type to SO4-Ca type. (2) Sulfuric acid significantly participated in carbonate weathering. (3) Weathering of silicate (main as silicified limestone) by H2CO3 and H2SO4 was accelerated. (4) Cation-exchange was enhanced to dominate groundwater geochemistry. Another striking finding is that sulfur and oxygen isotopes of sulfate can effectively distinguish sulfate sources related to mine activities and to trace Sb sources in karst groundwater.

Visible light-driven photoelectrocatalysis for simultaneous removal of oxytetracycline and Cu (II) based on plasmonic Bi/Bi2O3/TiO2 nanotubes

A visible light-driven photoelectrocatalytic system was constructed based on Bi/Bi2O3/TiO2 nanotubes (NTs) to treat wastewater containing oxytetracycline and Cu2+ mixed pollutants. The surface morphology, crystal phase, elemental composition, light absorption property and photoelectrochemical activity of the synthesized Bi/Bi2O3/TiO2 NTs were investigated. The composite film, Bi/Bi2O3/TiO2 NTs was used for the photoelectrochemical removal of oxytetracycline, and it had excellent visible light photoelectrocatalytic performance. Under optimal conditions, the composite film was simultaneously used to remove coexisting oxytetracycline-Cu2+. The study results show that the reduction of Cu2+ on cathode was promoted by oxytetracycline while the degradation of oxytetracycline on photoanode was slightly suppressed by Cu2+. Also, possible photoelectrocatalytic degradation pathways for oxytetracycline-Cu2+ were analyzed by HPLC-MS.

Simultaneous removal of antimony, chromium and aniline by forward osmosis membrane: Preparation, performance and mechanism

Antimony (Sb), chromium (Cr) and aniline are typical contaminants in printing and dyeing wastewater, which are toxic and have potential carcinogenicity to humans. The rejection performance of forward osmosis (FO) membranes for the mixed pollutants of Sb, Cr, and aniline under different cross-linking degree of polyamide (PA) selective layer, concentration and type of draw solution (DS) were analyzed. Results showed that the water flux of PAN-1.5LiCl FO membrane was about two times higher than that of unmodified membrane and the rejection of Sb, Cr, and aniline was 98.2%, 99.9%, and 92.6% with 0.5 M NaCl as DS, respectively. While NaCl concentration increased from 0.5 M to 2.0 M, the rejection of aniline enhanced from 92.6% to 95.2%. When 0.5 M Na2SO4 was used as DS, the rejection of aniline increased to 95.6% due to the relatively low water flux during FO process. The high rejection of Sb, Cr and aniline should be ascribed to the steric hindrance and electrostatic interaction between FO membrane and the contaminants. When secondary clarifier effluent from a wastewater treatment plant (WWTP) in a printing and dyeing factory was used as feed solution (FS), rejection efficiencies of Sb, Cr, aniline all attained over 98%.

Flower-Like Dual-Defective Z-Scheme Heterojunction g-C3N4/ZnIn2S4 High-Efficiency Photocatalytic Hydrogen Evolution and Degradation of Mixed Pollutants.

Graphitic carbon nitride (g-C3N4) with a porous nano-structure, nitrogen vacancies, and oxygen-doping was prepared by the calcination method. Then, it was combined with ZnIn2S4 nanosheets containing zinc vacancies to construct a three-dimensional (3D) flower-like Z-scheme heterojunction (pCN-N/ZIS-Z), which was used for photocatalytic hydrogen evolution and the degradation of mixed pollutants. The constructed Z-scheme heterojunction improved the efficiency of photogenerated charges separation and migration, and the large surface area and porous characteristics provided more active sites. Doping and defect engineering can change the bandgap structure to improve the utilization of visible light, and can also capture photogenerated electrons to inhibit recombination, so as to promote the use of photogenerated electron-hole pairs in the photocatalytic redox process. Heterojunction and defect engineering synergized to form a continuous and efficient conductive operation framework, which achieves the hydrogen production of pCN-N/ZIS-Z (9189.8 µmol·h−1·g−1) at 58.9 times that of g-C3N4 (155.9 µmol·h−1·g−1), and the degradation rates of methyl orange and metronidazole in the mixed solution were 98.7% and 92.5%, respectively. Our research provides potential ideas for constructing a green and environmentally friendly Z-scheme heterojunction catalyst based on defect engineering to address the energy crisis and environmental restoration.

Amino-functionalized Ti-metal-organic framework decorated BiOI sphere for simultaneous elimination of Cr(VI) and tetracycline

A subtle flower-like MIL-125-NH2@BiOI was fabricated by a facile solvothermal method for simultaneously eliminating Cr(VI)/tetracycline mixed pollutants under visible light. The strong interaction between amino in MIL-125-NH2 and Bi3+ of BiOI promotes the formation of this unique inlaid structure and enables the favorable contact between MIL-125-NH2 and BiOI, thus accelerating the transfer of charge carriers. Remarkably, MIL-125-NH2@BiOI displays a superior activity compared with that of two monomers for the photocatalytic reduction of Cr(VI) and degradation of tetracycline. More significantly, the photocatalytic efficiency can be further boosted in the coexistence of Cr(VI) and tetracycline, which is 1.8 and 1.6 times that of single Cr(VI) and tetracycline, respectively. The synergistic effect between Cr(VI) reduction and tetracycline oxidative degradation can further facilitate the separation of photo-induced electrons and holes, resulting in the improved efficiencies in the Cr(VI)/tetracycline coexistent environment. This work sheds light on that MOF-based photocatalysts possess huge potential for practical environmental remediation.

