An environmentally friendly strategy for reducing the environmental risks of heavy metals adsorbed by kaolinite.

Plenty of heavy metals (HMs) that are adsorbed on clay minerals (such as kaolinite), in addition to low molecular-weight organic acids (such as oxalic acid (OA)) with high activities, are widespread in the natural environment. In the present study, the effects of OA on the environmental behaviors of Pb2+/Cd2+ adsorbed by kaolinite have been investigated. The effectiveness and mechanisms of calcium silicate (CS) and magnesium silicate (MS) in reducing the environmental risks of the HMs have also been studied. The results showed that the releases of Pb2+/Cd2+ increased with an increasing concentration of OA. When different dosages of CS/MS were added to the aging system, a redistribution of HMs took place and the free form of Pb2+/Cd2+ decreased to very low levels. Also, the unextractable Pb2+/Cd2+ increased to high levels. Furthermore, a series of characterizations showed that the released HMs were re-captured by the CS/MS. In addition, the CS immobilized the OA in the solution during the aging process, which also facilitated an immobilization of the carbon element in the environment. In general, the present study has contributed to a further understanding of the transport behaviors of the HMs in natural environments, and of the interactions between CS (or MS), the environmental media, and the heavy metal contaminants. In addition, this study has also provided an eco-friendly strategy for an effective remediation of heavy metal pollution.

Influence of dissolved organic matter with different molecular weight from chicken manure on ferrihydrite adsorption and re-release of antimony(V).

Applying organic fertilizer is the main way to enhance soil fertility through the interfacial reaction between mineral and dissolved organic matter (DOM). However, the interfacial reaction between minerals and DOM may influence antimony(V) (Sb(V)) mobility in agricultural soils around antimony mines. In our study the ferrihydrite (Fh) was chosen as a representative mineral, to reveal the effect of its interaction with chicken manure organic fertilizer (CM-DOM) with Fh on Sb(V) migration. In this study, we investigated different organic matter molecular weights and C/Fe molar ratios. Our findings indicated that the addition of CM-DOM decreased the adsorption of Sb(V) by Fh and promoted the re-release of Sb(V) adsorbed on Fh. This effect was enhanced by increasing the C/Fe molar ratio. Fh mainly affects its interaction with Sb(V) through electrostatic gravitational interaction and ligand exchange, but the presence of CM-DOM weakens the electrostatic interaction between Fh and Sb(V) as well as competes with Sb(V) for the hydroxyl reactive site on Fh surface. In addition, the smaller molecular weight fraction (<10 kDa) of CM-DOM has higher aromaticity and hydrophobicity, which potentially leads to more intense competition with Sb(V) for the reaction sites on Fh. Therefore, the application of organic fertilizer may promote Sb(V) migration, posing significant risks to soil ecosystems and human health, which should be a concern in field soil cultivation.

Mixed solvent fabrication of tobermorite and the fixation of heavy metals in water and soil.

Here, tobermorite was prepared by a solvothermal technology using calcite and quartz with a mixed solvent of ethanol and water. Factors including reaction temperature, time and KOH content were studied to optimize the preparation procedure. To study the relationship between ethanol content-material structural characteristics-adsorption capacity, a series of materials were prepared in different mixed solvent proportions of ethanol and water, and their structural characteristics and adsorption capacity were compared. We found that the adsorption capacity of different samples for Pb2+ and Cd2+ was positively correlated with negatively correlated with the surface area and negatively correlated with the crystallinity of materials. Then, the material prepared by 30% ethanol solution (30-T) with the best adsorption performance was used for further research; the results were fitted by kinetic and thermodynamic models, and adsorbed materials were analyzed by various characterizations, suggesting that the adsorption process was ascribed to comprehensive pathways including ion exchange, chemical precipitation, and surface-complexation. Then, the 30-T was further used to remediate heavy metals contaminated soil, and the remediation effect was examined by the DTPA-extractable method and the European Community Bureau of Reference (BCR) sequential extraction method. The DTPA-extractable results showed that tobermorite observably reduced the bioavailability of Pb and Cd, and the BCR results suggested that the acid-soluble and reducible fractions of Pb and Cd were transformed to the oxidizable and residual fractions after remediation. In summary, tobermorite has great potential in the remediation of heavy metal polluted-aquatic environment/system and soil.

