Opportunities, challenges and modification methods of coal gangue as a sustainable soil conditioner-a review.

The persistent reliance on coal has resulted in the accumulation of substantial coal gangue, a globally recognized problematic solid waste with environmental risks. Given the coal gangue properties and global land degradation severity, the resourceful utilization of coal gangue as soil conditioners is believed to be a universally applicable, cost-effective, high-demand and environment-friendly model with broad application prospect. The direct application of raw coal gangue faces challenges of low active beneficial ingredients, inadequate water and fertilizer retention, presence of potentially toxic elements, resulting in limited efficacy and environmental contamination. This paper provided a comprehensive review of various modification methods (including mechanical, chemical, microbiological, thermal, hydrothermal and composite modifications) employed to enhance the soil improvement performance and reduce the environmental pollution of coal gangue. Furthermore, an analysis was conducted on the potential application of modified coal gangue as a muti-function soil conditioner based on its altered properties. The modified coal gangue is anticipated to effectively enhance soil quality, exhibiting significant potential in mitigating carbon emissions and facilitating soil carbon sequestration. This paper provided innovative ideas for future research on the comprehensive treatment of coal gangue and restoration of degraded soil in order to achieve the dual goals of zero-coal gangue waste and sustainable agriculture.

Functional group-specific reduction of Cr(VI) by low molecular weight organic acids in frozen solution: Kinetics, mechanism and DFT calculation.

Low molecular weight organic acids (LMWOA) are commonly present in natural water and play a pivotal role in the reduction of Cr(VI). In frozen solutions, the efficiency of Cr(VI) reduction is significantly enhanced due to the freezing concentration effect. However, this facilitation is found to be contingent upon the functional groups of LMWOA in this study. To be specific, LMWOA and Cr(VI) can form five-membered ring complexes, which greatly enhance electron transfer efficiency through Ligand-to-Metal Charge Transfer (LMCT). DFT calculations indicate that oxygen-containing groups located on carbon atoms at α positions play a crucial role in forming these complexes, ultimately determining the kinetics of Cr(VI) reduction. Moreover, freezing not only increases proton concentrations but also reduces free water molecule content in the liquid-like layer (LLL), thereby affecting LMWOA species through regulation of protonation and hydrolysis, and subsequently impacting reaction mechanisms. The stoichiometric ratios between LMWOA and Cr(VI) exceed theoretical values due to complexation with Cr(III). The reduction of Cr(VI) by LMWOA in frozen solutions is inhibited by soil solution, while the degree of inhibition varies among different types of LMWOA.

Is crystalline chromium phosphate environmentally stable? A study on the formation, dissolution and oxidation risk of CrPO4·6H2O.

Hexavalent chromium (Cr(VI)) contamination in soil and groundwater is usually remediated via reduction techniques. The formation of crystalline chromium phosphate (CrPO4·6 H2O) occurs as a byproduct during Cr(VI) remediation processes in the presence of phosphate, yet its stability in the environment has received limited attention. In this study, the formation conditions, structure, properties, and risks associated with the dissolution and oxidation of CrPO4·6 H2O were comprehensively assessed. Results showed that crystalline CrPO4·6 H2O was formed under pH 5 - 7 at room temperature. CrPO4·6 H2O exhibits higher dissolution risk compared to Cr(OH)3·3 H2O due to a long Cr-P bond (4.2 Å). H+ and OH- increased the risk of dissolution at pH 5 and 11, respectively, owing to the formation of CrH2PO42+ and Cr(OH)4-. In addition, under faintly acidic conditions, the high solubility of CrPO4·6 H2O increases the risk of oxidation; under neutral and weakly alkaline conditions, the presence of positively charged Cr(H2O)63+ structures on the surface elevates its susceptibility to contact and oxidation by δ-MnO2 compared to Cr(OH)3·3 H2O. Specifically, at pH 11, the conversion of CrPO4·6 H2O to Cr(OH)3·3 H2O results in similar oxidation risks for both Cr(III) precipitates.

Pressurized electro-osmotic dewatering treatment of sludge: focusing on the influences on nutrients for agricultural application.

