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Drying-rewetting (DW) cycles can significantly influence soil properties and microbial community composition, leading to direct or indirect changes in arsenic (As) toxicity, which inturn affects soil ecological functions. Despite this, there has been insufficient focus on accurately evaluating As ecotoxicity and its impact on soil ecological function under DW conditions. This study seeks to address this gap by examining the effects of DW on As toxicity and the characteristics of soil ecological function, specifically from the perspective of enzyme-based functional diversity. Our results reveal that compared to constant moisture conditions, DW treatment significantly increased the toxicity of As on alkaline phosphatase and β-glucosidase, with maximum inhibition rates observed at 46.29% and 21.54%, respectively. Conversely, for other tested enzymes including invertase, fluorescein diacetate hydrolase, and dehydrogenase, DW treatment decreased As toxicity, possibly be due to the different stability of these enzymes under varying soil moisture conditions. From an enzyme functional diversity perspective, DW treatment reduced the As toxicity, as evidenced by the reduced inhibition rates and a lower coefficient of variation. In conclusion, DW appears to enhance soil functional resilience against arsenic pollution. These findings contribute to a better understanding of changes in ecological functions in heavy metal-contaminated soils under dynamic environmental conditions, offering insights for improved monitoring and mitigation strategies for metalloids toxicity in natural environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

This work assessed the adsorption performance of three common PFAS compounds (PFOA, PFOS and PFHxS) on two water treatment sludges (WTS) and two biochars (commercial biomass biochar and semi-pilot scale biosolids biochar). Of the two WTS samples included in this study, one was sourced from poly-aluminium chloride (PAC) and the other from alum (Al 2 (SO 4 ) 3 ). The results of experiments using a single PFAS for adsorption reinforced established trends in affinity - the shorter-chained PFHxS was less adsorbed than PFOS, and the sulphates (PFOS) were more readily adsorbed than the acid (PFOA). Interestingly, PAC WTS, showed an excellent adsorption affinity for the shorter chained PFHxS (58.8%), than the alum WTS and biosolids biochar at 22.6% and 41.74%, respectively. The results also showed that the alum WTS was less effective at adsorption than the PAC WTS despite having a larger surface area. Taken together, the results suggest that the hydrophobicity of the sorbent and the chemistry of the coagulant were critical factors for understanding PFAS adsorption on WTS, while other factors, such as the concentration of aluminium and iron in the WTS could not explain the trends seen. For the biochar samples, the surface area and hydrophobicity are believed to be the main drivers in the different performances. Adsorption from the solution containing multiple PFAS was also investigated with PAC WTS and biosolids biochar, demonstrating comparable performance on overall adsorption. However, the PAC WTS performed better with the short-chain PFHxS than the biosolids biochar. While both PAC WTS and biosolids biochar are promising candidates for adsorption, the study highlights the need to explore further the mechanisms behind PFAS adsorption, which could be a highly variable source to understand better the potential for WTS to be utilized as a PFAS adsorbent., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Long-term input of agricultural chemicals such as pesticides into the soil can increase soil pollution, thereby affecting the productivity and quality of black soil. Triazine herbicide atrazine has been shown to have long-lasting residual effects in black soil. The atrazine residues affected soil biochemical properties, further leading to microbial metabolism restriction. It is necessary to explore the strategies to mitigate the limitations on microbial metabolism in atrazine-contaminated soils. Here, we evaluated the effect of the atrazine on microbial nutrient acquisition strategies as indicated by extracellular enzyme stoichiometry (EES) in four black soils. Atrazine degradation in soil followed the first-order kinetics model across various concentrations ranging from 10 to 100 mg kg -1 . We found that the atrazine was negatively correlated with the EES for C-, N-, and P-acquisition. Vector lengths and angles decreased and increased significantly with an increase of atrazine concentration in tested black soils except for Lishu soils. Moreover, the vector angles were >45° for tested four black soils, indicating that atrazine residue had the greatest P-limitation on soil microorganisms. Interestingly, microbial C- and P-limitations with different atrazine concentrations showed a strong linear relationship, especially in Qiqihar and Nongan soils. Atrazine treatment significantly negatively affected microbial metabolic limitation. Soil properties and EES interaction explained up to 88.2% for microbial C-/P-limitation. In conclusion, this study confirms the EES as a useful method in evaluating the effects of pesticides on microbial metabolic limitations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Per- and polyfluoroalkyl substances (PFAS) are chemically and thermally stable due to the presence of carbon-fluorine (C-F) bond in their molecular structures, hence have been previously formulated as firefighting ingredients. During