Rapid and efficient reduction of chromate by novel Pd/Fe@biomass derived from Enterococcus faecalis.

Efficient reduction of chromate is highly desirable for its detoxification and remediation of the contaminated environment. This study described a fusion of the concepts of precious metal biorecovery and fabrication of Pd/Fe@biomass derived from simulated wastewater. The effectiveness of Pd/Fe@biomass during reduction process of Cr(VI) was evaluated by comparing with pure nZVI, E. faecalis and Pd@biomass. Results showed that Pd(II) could be recovered by E. faecalis with Fe(II) as the electron donor, and precipitation could yield nZVI anchored onto Pd-loaded E. faecalis. The nano particles (NPs) on Pd/Fe@biomass were well-dispersed, which provided 2.70 folds specific surface area comparing with nZVI. Efficient Cr(VI) reduction could be achieved at a higher catalyst dosage, the most appropriated Pd/Fe molar ratio of 2% and a wide pH range. Typically, 0.5 mM Cr(VI) could be completely reduced in 5 min driven by Pd/Fe@biomass under the conditions of dosage of 1.0 g/L and pH 3. Moreover, the mechanisms of Cr(VI) reduction by Pd/Fe@biomass were proposed, which intimately related to nZVI electron donating capacities, Pd catalysis for hydrogenation and galvanic cell effects between Fe and Pd. Therefore, Pd/Fe@biomass could be an alternative for rapid and complete reduction of Cr(VI).

Regulatory mechanism of montmorillonite on antibiotic resistance genes in Escherichia coli induced by cadmium.

The emergence and spread of antibiotic resistance genes (ARGs) induced by the overuse of antibiotics has become a serious threat to public health. Heavy metals will bring longer-term selection pressure to ARGs when the concentration of their residues is higher than that of antibiotics in environmental media. To explore the potential roles of montmorillonite (Mt) in the emergence of ARGs under divalent cadmium ion (Cd2+) stress, Escherichia coli (E. coli) was induced continuously for 15 days under Cd2+ gradient concentrations (16, 32, 64, 96, and 128 µg∙mL-1) with and without Mt. Subsequently, antibiotic resistance testing, transcriptomics, transmission electron microscope, scanning electron microscopy, and Fourier transform infrared were conducted for analysis. The results of characterization analysis showed that Cd2+could enhance the expression of resistance genes such as penicillin, tetracycline, macrolactone, and chloramphenicol in E. coli. Moreover, compared with Cd2+, Mt-Cd could inhibit the promotion of these resistances by alleviating the expressions of genes involved in cell wall/membrane, protein synthesis, transport systems, signal transduction, and energy supply processes. Therefore, the study promoted the understanding of Cd2+ in triggering bacterial antibiotic resistance and highlighted a novel theme of clay's ability to mitigate ecological risk of antibiotic resistance caused by heavy metals. KEY POINTS: • Montmorillonite (Mt) could inhibit the promotion of antibiotic resistances. • E. coli formed a unique resistance mechanism by interacting with Mt and Cd2+. • Mt stimulated cellular signal transduction, cellular component, and energy supply.

Induction of zincophore pseudopaline secretion by Cr(VI) and intracellular formation of granules from nanocrystal aggregation by Cr(III) in Pseudomonas aeruginosa.

When microorganisms are challenged with toxic metals, intracellular granules are commonly observed, however, the exact nature of these granules is poorly understood. Here we show that when Pseudomonas aeruginosa CCTCC AB93066 were exposed to Cr(VI), Cr can enter the cell in the form of both Cr(VI) and Cr(III), and intracellular granules of several hundred nanometers were formed in the nucleoid region and were built up by aggregation of nanocrystals. We suggested that these nanocrystals are organic crystals. Transcriptomic profiles and liquid chromatography tandem mass spectrometry (LC-MS/MS) analysis indicated that pseudopaline (a metallophore that can complex with Zn2+) production and pseudopaline-Zn2+ import into bacterial cells were enhanced upon Cr(VI) exposure. It was proposed that pseudopaline can scavenge Zn2+ which is essential for transcription alteration and DNA repair. Excessive pseudopaline might precipitate as nanospheres in the nuclear region that are further agglomerated by Cr(III) to form larger granules. During this process, Cr(III) is sequestered and immobilized. Hence we revealed pseudopaline production and zinc acquisition is crucial for alleviation of Cr(VI) toxicity and intracellular granules are composed of organic nanospheres which are aggregated by Cr(III).