Sewage sludge requires effective dewatering and high nutrients retention before disposal for agricultural application. Pressurized electro-osmotic dewatering (PEOD) process with low energy consumption can effectively remove water from sludge, but the influences of PEOD process on nutrients for agricultural application still lacks in-depth research. In this study, the influences of PEOD process on nutrients for agricultural application were investigated, including organic matter, nitrogen, phosphorus, potassium and silicon contents. Layered experiments were conducted to investigate the layered variation of nutrients in sludge and to understand the potential change mechanisms. The experimental results showed that PEOD process caused small losses (<10%) of organic matter and total phosphorus (TP) in sludge, but caused 11.2-18.4% loss of total nitrogen (TN). PEOD process also caused 18.6-27.0% loss of total potassium (TK) and over 80% loss of available potassium in sludge, and could weaken the potential salt damage during the agricultural application of sludge. Furthermore, the available phosphorus content of sludge in the anode area increased significantly after the PEOD process, indicating that PEOD process could enhance the phosphorus bioavailability of sludge in the anode area. Besides, PEOD process caused a slight loss of silicon components in sludge, but improved the long-term silicon dissolution and release ability of sludge. This work could expand the knowledge about the influences of PEOD process on sludge nutrients and provide scientific guidance for the agricultural application of PEOD sludge.

Long-term stability and toxicity effects of three-dimensional electrokinetic remediation on chromium-contaminated soils.

The three-dimensional electrokinetic remediation (3D EKR) achieved efficient removal of chromium (Cr) from the soil through mechanisms including electromigration, electroosmosis, and redox reactions. In this study, the long-term stability, leaching toxicity, bioavailability, and phytotoxicity of Cr in remediated soils were systematically analyzed to comprehensively evaluate the effectiveness of the 3D EKR method. The results showed that the concentration of hexavalent chromium (Cr (VI)) in the leachate of the 3D EKR system with sulfidated nano-scale zerovalent iron (S-nZVI) was more than 40% lower than those of the other 3D electrode groups, and the time required to reach the level III standard of groundwater quality criterion in China (0.05 mg/L, GB/T 14848-2017) was significantly shortened. The stabilization of Cr(VI) in contaminated soil after 3D EKR was maintained for 300 pore volumes (PVs), indicating that the treated Cr(VI) had good long-term stability. The leaching toxicity and bioaccessibility of Cr were assessed by the synthetic precipitation leaching procedure (SPLP), the toxicity characteristic leaching procedure (TCLP), and the physiologically based extraction test (PBET). The concentration of Cr(VI) in the SPLP, TCLP, and PBET leachates of the S-nZVI group decreased by more than 25% compared to the other 3D electrode groups, corresponding to the decrease in leaching toxicity and bioavailability of the treated Cr during the 15-day remediation period. In addition, the germination rate of wheat seeds and the average biomass of wheat seedlings in the S-nZVI group under alkaline conditions (EE) were higher than those in the non-polluting group (Blank-OH), indicating that the remediated soil had no obvious toxicity to wheat. In summary, 3D EKR achieved a satisfactory and stable remediation effect on Cr-contaminated soil, especially when using S-nZVI as the 3D electrode.

Sulfite Poses a Risk of Hexavalent Chromium Rebound in Vadose Zone: A Challenge of the Stability of CrxFe1-x(OH)3.

Cr(VI) rebound is the primary risk associated with the reduction remediation of Cr(VI)-contaminated soil. The potential impact of sulfites, which can be produced by microbial activities or originate from sulfur-containing remediation agents, on the Cr(VI) rebound in the vadose zone has been overlooked. When sulfites are present, the stability of CrxFe1-x(OH)3 is compromised and significantly inferior to that of Cr(OH)3, as demonstrated in this paper. First, Fe acts as a catalyst for the conversion of adsorbed sulfite to SO4·-, which subsequently triggers the oxidation of Cr(III) and results in the rebound of Cr(VI). The heterogeneous catalysis by Fe on the surface of CrxFe1-x(OH)3 plays a predominant role, contributing to 78% of the actual oxidation of Cr(III) among all employed catalytic processes. The presence of ambient Cl- can exacerbate the rebound effect of Cr(VI) by promoting the generation of HOCl. Furthermore, a portion of released Cr(VI) was reduced to Cr(III) by dissolved sulfite in the presence of dissolved Fe as a catalyst, thereby increasing the dissolution and migration risk associated with CrxFe1-x(OH)3. Hence, the presence of sulfites results in a significant increase in the Cr(VI) rebound and Cr(III) release from CrxFe1-x(OH)3. This challenges the conventional understanding of the stability of CrxFe1-x(OH)3.