the firefighting process, however, owing to the high temperature, PFAS can be potentially degraded, particularly for PFAS precursors that contain non-C-F bonds, which is studied herein by exposing PFAS-contaminated soil in a muffle furnace oven. Different temperatures and time intervals are applied to the real soil sample to mimic the firing process and to evaluate the degradation and conversion of PFAS. This thermal treatment can not only degrade precursors (e.g. 6:2 fluorotelomer sulphonate), but also degrade perfluoroalkyl carboxylates (PFCA, e.g. perfluorooctanoic acid PFOA) and perfluoroalkyl sulfonates (PFSA, e.g. perfluorooctane sulfonate PFOS). The concentration dependence of the PFAS on temperature and time is fitted using a 2D Gaussian surface to simulate the complex thermal kinetic, and to compare with the traditional approach such as thermogravimetric analysis (TGA) (1D dependence on temperature only). The 2D simulation can directly visualise the thermal kinetic of individual or sum PFAS in the complex temperature-time plane, which depends on the sample background and particularly on the coexist PFAS precursors. Overall, this study provides a simple approach to monitor and optimise the thermal treatment of the PFAS-contaminated soil., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The application of parathion (PTH) in agriculture can result in its entry into the soil and threaten the soil environment. Monitoring the PTH residues and assessing toxicity on soil health are of paramount importance to the public. Herein, the dissipation of PTH and concomitant influence on microbial activities [FDA hydrolase (FDA‒H), microbial biomass carbon (MBC) and basal respiration (BR)] in coastal solonchaks were investigated. Results showed that the dissipation of PTH in tested soil declined linearly, and the half-lives varied from 5.6 to 56.8 days, depending on pollutant concentrations. The FDA‒H activity and MBC were negatively affected by PTH pollution and exhibited a significantly positive correlation. Two‒way ANOVA analysis demonstrated that microbial activities were affected not only by PTH dose and incubation time but also by their interactions. The integrated biomarker response (IBR/n) index values on day 120 were between 1.02 and 2.89, larger than those on day 1 during PTH dissipation. This implied that the soil quality did not recover though there was no PTH residue in the soil at the end of the experiment. These findings suggested that microbial activities integrated with IBR/n index could elucidate the hazardous impacts of PTH dissipation on biochemical cycling and microorganisms in soil., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Perfluorooctane sulfonate (PFOS) is a well-known global persistent organic pollutant of grave concern to ecological and human health. Toxicity of PFOS to animals and humans are well studied. Although few studies have reported the behavioral effect of PFOS on nematode Caenorhabditis elegans, it's transgenerational effects were seldom studied. Therefore, we investigated the toxicity of PFOS on several behavioral responses besides bioaccumulation and transgenerational effects in C. elegans. In contrast to the several published studies, we used lower concentrations (0.5-1000 μg/L or 0.001-2.0 μM) that are environmentally relevant and reported to occur close to the contaminated areas. The 48 h median lethal concentration of PFOS was found to be 3.15 μM (1575 μg/L). PFOS (≥0.01 μM) caused severe toxicity to locomotion, and this effect was even transferred to progeny. However, after a few generations, the defect was rectified in the progeny of single-time exposed parent nematodes. Whereas, continuous exposure at 0.001 μM PFOS, no visible defects were observed in the progeny. PFOS (≥0.01 μM) also significantly decreased the brood size in a concentration-dependent manner. Besides, lifespan was affected by the higher concentration of PFOS (≥1.0 μM). These two behavioral endpoints, lifespan and reproduction defects, became less severe in the progeny. Chemotaxis plasticity was also significantly retarded by ≥ 1.0 μM PFOS compared to the control group. Results indicate that PFOS can exert severe neurobehavioral defects that can be transferred from parents to their offspring. The findings of this study have significant implications for the risk assessment of perfluorinated substances in the environment., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Microplastics are among the ubiquitous contaminants in our environment. As emerging contaminants, microplastics are still facing with lots of challenges on the characterisation, including their capture, identification and visualisation, particularly from a complex background. For example, when we print documents using a laser printer, we are printing microplastics onto paper, because the plastics are the main ingredient of the toner powder mixture. Characterisation of these microplastic mixture meets an even more complicated challenge, because plastic's signals might be shielded by other toner powder ingredients such as the pigments, the dyes, the black carbon, and the paper fabrics as well. To solve this challenge, we employ various techniques, including SEM, TEM, XPS, FT-IR, TGA and Raman, to characterise the microplastics printed via the toner powders. Interestingly, we show that Raman can distinguish and visualise the distribution of the microplastics from the complex background of the mixture. We estimate the millions of toner powders, each of which is ~4-6 μm in size, are printed out per A4 sheet as