Assessing environmental fate of hexavalent chromium as influenced by fractionation of ferrihydrite with dissolved organic matter.

The dynamic interactions among iron (Fe) oxides, dissolved organic matter (DOM) and toxic trace metals play crucial roles in risk assessment and environmental remediation. Although the inhibitory effects of DOM on the iron oxides transformation process have been studied previously, there is still a lack of mechanistic and quantitative understanding on the kinetics of Cr(VI) and ferrihydrite transformation in the present of DOM. In this study, we investigated the fractionation process of DOM on ferrihydrite and its influence on the fate of Cr(VI) and transformation of ferrihydrite. The result of three-dimension excitation emission matrix (3D-EEM), Q-Exactive LC-MS/MS, X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) indicated that fulvic acid-like compounds of DOM were the mainly fractionated compounds on the surface of ferrihydrite, which further inhibited the transformation of ferrihydrite. Besides, bracewellite (CrO(OH)) generated as an accompanied mineral during the transformation of ferrihydrite in the present of Cr(VI). Based on the DFT theoretical calculation, we concluded that Cr(VI) mainly in the form of HCr O4- was more inclined to be adsorbed on iron-oxide tetrahedron by inner-sphere monodentate mononuclear configurations. The findings on the dynamic coupling among Fe oxide transformation and Cr(VI) sequestration under the effect of DOM provided the basis for accurately predicting the fate of trace elements and iron mineral.

Insights into photocatalytic degradation of phthalate esters over MSnO3 perovskites (M = Mg, Ca): Experiments and density functional theory.

In this study, the physicochemical and photocatalytic properties of two kinds of stannate perovskite oxides (MgSnO3 and CaSnO3) were investigated under simulated sunlight, where dimethyl phthalate (DMP) and diethyl phthalate (DEP) were selected as the probe pollutants. The results of photochemical characterization showed that MgSnO3 perovskite exhibited better photocatalytic performance than CaSnO3 perovskite. MgSnO3 perovskite could effectively degrade 75% of DMP and 79% of DEP through pseudo-first-order reaction kinetics, which remained good in pH 3.0 to 9.0. Quenching experiments and electron paramagnetic resonance (EPR) characterization indicated that photogenerated holes (h+), superoxide (O2-), and hydroxyl radicals (OH) worked in the photo-degradation, while O2- played the most important role. Furthermore, intermediates identification and density functional theory (DFT) calculations were used to explore the degradation mechanism. For both DMP and DEP, the reactive oxygen species (ROS, including O2- and OH) were responsible for the hydroxylation of benzene ring and the breaking of the aliphatic chain, while h+ was prone to break the aliphatic chain. This work is expected to provide new insights on the photocatalytic mechanism of stannate perovskites for environmental remediation.

Efficient separation of aluminum foil from mixed-type spent lithium-ion power batteries.

The disposal of spent lithium-ion power batteries (LIBs) has become an important research topic owing to the booming market for electric vehicles. However, the recovery efficiency of the alkaline solution and organic solvent methods currently used to separate Al foil from cathode materials still has room for improvement. The insufficient separation of Al foil and complexity of the battery types present obstacles to the extraction of valuable metals using simple processes. In this study, an efficient approach is developed to separate the Al foil in mixed-type spent LIBs (M-LIBs), namely, LiNixCoyMnzO2 (NCM), LiFePO4 (LFP), and LiMn2O4 (LMO) LIBs, by controlled pyrolysis. Hundred percent of the Al foil was recovered at the temperature of 450 °C, holding time of 60 min, and heating rate of 10 °C/min. The purity of Al in the recovered foil was 99.41 %, 99.83 % and 99.92 %, and the recovery efficiency of the active cathode materials was 96.01 %, 99.80 % and 99.15 % for NCM, LFP and LMO, respectively, without the loss of active cathode materials. The obtained active cathode materials exhibited a favorable crystalline structure, and the average particle diameter was reduced from 300.497 to 24.316 µm with a smaller and looser morphology. The process could be well fitted with the Friedman differential equation, and the correlation coefficients were higher than 0.99. The efficient separation could be attributed to the complete rupture of long chain -(CH2CF2)-n bonds in the poly (vinylidene difluoride) (PVDF) binder, which resulted in the formation of HF, trifluorobenzene, alkanes, and gaseous single molecule CH2CF2. Therefore, this work potentially provides an alternative approach for the efficient separation of Al foil in M-LIBs, thereby simplifying the process and achieving lower cost, reduced loss of valuable metals, and higher recovery efficiency.