Effects of voltage and pressure on sludge electro-dewatering process and the dewatering mechanisms investigation.

Electro-dewatering technology shows a good application prospect because of its high efficiency in removing water from sludge and low energy consumption, but the potential mechanisms of sludge electro-dewatering have not been investigated in depth, which seriously limits the further development and application of electro-dewatering technology. In this study, the effects of voltage and pressure on sludge electro-dewatering performance, physicochemical characteristics and extracellular polymeric substances (EPS) compositions and distributions were investigated. The spatial distributions of EPS main components, including polysaccharide (PS) and protein (PN), were characterized by a confocal laser scanning microscopy (CLSM). The experimental results showed that under the conditions of a voltage of 40 V and a pressure of 90 kPa, the moisture content of sludge was reduced from 83.15% to 53.12%, and the bound water content of sludge in the anode layer, middle layer and cathode layer were decreased significantly from 1.16 g/g dry solid (DS) to 0.20, 0.47 and 0.35 g/g DS, respectively. The PN content of EPS in anode layer was significantly lower than that in cathode layer due to the electrochemical oxidation, while the variation of PS content showed the opposite trend, which agreed with the results visualized by CLSM. Pearson's correlation coefficient and hierarchical cluster analysis revealed that PN in TB-EPS was the major factor influencing the effect of sludge electro-dewatering. This work can be helpful to understand the potential mechanisms of electro-dewatering and provide theoretical support for the further popularization and application of electro-dewatering technology.

Research on Treatment of Oily Sludge from the Tank Bottom by Ball Milling Combined with Ozone-Catalyzed Oxidation.

Difficult separation of oil-solid phase and high fine content of the recovered oil were two problems in the treatment of oily sludge from the tank bottom by the hot water-based extraction process. To solve the problems, one technology with "ball milling + ozone-catalyzed oxidation" as the core was studied, and the process parameters of ball milling and ozone-catalyzed oxidation were respectively optimized. After ball milling treatment, the oil content of dry oily sludge decreased from 33.9 to 10.2%. Then, an ozone catalytic oxidation treatment technology with aluminum ore as the catalyst was developed to further treat this stubborn oily sludge. Under the optimal conditions, the oil content of oily sludge could be further reduced to 0.28%, which met the treatment and disposal requirements stipulated in GB4284-2018. For further research on the contribution of the catalyst to the ozone catalytic oxidation system, the reaction activation energy and reaction rates of ozone oxidation and ozone catalytic oxidation were compared from the perspective of kinetics. The results showed that, with the catalyst addition, the reaction rate constants increased about three times and the reaction activation energy reduced 82.26%, which showed the effectiveness of the catalyst on the kinetics quantitatively. The combined process with "ball milling + ozone-catalyzed oxidation" as the core can solve the two problems in the treatment of oily sludge from the tank bottom by hot water-based extraction and provides a reference for the harmless and resourceful treatment of oily sludge from the tank bottom.

Comprehensive reutilization of iron in iron ore tailings: preparation and characterization of magnetic flocculants.

A large number of iron ore tailings (IOTs) are produced in steel industry, posing threat to the environment during its storage and disposal. To effectively reutilize Fe in IOTs, we propose a comprehensive utilization scheme: (1) most Fe in IOTs is extracted by concentrated hydrochloric acid to form FeCl3 flocculants; (2) after separation from the FeCl3 flocculants, a small amount of Fe is absorbed on the residue solids, which is further washed out to synthesize micron Fe3O4 as magnetic seeds. Results show that the as-synthetic FeCl3 flocculants meet the product standard for FeCl3 flocculants in China (GB/T 4482-2018) after a series of treatments including rotary evaporation, neutralization, and dilution and have comparable performance with commercial polyaluminum chloride (PAC) and polyaluminum ferric chloride (PAFC). Moreover, the addition of synthetic superparamagnetic Fe3O4 (as magnetic seeds) doubled the flocculation rate compared with as-synthetic FeCl3 flocculants alone. Finally, the reutilization of Fe in IOTs can create a direct economic value of ¥ 1.27/kg IOTs, and produce 745 g high-silicon residues for further reutilization, which indicates that our comprehensive utilization scheme is of great application potential.