microplastics. The findings send a strong warning that millions of microplastics might be generated from the printing activities in our daily lives., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Nitrogen amendment is known to effectively enhance the bioremediation of hydrocarbon-contaminated soil, but the nitrogen metabolism in this process is not well understood. To unravel the nitrogen metabolic pathway(s) of diesel contaminated soil, six types of nitrogen sources were added to the diesel contaminated soil. Changes in microbial community and soil enzyme genes were investigated by metagenomics analysis and chemical analysis through a 30-day incubation study. The results showed that ammonium based nitrogen sources significantly accelerated the degradation of total petroleum hydrocarbon (TPH) (79-81%) compared to the control treatment (38%) and other non-ammonium based nitrogen amendments (43-57%). Different types of nitrogen sources could dramatically change the microbial community structure and soil enzyme gene abundance. Proteobacteria and Actinobacteria were identified as the two dominant phyla in the remediation of diesel contaminated soil. Metagenomics analysis revealed that the preferred metabolic pathway of nitrogen was from ammonium to glutamate via glutamine, and the enzymes governing this transformation were glutamine synthetase and glutamate synthetase; while in nitrate based amendment, the conversion from nitrite to ammonium was restrained by the low abundance of nitrite reductase enzyme and therefore retarded the TPH degradation rate. It is concluded that during the process of nitrogen enhanced bioremediation, the most efficient nitrogen cycling direction was from ammonium to glutamine, then to glutamate, and finally joined with carbon metabolism after transforming to 2-oxoglutarate., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Fenamiphos is a neurotoxic organophosphorus pesticide used widely to control pests of crops. Fenamiphos and its toxic oxidation products have been detected in surface and groundwaters. A novel enzyme capable of hydrolysing P-O-C bond of fenamiphos is purified from Microbacterium esteraromaticum MM1 total cellular protein using a combination of methods. The purified fenamiphos hydrolysing enzyme (FHE) was identified as enolase (phosphopyruvate hydratase), a housekeeping enzyme with molecular mass and pI value of 45 kDa and 4.5, respectively. The optimum pH and temperature for the activity of the FHE are 7 and 25 °C, respectively. We studied the influence of metal ions and inhibitors on the enzyme activity. The enzyme was strongly activated by Mg 2+ whereas Hg 2+ and phenylmethyl sulfonyl fluoride (PMSF) inhibited the enzyme. The kinetic parameters, K m and V max for fenamiphos hydrolysis were estimated to be 584.15 ± 16.22 μM and 6.46 ± 0.13 μM min -1 , respectively. The FHE was functionally active against its original substrate (2-phosphoglycerate) with K m value of 5.82 ± 1.42 μM and V max of 4.2 ± 0.1 μM min -1 . This enzyme has great potential for its application in the detoxification of fenamiphos and its warfare homologs. To our knowledge, this is the first report on the purification of fenamiphos hydrolysing enzyme., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Soil as a heterogeneous mass is composed of different size aggregates. The distribution of different arsenic (As) fractions in soil aggregates is vital to assess the potential risk of As pollution. In this study, soil samples were aged for 4 months with different arsenate [As(V)] concentrations. Dry sieving method was used to obtain five different size aggregates and the content of As in these fractions was determined. The results showed that P4 (0.1-0.25 mm) contained the highest organic matter (OM) than other size aggregates. After 4 months of ageing, available phosphorus (AP) content increased with the increase of As(V) concentration among 5 aggregates. The distribution of different arsenic fractions among 5 aggregates was similar. The relative contents of water-soluble (F1), exchangeable (F2) and carbonate (F3) fractions increased with the increase in As concentration, while the residual fraction (F7) decreased sharply. Humic-bound (F4), and Fe and Mn oxide bound fractions (F5) were about 35% and 20% respectively, after 4 months of As(V) ageing. Generally, the alkaline phosphatase (ALP) activities of P4 were lowest among five aggregates under each concentration of As(V). Moreover, F2 and F3 exhibited a strong inhibition of ALP activity. This study demonstrates that not only water-soluble and exchangeable arsenic but also humic-bound fraction should be considered when assessing As bioavailability and toxicity., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Endpoint assessment using biological systems in combination with the chemical analysis is important for evaluating the residual effect of contaminants following remediation. In this study, the level of residual toxicity of polycyclic aromatic hydrocarbons (PAHs) after 120 days of phytoremediation with five different plant species:- maize (Zea mays), Sudan grass (Sorghum sudanense), vetiver (Vetiveria zizanioides), sunflower (Helianthus annuus) and wallaby grass (Austrodanthonia sp.) has been evaluated by ecotoxicological tests such as root nodulation and leghaemoglobin assay using garden pea (Pisum sativum) and acute, chronic and genotoxicity assays using earthworm (Eisenia fetida). The phytoremediated soil exhibited lesser toxicity supporting improved root nodulation and leghaemoglobin content in P. sativum and