Batch interaction of emerging tetracycline contaminant with novel phosphoric acid activated corn straw porous carbon: Adsorption rate and nature of mechanism.

In this work, corn straw (CS) based porous carbon was prepared by one-step phosphoric acid (H3PO4) low temperature activation. The impregnation ratios (H3PO4/CS, g/g) played an important role in the pore development. ACS300-1 engineered at 300 °C and the impregnation ratio of 1.0 showed the maximal specific surface area of 463.89 m2/g with total pore volume of 0.387 cm3/g, attaining a high tetracycline (TC) uptake of 227.3 mg/g. The adsorption of TC onto ACS300-1 was found tolerant with wide pH (2.0-10.0) and high ionic strength (0 - 0.5 M). The adsorption data can be fitted well by the pseudo-second order kinetic model and Langmuir isotherm model. The endothermic and spontaneous properties of the adsorption system was implied by Thermodynamic study. The findings of the current work conclude that one-step H3PO4 activation is a green and promising method for corn straw based porous carbon that may be found with great potentials in antibiotic containing wastewater treatment.

Efficient degradation of sodium diclofenac via heterogeneous Fenton reaction boosted by Pd/Fe@Fe3O4 nanoparticles derived from bio-recovered palladium.

Dehalogenation of emerging pollutants has attracted worldwide attention. In this study, novel bio-Pd/Fe@Fe3O4 nanoparticles (NPs) were proposed to boost the heterogeneous Fenton reaction for degradation of sodium diclofenac (DCF). Specifically, Enterococcus faecalis (E. faecalis) was employed to achieve bio-recovered palladium (bio-Pd). Results showed that expected preparation of bio-Pd/Fe@Fe3O4 NPs was confirmed by various characterization techniques. The prepared bio-Pd/Fe@Fe3O4 NPs were spherical morphology with average size of 9 nm. Under the optimum conditions, the removal efficiency of 10 mg/L DCF in 20 min and 40 min reached as high as 94.69% and 99.65%, respectively. The dechlorination and mineralization efficiencies of DCF were 85.16% and 59.21% in 120 min, respectively. The main degradation pathway of DCF was complete mineralization with the final products CO2, chloride ions and H2O. The improvement of dechlorination efficiency was ascribed to the accelerated corrosion of nano zero valent iron (nZVI) by Pd/Fe galvanic effect and the rise of active hydrogen. Meanwhile, more ferrous ions were released into this solution, resulting in the higher heterogeneous Fenton reaction rate driven by bio-Pd/Fe@Fe3O4 NPs. Therefore, the findings suggested that bio-Pd/Fe@Fe3O4 NPs were effective catalysts for DCF dechlorination and mineralization. The work provided a novel strategy for degradation of halogen-containing environmental pollutants.

Performance evaluation of integrated adsorption-nanofiltration system for emerging compounds removal: Exemplified by caffeine, diclofenac and octylphenol.

Emerging pollutants introduced into surface water pose potential hazards to the safety of drinking water. In this study, the removal performance of three emerging compounds (exemplified by caffeine, diclofenac and octylphenol, with different physico-chemical properties) from synthetic water and source water by combining activated carbon (AC) adsorption and nanofiltration (NF) membrane processes was evaluated and analyzed. Results from synthetic water showed that the adsorption isotherms modeled well with the Langmuir equation. The removal performance of target compounds by AC-NF system was more remarkable than that of NF-AC combination. In the source water system, the integrated AC-NF process with coagulation pretreatment (the alum dosage of 60 mg/L) achieved satisfactory performance (the removal efficiencies of three target compounds reached > 95%). Results showed the electrostatic interaction and pollutant hydrophobicity determined the behavior and the fate of selected PPCPs/EDCs during the sequential treatment process of coagulation, activated carbon adsorption, and NF membrane separation. Finally, the AC and NF membranes were analyzed by Fourier transform infrared spectroscopy and scanning electron microscopy to understand the mechanisms, i.e. electrostatic and hydrophobic effects on the total removal process. It suggests that the integrated AC-NF process with coagulation pretreatment should be a feasible approach for removing emerging compounds in waterworks.