Remediation of hexavalent chromium in contaminated soil using amorphous iron pyrite: Effect on leachability, bioaccessibility, phytotoxicity and long-term stability.

A large amounts of arable land is facing a high risk of hexavalent chromium (Cr(VI)) pollution, which requires remediation using a low toxic agent. In this study, the remediation effect of amorphous iron pyrite (FeS2(am)) on Cr(VI) in Cr(VI)-contaminated soil was evaluated by systematically analyzing the variation of the leachability, bioaccessibility, phytotoxicity, and long-term stability of the remediated soil. The effectiveness of FeS2(am) on the leachability was assessed by alkaline digestion and the toxicity characteristic leaching procedure (TCLP); the effect on the bioaccessibility was evaluated via the physiologically based extraction test (PBET) and the Tessier sequential extraction; the effect on the phytotoxicity was assessed via phytotoxicity bioassay (seed germination experiments) based on rape (Brassica napus L.) and cucumber (Cucumis Sativus L.), and the long-term stability of the Cr(VI)-remediated soil was appraised using column tests with groundwater and acid rain as the influents. The results show that FeS2(am), with a stoichiometry of 4× exhibited a high efficiency in the remediation of Cr(VI) and decreased its leachability and bioaccessibility during the 30-day remediation period. In addition, seed germination rate, accumulation and translocation of Cr, and root and shoot elongation of rape and cucumber of remediated soil are not significantly different from those of clean soil, illustrating that FeS2(am) is suitable for remediating Cr(VI) contaminated arable soil. The stabilization of Cr(VI) in contaminated soil using FeS2(am) was maintained for 1575 days. The long-term effectiveness was further confirmed by the increasing amount of free Fe and Mn in the effluent and the decreasing redox potential. In summary, FeS2(am) has an excellent efficiency for the remediation of Cr(VI), demonstrating it is a very promising alternative for use in the contaminated arable soil.

Distribution and transformation behaviors of heavy metals and phosphorus during hydrothermal carbonization of sewage sludge.

This study investigated the distribution and transformation behaviors of heavy metals (HMs) and phosphorus (P) during hydrothermal carbonization (HTC) of sewage sludge. In addition to a large reduction in sludge volume, HTC significantly decreased the exchangeable fraction of HMs (Zn, Cu, Cr, Ni, and Mn) and increased their residual fraction, which resulted in immobilization of HMs accumulated in hydrochar. The ecological toxicity of HMs was greatly reduced, and all HMs exhibited their lowest risk levels after HTC at 220 °C for 1 h in 2% H2SO4 solution. Most of the P (~ 97%) in the input sludge remained in the hydrochar after HTC. HTC facilitated transformation of organic P to inorganic P and promoted conversion of apatite P to non-apatite inorganic P under acidic conditions. The feasibility of recovering P from sludge by HTC was verified by an acid extraction experiment utilizing hydrochar, which recovered more than 90% P. Graphical abstract.

Characteristics and long-term effects of stabilized nanoscale ferrous sulfide immobilized hexavalent chromium in soil.