reducing DNA damage in E. fetida when compared to contaminated soil before remediation. Also, the results of the ecotoxicological assays with the legume and earthworm performed in this study complemented the results obtained by the chemical analysis of PAHs in phytoremediated soil. Therefore, these findings provide a basis for a framework in which remediation efficacy of PAHs-contaminated sites can be evaluated effectively with simple ecotoxicological bioassays using legumes and earthworms., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The functional stability of soil enzymes is fundamental to the sustainability of soil biochemical processes and is affected by many environmental stressors. This study focused on the influences of long-term arsenic (As) contamination on soil enzyme functional stability: the resistance (ratio of the disturbed to control) and resilience (integrated recovery rate) of soil enzyme activities (β-glucosidase, urease, acid phosphatase, fluorescein diacetate (FDA) hydrolase) over 30 days incubation after an experimental heat disturbance (50 o C for 18 h). Results showed that the resistance of soil enzymes to heat disturbance differed among the enzyme types and followed the order: urease > β-glucosidase > acid phosphatase > FDA hydrolase. Urease activity was generally not affected and showed high stability against heat disturbance. The β-glucosidase activity recovered to the control level by 30 days, while 80% and 90% recovery on average occurred for acid phosphatase and FDA hydrolase, respectively. Long-term As contamination altered soil enzyme functional resistance and resilience to heat disturbance and resulted in three kinds of responses: (i) no apparent alteration (urease); (ii) moderate As contamination increased enzyme heat resistance (β-glucosidase); (iii) the resistance and resilience decreased with increasing As concentration (acid phosphatase and FDA hydrolase). The results demonstrated that different enzyme-catalytic biochemical processes have different functional stabilities under combined As and heat disturbance, and the negative changes in the soil enzyme activity led to losses in soil functions. Our study provides further evidence on the impacts of heavy metal/metalloid on soil enzyme functional stability in response to additional disturbance., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In this present study, the biocorrosion behaviour of Bacillus thuringiensis EN2 and B. oleronius EN9 on copper metal CW024A (Cu) in cooling water system (1% chloride) were evaluated using weight loss, electrochemical impedance spectroscopy (EIS) and surface analysis. In presence of EN2 and EN9, the corrosion rates (CR) were higher, about 0.021 mm/y and 0.032 mm/y than control system (0.004 mm/y). On the other hand, the presence of corrosion inhibitor 2-mercaptopyridine (2-MCP) with bacteria (EN2 and EN9), the biofilm on metal surface was highly inhibited and thus reduces the corrosion rate (CR: 0.004 mm/y). The electrochemical behaviour of CW024A metal was correlated with the adsorbed corrosion inhibitor film and biofilm. Atomic force microscopy (AFM) analysis revealed that the presence of EN2 and EN9 more pits was observed on the metal surface rather than 2-MCP system. EIS confirms the inhibitor act as cathodic type of inhibitor and thus leads to the inhibition of CR. Overall, this work concluded that corrosion inhibitor (2-MCP) inhibits, the bacterial biofilm formation on the metal surface due to the formation of productive layer on metal surface as coordination of NH bond. Which leads to the reduction of bacterial attachment and thus higher corrosion inhibition efficiency (75%) obtained. This is the first work disclosing the role of 2-MCP formulations as potent anti-bacterial and corrosion inhibition efficiency on copper metal in cooling water tower environment., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The biodegradation potential of three bacterial cultures isolated from the rhizosphere of maize (Zea mays) and Sudan grass (Sorghum sudanense) grown in PAHs contaminated soils to degrade benzo[a]pyrene (BaP) and pyrene (PYR) was assessed. Of the three bacterial cultures isolated, two belonged to Gram-positive bacteria of phylum Actinobacteria namely Arthrobacter sp. MAL3 and Microbacterium sp. MAL2. The Gram-negative bacterial culture was Stenotrophomonas sp. MAL1, from the phylum Proteobacteria. The cultures were grown in the presence of BaP and PYR as sole carbon sources and with the addition of low molecular weight organic acids (LMWOAs) mixture. After 10-14 days of exposure, all the bacterial isolates exhibited a complete degradation of PYR with the addition of LMWOAs mixture, whereas only 38.7% of BaP was degraded by Stenotrophomonas sp. MAL1 with the addition of LMWOAs mixture. In addition, enhanced PAHs biodegradation by bacterial culture was observed when the PAHs present as mixture (BaP + PYR) with the addition of LMWOAs. Dioxygenase genes were detected in Stenotrophomonas sp. MAL1 (phnAC), and Arthrobacter sp. MAL3 (nidA and PAH-RHDα). Therefore, this study provides new insights on the influence of LMWOAs in enhancing the degradation of high molecular weight (HMW) PAHs in soil by rhizosphere bacterial cultures., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Polycyclic aromatic hydrocarbons are an important group of persistent organic pollutants. Using plants to remediate PAHs has been recognized as a cost-effective and environmentally friendly technique. However, the overall impact of PAHs on the regulation of plant metabolism has not