Environmental application of MgMn-layered double oxide for simultaneous efficient removal of tetracycline and Cd pollution: Performance and mechanism.

The MgMn-layered double oxide (MgMn-LDO), which was fabricated by calcining MgMn-layered double hydroxide (MgMn-LDH), was used to remove tetracycline (TC) and cadmium (Cd) pollution. In MgMn-LDO activated peroxymonosulfate (PMS) system, 97.1% of TC was degraded within 20 min. The high oxidizing sites exposed on MgMn-LDO surface played a main role on activating PMS to generate OH, SO4-, O2- and 1O2 (the key species) for TC degradation. MgMn-LDO could keep excellent degradation performance in a wide range of pH (from 4 to 10). The degradation degree of TC in distilled water is basically the same as that in Pearl River water, and even above 80% of TC could be degraded in human urine. The good reusability and high structure stability of MgMn-LDO were further verified. Meanwhile, Cd immobilization on MgMn-LDO reached equilibrium within 10 min, and its maximum fixed quantity was 8.234 mmol g-1 (922.208 mg g-1). The outstanding Cd fixed ability resulted from the formation of CdCO3 and Cd (OH)2. In combined system, the existence of TC promoted the immobilization of Cd on MgMn-LDO. Low concentration of Cd (0.0125 mM) had synergism effect on TC degradation, while high concentration of Cd (0.025 and 0.05 mM) had inhibiting action. Finally, a column filled with MgMn-LDO was designed for repairing TC and Cd pollution hierarchically. This study provided an effective strategy to clean up the organic-heavy metal combined pollution.

Immobilization of Sphingomonas sp. GY2B in polyvinyl alcohol-alginate-kaolin beads for efficient degradation of phenol against unfavorable environmental factors.

In this study, batch experiments were carried out to evaluate the biodegradation of phenol by Sphingomonas sp. GY2B, which were immobilized in polyvinyl alcohol (PVA)-sodium alginate-kaolin beads under different conditions. The optimal degradation performance was achieved by GY2B immobilized in beads containing 1.0% (w/v) of kaolin, 10% (w/v) of PVA, 0.3% (w/v) of sodium alginate, 10% (v/v) of biomass dosage, and exposed to an initial phenol concentration of 100 mg/L. The experimental results indicated that PVA-sodium alginate-kaolin beads can accelerate the degradation rate of phenol by reducing the degradation time and also improve degradation rate. The biodegradation rate of phenol by immobilized cells (16.79 ±â€¯0.81 mg/(L·h)) was significantly higher than that of free cells (11.49 ±â€¯1.29 mg/(L·h)) under the above optimal conditions. GY2B immobilized on beads was more competent than free GY2B in degradation under conditions with high phenol concentrations (up to 300 mg/L) and in strong acidic (pH = 1) and alkaline (pH = 12) environments. Higher phenol concentrations inhibit the biomass and reduce the biodegradation rate, while the lower biodegradation rate at low initial phenol concentrations is attributed to mass transfer limitations. The Haldane inhibitory model was in agreement with the experimental data well, revealing that phenol showed a considerable inhibitory effect on the biodegradation by Sphingomonas sp. GY2B, especially at concentrations higher than 90 mg/L. Intra-particle diffusion model analysis suggests that adsorption of phenol by immobilized beads was controlled by both rapid surface adsorption as well as pore diffusion mechanism. It's worth noting that the presence of 1 mg/L Cr(VI) enhanced the biodegradation of phenol by free cells, while Cr(VI) showed no obvious impact on the removal of phenol by immobilized cells. In addition, immobilized cells were reused 16 times and removed 99.5% phenol, and when stored at 4 °C for 90 days, more than 99% phenol was removed. These results showed that immobilized cells can significantly improve the microbial degradation performance, and protect microorganisms against unfavorable environment. It is implied that PVA -sodium alginate-kaolin beads have great potential to be applied in a practical and economical phenolic wastewater treatment system.

Simultaneous electricity production and antibiotics removal by microbial fuel cells.