Based on the phenomenon of soil polluted by Hexavalent chromium (Cr(VI)), this study systematically examined the efficiency, stability and feasibility of using sodium carboxymethyl cellulose-stabilized nanoscale ferrous sulfide (CMC-nFeS) to immobilize Cr(VI) in contaminated soil. The experiments described herein showed CMC-nFeS exhibited superior dispersity and a higher antioxidative effect than nFeS alone. Batch tests indicated the nanoparticles could effectively immobilize Cr(VI) in soil. At Cr(VI) concentrations of 56.01-502.21 mg/kg, the reducing capacity of CMC-nFeS was 54.68-198.74 mg Cr(VI)/g FeS. Following treatment with CMC-nFeS, the leachabilities of Cr(VI) and Crtotal determined by the Toxicity Characteristic Leaching Procedure (TCLP), Synthetic Precipitation Leaching Procedure (SPLP) and Physiologically Based Extraction Test (PBET) decreased significantly after 24 h and remained stable for 90 days. Column tests with water and simulated acid rain showed the injection of CMC-nFeS significantly increased the fixed Cr concentration and the procedure was environmentally friendly. Furthermore, analysis of the reaction mechanism demonstrated the best removal obtained in a neutral environment and Cr(VI) was reduced and immobilized in the form of Cr(OH)3 and Fe0.75Cr0.25OOH confirmed by SEM-EDS and XPS analysis.

Reduction and immobilization of hexavalent chromium in chromite ore processing residue using amorphous FeS2.

In this work, a series of long-term treatment trials were conducted to evaluate the remediation performance of amorphous iron pyrite (FeS2(am)) toward hexavalent chromium (Cr(VI)) in chromite ore processing residue (COPR). The effectiveness of FeS2(am) was assessed using alkaline digestion, the synthetic precipitation leaching procedure (SPLP) and the physiologically based extraction test (PBET). Reaction mechanisms were explored by monitoring the changes in the solid pH, redox potential (Eh), the chemical states of relevant elements as well as the crystal forms present in COPR. The results showed that, using a proper dosage, the total content of Cr and Cr(VI) in the leachate from treated COPR met the Chinese standard regulatory limits for the extraction toxicity of hazardous wastes (GB 5085.3-2007). In addition, the in vitro bioaccessibility of Cr(VI) in COPR was also significantly reduced. Moreover, the remediation effect was maintained for the subsequent six months. This long-term effect was attributed to the presence of reductive sulfur (S) species and Fe(II) that remained even after 180 days of treatment, which were identified using high-resolution X-ray photoelectron spectroscopy (HR-XPS) and X-ray diffraction (XRD). To maximize the effect of FeS2(am), 5% lime was employed as an additive to adjust the pH and thus contributed to Cr(VI) reduction and immobilization. To remediate COPR within 30 days, the use of 5% lime and a specific FeS2(am) dosage (FeS2(am):Cr(VI) = 1.25:1) is recommended based on the results. For rapid remediation (< 1 day), the use of 5% lime and a 2.5:1 FeS2(am):Cr(VI) ratio is recommended. In comparison with widely studied reductants, FeS2(am) showed excellent efficiency for the remediation of COPR over both short- and long-term treatment trials, demonstrating it is a very promising alternative treatment method.

Remediation of hexavalent chromium contamination in chromite ore processing residue by sodium dithionite and sodium phosphate addition and its mechanism.

Large amounts of chromite ore processing residue (COPR) wastes have been deposited in many countries worldwide, generating significant contamination issues from the highly mobile and toxic hexavalent chromium species (Cr(VI)). In this study, sodium dithionite (Na2S2O4) was used to reduce Cr(VI) to Cr(III) in COPR containing high available Fe, and then sodium phosphate (Na3PO4) was utilized to further immobilize Cr(III), via a two-step procedure (TSP). Remediation and immobilization processes and mechanisms were systematically investigated using batch experiments, sequential extraction studies, X-ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS). Results showed that Na2S2O4 effectively reduced Cr(VI) to Cr(III), catalyzed by Fe(III). The subsequent addition of Na3PO4 further immobilized Cr(III) by the formation of crystalline CrPO4·6H2O. However, addition of Na3PO4 simultaneously with Na2S2O4 (via a one-step procedure, OSP) impeded Cr(VI) reduction due to the competitive reaction of Na3PO4 and Na2S2O4 with Fe(III). Thus, the remediation efficiency of the TSP was much higher than the corresponding OSP. Using an optimal dosage in the two-step procedure (Na2S2O4 at a dosage of 12× the stoichiometric requirement for 15 days, and then Na3PO4 in a molar ratio (i.e. Na3PO4: initial Cr(VI)) of 4:1 for another 15 days), the total dissolved Cr in the leachate determined via Toxicity Characteristic Leaching Procedure (TCLP Cr) testing of our samples was reduced to 3.8 mg/L (from an initial TCLP Cr of 112.2 mg/L, i.e. at >96% efficiency).