Developmental alterations, teratogenic effects, and oxidative disruption induced by ibuprofen, aluminum, and their binary mixture on Danio rerio

Several studies highlighted the ubiquitous presence of ibuprofen and aluminum in the aquatic environment around the world and demonstrated their potential to induce embryotoxic and teratogenic defects on aquatic species individually. Although studies that evaluate developmental alterations induced by mixtures of these pollutants are scarce; and, since environmental contamination presented in the form of a mixture of toxicants with different chemical properties and toxicity mechanisms capable of generating interactions; the objective of this study was to evaluate the developmental defects, teratogenic alterations, and oxidative stress induced by individual forms and the mixture of ibuprofen (IBU) and aluminum (Al) on zebrafish embryos. Oocytes exposed to environmentally relevant concentrations of IBU (0.1–20 μg L-1) and Al (0.01–8 mg L-1) and one binary mixture. The LC50 and EC50 were obtained to calculate the teratogenic index (TI). The IBU LC50, EC50, and TI were 8.06 μg L-1, 2.85 μg L-1 and 2.82. In contrast, Al LC50 was 5.0 mg L-1with an EC50 of 3.58 mg L-1 and TI of 1.39. The main alterations observed for individual compounds were hatching alterations, head malformation, skeletal deformities, hypopigmentation, pericardial edema, and heart rate impairment. The mixture also showed significant delays to embryonic development.Moreover, oxidative stress biomarkers of cellular oxidation and antioxidant defenses at 72 and 96 hpf significantly increased. Results show that environmentally relevant concentrations of ibuprofen (IBU), aluminum (Al), and their mixture promote a series of developmental defects, teratogenic effects, and oxidative disruption on D. rerio embryos, and the interaction of both substances altered the response. In conclusion, morphological and biochemical tests are suitable tools for assessing the health risk of aquatic wildlife by exposure to individual and mixed pollutants in freshwater bodies.

Prediction on the combined toxicities of stimulation-only and inhibition-only contaminants using improved inverse distance weighted interpolation

The evaluation of ecological risks of contaminant mixtures to organisms is very challenging due to the non-linear response of organisms to each component, especially under the co-existence of both stimulators and inhibitors. Whether the stimulatory effect can reduce or even offset the inhibitory effect would be critical to the risk assessment and the treatment measures of mixed pollutants. Here, the combined toxicity of sodium fluoride (NaF), a stimulator with stimulation rate >100%, and six compounds that cannot induce hormesis (four ionic liquids (ILs) and two pesticides) were studied. The time-dependent toxicity of each toxicant on Vibrio qinghaiensis sp.-Q67 was investigated at 0.25, 2, 4, 6, 8, 10 and 12 h. Results showed that four ILs and two pesticides failed to induce hormesis, while NaF induced hormesis from 2 to 6 h and induced stimulation only after 6 h and reached its maximum (650%) at 12 h. All mixture rays with NaF induced hormesis at different times. In the four NaF-IL mixture systems, the absolute value of maximum stimulation demonstrated an upwards and then a downwards trend with the increasing of mixture ratio of IL. In two NaF-pesticide systems, the maximum stimulation effect declined with the increasing of the mixture ratio of pesticide. The toxicities of the mixture were successfully predicted by the improved inverse distance weighted interpolation, which are not able to be predicted by the commonly used concentration addition or independent action models. This paper shed lights on evaluating the hormesis of mixtures and the ecological risk of fluoride.

Application of the Paracentrotus lividus sea-urchin embryo-larval bioassay to the marine pollution biomonitoring program in the Tunisian coast.

The pollution of the marine environment by treated and untreated effluents has increased due to human activities. Monitoring the marine ecosystem is nowadays a global concern. In this work, we evaluated the effect of contaminated and uncontaminated seawater, from different Tunisian coastal areas, on the fertilization, gastrulation, and embryo-larval development events of sea urchins (Paracentrotus lividus). The station of Salakta (SA) is considered as a control station, while the stations of Hamdoun Wadi (HW), Port of Monastir (PM), Karaia Monastir (KM), Teboulba (TE), and Khniss Lagoon (KL) are considered to be contaminated stations. The analysis of seawater physicochemical characteristics showed that levels of the total suspended matter (TSM), chemical oxygen demand (COD), biochemical oxygen demand (BOD), total organic carbon (TOC), and nitrate (NO3-) were lower in the seawater of the reference site Salakta (SA) when compared to those of the contaminated seawater sites. In addition, a very strong variation in the levels of trace metals in seawaters sampled in the studied sites was noted. In fact, the highest concentrations of Pb and Cu were observed in Hamdoun Wadi (HW), port of Monastir (PM), and Karaia Monastir (KM), while the highest concentration of Zn was noted in the Teboulba lagoon (TE) and Khniss (LK). Alterations in physicochemical characteristics as well as elevated trace metal levels in the studied seawater samples were correlated with reduced fertility rate, gastrulation rate, and the frequency of normal sea urchin larvae. The total absence of normal sea urchin pluteus larvae in the sea waters of heavily polluted sites proves the great sensitivity of the larval frequency to mixed pollution. This work recommends the utility of urchin fertilization and gastrulation rates and normal pluteus larval frequencies as useful bioassays to monitor the exposure of marine ecosystems to mixed pollution.