The removal of antibiotics is crucial for improvement of water quality in animal wastewater treatment. In this paper, the performance of microbial fuel cell (MFC) in terms of degradation of typical antibiotics was investigated. Electricity was successfully produced by using sludge supernatant mixtures and synthesized animal wastewater as inoculation in MFC. Results demonstrated that the stable voltage, the maximum power density and internal resistance of anaerobic self-electrolysis (ASE) -112 and ASE-116 without antibiotics addition were 0.574 V, 5.78 W m-3 and 28.06 Ω, and 0.565 V, 5.82 W m-3 and 29.38 Ω, respectively. Moreover, when adding aureomycin, sulfadimidine, roxithromycin and norfloxacin into the reactors, the performance of MFC was inhibited (0.51 V-0.41 V), while the output voltage was improved with the decreased concentration of antibiotics. However, the removal efficiency of ammonia nitrogen (NH3-N) and total phosphorus (TP) were both obviously enhanced. Simultaneously, LC-MS analysis showed that the removal efficiency of aureomycin, roxithromycin and norfloxacin were all 100% and the removal efficiency of sulfadimidine also reached 99.9%. These results indicated that antibiotics displayed significantly inhibitions for electricity performance but improved the quality of water simultaneously.

Immobilization of Acidithiobacillus ferrooxidans on cotton gauze for biological oxidation of ferrous ions in a batch bioreactor.

The ability of Acidithiobacillus ferrooxidans to oxidize ferrous iron has been extensively studied in bioleaching to recover metal resources. Although immobilization of A. ferrooxidans is of great importance to achieve high bioleaching performance in practical application, the reported approaches of immobilization of A. ferrooxidans are still limited. This paper is attempting to develop a novel method to immobilize A. ferrooxidans by a less-costly effective carrier from zeolite, activated carbon, and cotton gauze. The results showed that cotton gauze was the most suitable carrier to immobilize A. ferrooxidans cells in comparison with zeolite and activated carbon. Acidithiobacillus ferrooxidans immobilized on the cotton gauze by gravity dehydration could achieve an average ferrous iron oxidation rate of 0.73 g/(L·h). Furthermore, the ferrous iron oxidation ratio attained in the bioreactor under batch operation was maintained above 97.83%. All results indicated that cotton gauze could be an efficient carrier for immobilizing A. ferrooxidans cells for the biooxidation of ferrous ions.

FeOOH-loaded MnO2 nano-composite: An efficient emergency material for thallium pollution incident.

A FeOOH-loaded MnO2 nano-composite was developed as an emergency material for Tl(I) pollution incident. Structural characterizations showed that FeOOH successfully loaded onto MnO2, the nanosheet-flower structure and high surface area (191 m2 g-1) of material contributed to the excellent performance for Tl(I) removal. FeOOH-loaded MnO2 with a Fe/Mn molar ratio of 1:2 exhibited a noticeable enhanced capacity for Tl(I) removal compared to that of pure MnO2. The outstanding performance for Tl(I) removal involves in extremely high efficiency (achieved equilibrium and drinking water standard within 4 min) and the large maximum adsorption capacity (450 mg g-1). Both the control-experiment and XPS characterization proved that the removal mechanism of Tl(I) on FeOOH-loaded MnO2 included adsorption and oxidation: the oxidation of MnO2 played an important role for Tl(I) removal, and the adsorption of FeOOH loaded on MnO2 enhanced Tl(I) purification at the same time. In-depth purification of Tl(I) had reach drinking water standards (0.1 µg L-1) at pH above 7, and there wasn't security risk produced from the dissolution of Mn2+ and Fe2+. Moreover, the as-prepared material could be utilized as a recyclable adsorbent regenerated by using NaOH-NaClO binary solution. Therefore, the synthesized FeOOH-loaded MnO2 in this study has the potential to be applied as an emergency material for thallium pollution incident.

Ecotoxicity monitoring and bioindicator screening of oil-contaminated soil during bioremediation.