yet been explored. In this study, we analyzed the alteration in the maize (Zea mays L.) metabolome on exposure to high molecular weight PAHs such as benzo[a]pyrene (BaP) and pyrene (PYR) in a hydroponic medium, individually and as a mixture (BaP + PYR) using GC-MS. The differences in the metabolites were analyzed using XCMS (an acronym for various forms (X) of chromatography-mass spectrometry), an online-based data analysis tool. A significant variation in metabolites was observed between treatment groups and the unspiked control group. The univariate, multivariate and pathway impact analysis showed there were more significant alterations in metabolic profiles between individual PAHs and the mixture of BaP and PYR. The marked changes in the metabolites of galactose metabolism and aminoacyl tRNA biosynthesis in PAHs treated maize leaves exhibit the adaptive defensive mechanisms for individual and PAHs mixture. Therefore, the metabolomics approach is essential for an understanding of the complex biochemical responses of plants to PAHs contaminants. This knowledge will shed new light in the field of phytoremediation, bio-monitoring, and environmental risk assessment., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Soil contamination with total petroleum hydrocarbons (TPH) is widespread throughout the globe due to the massive production of TPH anthropogenically and its occurrence in the soil. TPH is toxic to beneficial soil organisms and humans and thus has become a serious concern among the public. Traditionally TPH toxicity in the soil is estimated based on chemical fractions and a range of bioassays including plants, invertebrates and microorganisms. There is a large inconsistency among ecotoxicology data using these assays due to the nature of TPH and their weathering. Therefore, in this article, we critically reviewed the weathered conditions of TPH, the potential fate in soil and the bioindicators for the assessment of the ecotoxicity. Based on the current research and the state-of-the-art problem, we also highlighted key recommendations for future research scope for the real-world solution of the ecotoxicological studies of hydrocarbons., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The increasing production of graphene raised concerns about their releasing into sewage sludge, however, there is little information about graphene impacting on the growth of bacteria and hence their bioleaching of metal ions from sewages sludge. In this study, we reported that Acidithiobacillus sp., isolated from sewages, were used to bioleach Cu 2+ and Zn 2+ from sewages sludge in the presence of graphene. The negative effect on the growth of Acidithiobacillus sp. and dose-dependent were observed in presence of graphene, where the optical density (OD 420 ) of the culture decreased from 0.163 to 0.045, while the bioleaching efficiency of Cu 2+ (70%-16%) and Zn 2+ (80%-48%) were also reduced when the graphene dose decreased from 50 mg L -1 to 1 mg L -1 . Furthermore, scanning electron microscopy (SEM) and atomic force microscopy (AFM) confirmed that the direct contacts between graphene and cell at 1 mg L -1 graphene caused cell membrane disruption, while Acidithiobacillus sp. grew better by forming dense biofilms around the suspended graphene at a 50 mg L -1 . LIVE/DEAD staining further demonstrated that almost no live cells were detected at 1 mg L -1 graphene. The toxicity of graphene could generally be explained by depending on the concentration of graphene. The new findings provide an insight into dose dependence, which impacted on the growth of Acidithiobacillus sp. and their bioleaching of metal ion from sludge., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The phytoremediation potential of 14 different plant species belonging to C3 and C4 carbon fixation pathway for soils spiked with polycyclic aromatic hydrocarbons (PAHs) such as benzo[a]pyrene (B[a]P) and pyrene (PYR) was investigated. A glasshouse experiment was conducted to measure the changes in morphological, physiological, biochemical parameters and the bioaccumulation and biodegradation ability of the plants in soils spiked with 48 and 194 mg kg -1 of B[a]P and PYR, respectively. The per cent removal efficacy of B[a]P and PYR by the tested plant species over a period of 50 days was from 6 to 26% and 14 to 40% respectively. The maximum removal of both B[a]P and PYR was observed in Sudan grass (C4), vetiver (C4), maize (C4), and sunflower (C3). In terms of accumulation in root and shoot, the concentration of PYR was higher in both C3 and C4 plant species when compared to B[a]P. Overall the results indicated that C4 plants were more efficient than their C3 counterparts in terms of morphological, physiological, biochemical and degradation ability of PAHs., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Improving the anode configuration to enhance biocompatibility and accelerate electron shuttling is critical for efficient energy recovery in microbial fuel cells (MFCs). In this paper, green reduced graphene nanocomposite was successfully coated using layer-by-layer assembly technique onto carbon brush anode. The modified anode achieved a 3.2-fold higher power density of 33.7 W m -3 at a current density of 69.4 A m -3 with a 75% shorter start period. As revealed in the characterization, the green synthesized nanocomposite film affords larger surface roughness for microbial colonization. Besides, gold nanoparticles, which anchored on graphene sheets, promise the relatively high electroactive sites and facilitate electron transfer from electricigens to the anode. The reduction-oxidation peaks in cyclic voltammograms indicated the mechanism of surface cytochromes facilitated current generation while the electrochemical impedance spectroscopy confirmed the enhanced electron transfer from surface cytochrome to electrode. The green synthesis process has the potential to generate a high performing anode in further applications of MFCs., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