Extraction of rare earth elements from a contaminated cropland soil using nitric acid, citric acid, and EDTA.

Rare earth elements (REEs) contamination to the surrounding soil has increased the concerns of health risk to the local residents. Soil washing was first attempted in our study to remediate REEs-contaminated cropland soil using nitric acid, citric acid, and ethylene diamine tetraacetic acid (EDTA) for soil decontamination and possible recovery of REEs. The extraction time, washing agent concentration, and pH value of the washing solution were optimized. The sequential extraction analysis proposed by Tessier was adopted to study the speciation changes of the REEs before and after soil washing. The extract containing citric acid was dried to obtain solid for the X-ray fluorescence (XRF) analysis. The results revealed that the optimal extraction time was 72 h, and the REEs extraction efficiency increased as the agent concentration increased from 0.01 to 0.1 mol/L. EDTA was efficient to extract REEs over a wide range of pH values, while citric acid was around pH 6.0. Under optimized conditions, the average extraction efficiencies of the major REEs in the contaminated soil were 70.96%, 64.38%, and 62.12% by EDTA, nitric acid, and citric acid, respectively. The sequential extraction analyses revealed that most soil-bounded REEs were mobilized or extracted except for those in the residual fraction. Under a comprehensive consideration of the extraction efficiency and the environmental impact, citric acid was recommended as the most suitable agent for extraction of the REEs from the contaminated cropland soils. The XRF analysis revealed that Mn, Al, Si, Pb, Fe, and REEs were the major elements in the extract indicating a possibile recovery of the REEs.

Kinetics and mechanisms of amorphous FeS2 induced Cr(VI) reduction.

A novel reductant, amorphous FeS2 (FeS2(am)) was synthesized to remove hexavalent chromium (Cr(VI)). The stoichiometry, kinetics and mechanisms of FeS2(am) induced Cr(VI) reduction were studied under anaerobic conditions with a pH range of 5.0-13.0. Results showed that FeS2(am) was efficient in removing aqueous Cr(VI) with a stoichiometry of Cr(VI): FeS2(am) ∼1: 0.9. Moreover, the reduction kinetics decreased with the growth of pH within the pH range from 5.0 to 10.0, but increased within pH 10.0-13.0. The dissolution kinetics of FeS2(am) was found to be mainly responsible for the varied Cr(VI) reduction kinetics, and the mechanisms involved in the reduction process were further confirmed by X-ray photoelectron spectroscopy analysis. In addition, O2 was found to compete with Cr(VI) in the reduction process and subsequently impede the Cr(VI) reduction rate.

A novel method for harmless disposal and resource reutilization of steel wire rope sludges.

Rapid development of steel wire rope industry has led to the generation of large quantities of pickling sludge, which causes significant ecological problems and considerable negative environmental effects. In this study, a novel method was proposed for harmless disposal and resource reutilization of the steel wire rope sludge. Based on the method, two steel wire rope sludges (the Pb sludge and the Zn sludge) were firstly extracted by hydrochloric or sulfuric acid and then mixed with the hydrochloride acid extracting solution of aluminum skimmings to produce composite polyaluminum ferric flocculants. The optimum conditions (acid concentration, w/v ratio, reaction time, and reaction temperature) for acid extraction of the sludges were studied. Results showed that 97.03 % of Pb sludge and 96.20 % of Zn sludge were extracted. Leaching potential of the residues after acid extraction was evaluated, and a proposed treatment for the residues had been instructed. The obtained flocculant products were used to purify the real domestic wastewater and showed an equivalent or better performance than the commercial ones. This method is environmental-friendly and cost-effective when compared with the conventional sludge treatments.

Degradation of cis- and trans-(4-methylcyclohexyl) methanol in activated sludge.