A series of toxicity bioassays was conducted to monitor the ecotoxicity of soils in the different phases of bioremediation. Artificially oil-contaminated soil was inoculated with a petroleum hydrocarbon-degrading bacterial consortium containing Burkholderia cepacia GS3C, Sphingomonas GY2B and Pandoraea pnomenusa GP3B strains adapted to crude oil. Soil ecotoxicity in different phases of bioremediation was examined by monitoring total petroleum hydrocarbons, soil enzyme activities, phytotoxicity (inhibition of seed germination and plant growth), malonaldehyde content, superoxide dismutase activity and bacterial luminescence. Although the total petroleum hydrocarbon (TPH) concentration in soil was reduced by 64.4%, forty days after bioremediation, the phytotoxicity and Photobacterium phosphoreum ecotoxicity test results indicated an initial increase in ecotoxicity, suggesting the formation of intermediate metabolites characterized by high toxicity and low bioavailability during bioremediation. The ecotoxicity values are a more valid indicator for evaluating the effectiveness of bioremediation techniques compared with only using the total petroleum hydrocarbon concentrations. Among all of the potential indicators that could be used to evaluate the effectiveness of bioremediation techniques, soil enzyme activities, phytotoxicity (inhibition of plant height, shoot weight and root fresh weight), malonaldehyde content, superoxide dismutase activity and luminescence of P. phosphoreum were the most sensitive.

Simultaneous heavy metals removal and municipal sewage sludge dewaterability improvement in bioleaching processes by various inoculums.

The heavy metals content and dewaterability of municipal sewage sludge (MSS) are important parameters affecting its subsequent disposal and land application. Six kinds of inoculums were prepared to examine the characteristics of heavy metals removal and MSS dewaterability improvement in bioleaching processes. The results showed that Cu, Zn and Cd bioleaching efficiencies (12 days) were 81-91, 87-93 and 81-89%, respectively, which were significantly higher than those of Fe-S control (P < 0.05) and blank control (P < 0.01). The bioleaching boosted by the prepared inoculums could also significantly enhance MSS dewaterability (P < 0.01). The centrifugal dehydration efficiency of MSS rose from 73.00 to 90.00% at day 12. Microscopic observations and energy dispersive spectrum analysis demonstrated that the dewaterability improvement might be attributed to the changes of sludge structure from flocculent to obvious granular and the formation of secondary minerals mainly consisting of iron, oxygen and sulfur elements. The results above demonstrated that bacterial consortium enriched from acid mine drainage (AMD) was suitable to boost sludge bioleaching for heavy metals removal and dewaterability improvement. It also suggested that the synergy of sulfur/ferrous-oxidizing bacteria (SFOB) enriched from AMD and the cooperation of exogenous and indigenous SFOB significantly promoted bioleaching efficiencies.

Understanding the role of clay minerals in the chromium(VI) bioremoval by Pseudomonas aeruginosa CCTCC AB93066 under growth condition: microscopic, spectroscopic and kinetic analysis.

Laboratory batch experiments were conducted to investigate the role of clay minerals, e.g., kaolinite and vermiculite, in microbial Cr(VI) reduction by Pseudomonas aeruginosa under growth condition in glucose-amended mediums as a method for treating Cr(VI)-contaminated subsurface environment such as soil. Our results indicated that glucose could acted as an essential electron donor, and clay minerals significantly enhanced microbial Cr(VI) reduction rates by improving the consumption rate of glucose and stimulating the growth and propagation of P. aeruginosa. Cr(VI) bioreduction by both free cells and clay minerals-amended cells followed the pseudo-first-order kinetic model, with the latter one fitting better. The mass balance analyses and X-ray photoelectron spectroscopy analysis found that Cr(VI) was reduced to Cr(III) and the adsorption of total chromium on clay minerals-bacteria complex was small, implying that Cr(VI) bioremoval was not mainly due to the adsorption of Cr(VI) onto cells or clay minerals or clay minerals-cells complex but mainly due to the Cr(VI) reduction capacity of P. aeruginosa under the experimental conditions studied (e.g., pH 7). Atomic force microscopy revealed that the addition of clay minerals (e.g. vermiculite) decreased the surface roughness of Cr(VI)-laden cells and changed the cell morphology and dimension. Fourier transform infrared spectroscopy revealed that organic matters such as aliphatic species and/or proteins played an important role in the combination of cells and clay minerals. Scanning electron microscopy confirmed the attachment of cells on the surface of clay minerals, indicating that clay minerals could provide a microenvironment to protect cells from Cr(VI) toxicity and serve as growth-supporting materials. These findings manifested the underlying influence of clay minerals on microbial reduction of Cr(VI) and gave an understanding of the interaction between pollutants, the environment and the biota.