We developed a smartphone app-based monitoring tool for the detection of anionic surfactants (AS), including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). Akin to the methylene blue active substances (MBAS), liquid-phase extraction (LPE) is employed to extract the hydrophobic ion-pair of dye (ethyl violet)-AS to an organic phase (ethyl acetate). The colour (RGB) of the organic phase is read using a smartphone camera with the help of a reading kit. The value of RGB is carefully corrected and linked to the concentration of ASs with a standard deviation of <10% in the 10-1000 ppb (part per billion) range. In order to avoid the interference arising from inorganic anions (such as those found in tap water and groundwater), the water sample is pre-treated either by solid-phase extraction (SPE), which takes ∼30 min, or by dual liquid-phase extraction (dual-LPE, developed by us), which takes ∼5 min. In the latter case, the organic phase of the first LPE (equilibrium with water sample) is transferred and subjected to a second LPE (equilibrium with Milli-Q water) to remove any potential background interference. In the meantime, SPE can also pre-concentrate ASs at 100-1000 times (in volume) to benefit the sensitivity. Consequently, our smartphone app can detect PFOA spiked in tap/groundwater with an LOD of 10 ppb (∼12 nM, dual-LPE of ∼5 min), or 0.5 ppb (∼1.2 nM, SPE of ∼3 h), suggesting that it has the potential to succeed as a pre-screening tool for on-site application and in common laboratory tests., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Sorption and desorption are critical processes to control the mobility and biotoxicity of cadmium (Cd) in soils. It is known that attendant anion species of heavy metals could affect metal adsorption on soils and might further alter their biotoxicity. However, for Cd, the influence of attendant anions on its sorption in soils and subsequent toxicity on soil enzymes are still unknown. In this work, four Cd compounds with different salt anions (SO 4 2- , NO 3 - , Cl - , and Ac - ) were selected to investigate their impact of on the sorption, soil dehydrogenase activity (DHA) and alkaline phosphatase activity (ALP). Thus, a series of simulated Cd pollution batch experiments including measuring adsorption-desorption behavior of Cd on soils and soil enzyme activities were carried out. Results showed that CdSO 4 exhibited highest sorption capacity among the tested soils except in Hunan soil. The Cd sorption with NO 3 - displayed a similar behavior with Cl - on all tested soils. Compared with soil properties, all four kinds of anions on Cd sorption played a more significant role affecting Cd ecological toxicity to soil DHA and ALP. Cd in acetate or nitrate form appears more sensitive towards DHA than sulphate and chloride, while the later pair is more toxic towards ALP than the former. These results have important implications for evaluation of Cd contamination using soil enzyme as bioindicator., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Arsenic (As) and zinc (Zn) are common co-contaminants in mining impacted soils. Their interaction on solubility and toxicity when present concurrently is not well understood in natural systems. The aim of this study was to observe their interaction in solubility (soil-solution), bioaccumulation (shoot uptake) and toxicity to cucumber (Cucumis sativa L) conducting 4 weeks pot study in 5 different soils spiked with As (0, 2, 4, 8 to 1024 mg kg -1 ) individually and with Zn at two phytotoxic doses. The As pore-water concentration was significantly reduced (df = 289, Adjusted R 2  = 0.84, p < 0.01) in the presence of Zn in the whole dataset, whereas Zn and Zn 2+ activity in pore-water was reduced significantly only in the two alkaline soils. This outcome may be due to adsorption/surface precipitation or tertiary bridging complexation. No homogenous precipitation of zinc arsenate could be established using electron microscopy, XRD or even equilibrium calculations. For bioaccumulation phase, no significant effect of Zn on As uptake was observed except acidic MG soil whereas, Zn uptake was significantly reduced (p < 0.05) by As in whole dataset. However, an additive response was observed mostly except acidic MG soil. The synergistic response (more than additive) was predominant in this soil for a wide range of inhibition concentration (0-80%) at both Zn EC10 and EC50 levels. Since additive response is mostly considered in risk assessment for mixtures, precautions should be implemented for assessment of toxicity for As-Zn mixture in acidic soil due to their synergistic response in some soils., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Sites contaminated with chemical pollutants represent a growing challenge, and remediation of such lands is of international concern. Risk-based land management (RBLM) is an emerging approach that integrates risk assessment practices with more traditional site-specific investigations and remediation activities. Developing countries are yet to adopt RBLM strategies for remediation. RBLM is considered to be practical, scientifically