Crude (4-methylcyclohexyl)methanol (MCHM) caused extensive contamination of drinking water, wastewater, and the environment during the 2014 West Virginia Chemical Spill. However, information related to the environmental degradation of cis- and trans-4-MCHM, the main components of the crude 4-MCHM mixture, remains largely unknown. This study is among the first to investigate the degradation kinetics and transformation of 4-MCHM isomers in activated sludge. The 4-MCHM loss was mainly due to biodegradation to form carbon dioxide (CO2), plus acetic, propionic, isobutyric, and isovaleric acids with little contribution from adsorption. The biodegradation of 4-MCHM isomers followed the first-order kinetic model with half-lives higher than 0.50 days. Nitrate augmented the degradation of 4-MCHM isomers, while glucose and acetate decreased their degradation. One 4-MCHM-degrading bacterium isolated from activated sludge was identified as Acinetobacter bouvetii strain EU40 based on 16S rRNA gene sequences. This study will enhance the prediction of the environmental fate of 4-MCHM in water treatment systems.

Aerobic and anaerobic microbial degradation of crude (4-methylcyclohexyl)methanol in river sediments.

Cyclohexane and some of its derivatives have been a major concern because of their significant adverse human health effects and widespread occurrence in the environment. The 2014 West Virginia chemical spill has raised public attention to (4-methylcyclohexyl)methanol (4-MCHM), one cyclohexane derivative, which is widely used in coal processing but largely ignored. In particular, the environmental fate of its primary components, cis- and trans-4-MCHM, remains largely unexplored. This study aimed to investigate the degradation kinetics and mineralization of cis- and trans-4-MCHM by sediment microorganisms under aerobic and anaerobic conditions. We found the removal of cis- and trans-4-MCHM was mainly attributed to biodegradation with little contribution from sorption. A nearly complete aerobic degradation of 4-MCHM occurred within 14 days, whereas the anaerobic degradation was reluctant with residual percentages of 62.6% of cis-4-MCHM and 85.0% of trans-4-MCHM after 16-day incubation. The cis-4-MCHM was degraded faster than the trans under both aerobic and anaerobic conditions, indicating an isomer-specific degradation could occur during the 4-MCHM degradation. Nitrate addition enhanced 4-MCHM mineralization by about 50% under both aerobic and anaerobic conditions. Both cis- and trans-4-MCHM fit well with the first-order kinetic model with respective degradation rates of 0.46-0.52 and 0.19-0.31 day(-)(1) under aerobic condition. Respective degradation rates of 0.041-0.095 and 0.013-0.052 day(-)(1) occurred under anaerobic condition. One bacterial strain capable of effectively degrading 4-MCHM isomers was isolated from river sediments and identified as Bacillus pumilus at the species level based on 16S rRNA gene sequence and 97% identity. Our findings will provide critical information for improving the prediction of the environmental fate of 4-MCHM and other cyclohexane derivatives with similar structure as well as enhancing the development of feasible treatment technologies to mitigate these compounds.

Lead toxicity to the performance, viability, and community composition of activated sludge microorganisms.

Lead (Pb) is a prominent toxic metal in natural and engineered systems. Current knowledge on Pb toxicity to the activated sludge has been limited to short-term (≤24 h) toxicity. The effect of extended Pb exposure on process performance, bacterial viability, and community compositions remains unknown. We quantified the 24-h and 7-day Pb toxicity to chemical oxygen demand (COD) and NH3­N removal, bacterial viability, and community compositions using lab-scale experiments. Our results showed that 7-day toxicity was significantly higher than the short-term 24-h toxicity. Ammonia-oxidizing bacteria were more susceptible than the heterotrophs to Pb toxicity. The specific oxygen uptake rate responded quickly to Pb addition and could serve as a rapid indicator for detecting Pb pollutions. Microbial viability decreased linearly with the amount of added Pb at extended exposure. The bacterial community diversity was markedly reduced with elevated Pb concentrations. Surface analysis suggested that the adsorbed form of Pb could have contributed to its toxicity along with the dissolved form. Our study provides for the first time a systematic investigation of the effect of extended exposure of Pb on the performance and microbiology of aerobic treatment processes, and it indicates that long-term Pb toxicity has been underappreciated by previous studies.