defensible and cost-efficient. However, it is inherently limited by: firstly, the accuracy of risk assessment models used; secondly, ramifications of the fact that they are more likely to leave contamination in place; and thirdly, uncertainties involved and having to consider the total concentrations of all contaminants in soils that overestimate the potential risks from exposure to the contaminants. Consideration of contaminant bioavailability as the underlying basis for risk assessment and setting remediation goals of those contaminated lands that pose a risk to environmental and human health may lead to the development of a more sophisticated risk-based approach. However, employing the bioavailability concept in RBLM has not been extensively studied and/or legalized. This review highlights the extent of global land contamination, and the concept of risk-based assessment and management of contaminated sites including its advantages and disadvantages. Furthermore, the concept of bioavailability-based RBLM strategy has been proposed, and the challenges of RBLM and the priority areas for future research are summarized. Thus, the present review may help achieve a better understanding and successful implementation of a sustainable bioavailability-based RBLM strategy., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Bioremediation plays an important role in oil spill management and bio-electrochemical treatment systems are supposed to represent a new technology for both effective remediation and energy recovery. Diesel removal rate increased by four times in microbial fuel cells (MFCs) since the electrode served as an electron acceptor, and high power density (29.05 W m -3 ) at current density 72.38 A m -3 was achieved using diesel (v/v 1%) as the sole substrate. As revealed by Scanning electron microscope images, carbon fibres in the anode electrode were covered with biofilm and the bacterial colloids which build the link between carbon fibres and enhance electron transmission. Trace metabolites produced during the anaerobic biodegradation were identified by gas chromatography-mass spectrometry. These metabolites may act as emulsifying agents that benefit oil dispersion and play a vital role in bioremediation of oil spills in field applications., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

For more than a decade, the primary focus of environmental experts has been to adopt risk-based management approaches to cleanup PAH polluted sites that pose potentially destructive ecological consequences. This focus had led to the development of several physical, chemical, thermal and biological technologies that are widely implementable. Established remedial options available for treating PAH contaminated soils are incineration, thermal conduction, solvent extraction/soil washing, chemical oxidation, bioaugmentation, biostimulation, phytoremediation, composting/biopiles and bioreactors. Integrating physico-chemical and biological technologies is also widely practiced for better cleanup of PAH contaminated soils. Electrokinetic remediation, vermiremediation and biocatalyst assisted remediation are still at the development stage. Though several treatment methods to remediate PAH polluted soils currently exist, a comprehensive overview of all the available remediation technologies to date is necessary so that the right technology for field-level success is chosen. The objective of this review is to provide a critical overview in this respect, focusing only on the treatment options available for field soils and ignoring the spiked ones. The authors also propose the development of novel multifunctional green and sustainable systems like mixed cell culture system, biosurfactant flushing, transgenic approaches and nanoremediation in order to overcome the existing soil- contaminant- and microbial-associated technological limitations in tackling high molecular weight PAHs. The ultimate objective is to ensure the successful remediation of long-term PAH contaminated soils., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

An isolate of Cupriavidus (strain MTS-7) was identified from a long-term PAHs and heavy metals mixed contaminated soil with the potential to biodegrade both LMW and HMW PAHs with added unique traits of acid and alkali tolerance, heavy metal tolerance, self-nutrient assimilation by N fixation and P solubilization. This strain completely degraded the model 3 (150 mg L(-1) Phe), 4 (150 mg L(-1) Pyr) and 5 (50 mg L(-1) BaP) ring PAHs in 4, 20 and 30 days, respectively. It could mineralize 90-100% of PAHs (200 mg L(-1) of Phe and Pyr) within 15 days across pH ranging from 5 to 8 and even in the presence of toxic metal contaminations. During biodegradation, the minimum inhibitory concentrations were 5 (Cu(2+)) and 3 (Cd(2+), Pb(2+), Zn(2+)) mg L(-1) of the potentially bioavailable metal ions and over 17 mg L(-1) metal levels was lethal for the microbe. Further, it could fix 217-274 μg mL(-1) of N and solubilize 79-135 μg mL(-1) of P while PAHs degradation. MTS-7 as a superior candidate could be thus used in the enhanced bioaugmentation and/or phytoremediation of long-term mixed contaminated sites., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The bioaccessibility of lead (Pb) in contaminated soils has been extensively studied, including the influence of soil properties on Pb bioaccessibility. However, little is known about the effects of other metals/metalloid, such as arsenic (As), cadmium (Cd) on the bioaccessibility of Pb, i.e. whether As or Cd could increase or decrease the solubility of Pb in human gastrointestinal tract when Pb-contaminated soil and As-contaminated (or Cd-contaminated) soil are ingested simultaneously. Furthermore, it is far from clear that if soil property could make a difference to these effects. In this study, seven types of soils were collected in Australia and spiked with As, Cd or Pb. Gastric bioaccessibility of Pb ranged from 44 ± 0.9% to 100 ± 6.7% whilst intestinal bioaccessibility dropped to 1 ± 0.2% to 36 ± 1.7%. Statistical analysis shows total Pb in soil was the most significant controller for bioaccessible Pb. Effects of As and Cd on the bioaccessibility of Pb in simulated human digestive system were studied by mixing As-spiked soil (or Cd-spiked soil) with Pb-spiked soil of the same type during bioaccessibility test. Results reveal that neither As nor Cd had impact on Pb bioaccessibility, which indicates when As, Cd and Pb aged in soils separately, they may behave independently in the bioaccessibility measuring system. This finding can be part of evidence to assume additive effect when it comes to estimate the bioaccessibility of mixtures of independently-aged As and Pb (or Cd and Pb) in soils., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Recent decades have seen a growing popularity of in vitro bioaccessibility being utilised as a screening tool in human health risk assessment. However the existing bioaccessibility studies only focus on single contaminant. Considering human are likely to ingest multi-contaminants, these contaminants could interact within human gastrointestinal tract which may lead to an increase or decrease in bioaccessibility. In this study, seven different types of soil were spiked with arsenic (As) or cadmium (Cd) and aged for one year. The effects of soil properties on the bioaccessibility were examined. Moreover, the interaction between As and Cd in simulated human digestive system was studied by mixing As-spiked soil with Cd-spiked soil of the same type during bioaccessibility test. Results shows the bioaccessibility of As ranged from 40 ± 2.8 to 95 ± 1.3% in the gastric phase and 16 ± 2.0 to 96 ± 0.8% in the intestinal phase whilst a significant difference was observed between Cd gastric bioaccessibility (72 ± 4.3 to 99 ± 0.8%) and intestinal bioaccessibility (6.2 ± 0.3 to 45 ± 2.7%). Organic carbon, iron oxide and aluminium oxide were key parameters influencing the bioaccessibility of As (gastric and intestinal phases) and Cd (intestinal phase). No interactions between As and Cd during bioaccessibility test were observed in any soils, which indicates As and Cd may age independently and did not interact while being solubilised during bioaccessibility test. Thus additive effect may be proposed when estimating the bioaccessibility of mixtures of independently-aged As and Cd in soils., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

A mercury resistant bacterial strain, SA2, was isolated from soil contaminated with mercury. The 16S rRNA gene sequence of this isolate showed 99% sequence similarity to the genera Sphingobium and Sphingomonas of α-proteobacteria group. However, the isolate formed a distinct phyletic line with the genus Sphingobium suggesting the strain belongs to Sphingobium sp. Toxicity studies indicated resistance to high levels of mercury with estimated EC50 values 4.5 mg L(-1) and 44.15 mg L(-1) and MIC values 5.1 mg L(-1) and 48.48 mg L(-1) in minimal and rich media, respectively. The strain SA2 was able to volatilize mercury by producing mercuric reductase enzyme which makes it potential candidate for remediating mercury. ICP-QQQ-MS analysis of Hg supplemented culture solutions confirmed that almost 79% mercury in the culture suspension was volatilized in 6 h. A very small amount of mercury was observed to accumulate in cell pellets which was also evident according to ESEM-EDX analysis. The mercuric reductase gene merA was amplified and sequenced. The deduced amino acid sequence demonstrated sequence homology with α-proteobacteria and Ascomycota group., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Barite contamination of soil commonly occurs from either barite mining or explorative drilling operations. This work reported in vitro data for barite contaminated soils using the physiologically based extraction test (PBET) methodology. The existence of barite in plant tissue and the possibility of 'biomineralised' zones was also investigated using Scanning Electron Microscopy. Soils with low barium (Ba) concentrations showed a higher proportion of Ba extractability than barite rich samples. Barium uptake to spinach from soil was different between short term spiking studies and field weathered soils. Furthermore, Ba crystals were not evident in spinach tissue or acid digest solutions grown in barium nitrate spiked soils despite high accumulation. Barite was found in the plant digest solutions from barite contaminated soils only. Results indicate that under the conservative assumptions made, a child would need to consume extreme quantities of soil over an extended period to cause chronic health problems., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The remediation of toxic persistent organic contaminants in the environment has raised a need for effective cleanup methods. In this study, an integrated remediation technique based on biodegradation of naphthalene using Bacillus fusiformis and Fenton oxidation of their degraded metabolites using nanoscale zero-valent iron (nZVI). A 99.0% naphthalene was biodegraded by B. fusiformis in 96h, while only 59.4% chemical oxygen demand (COD) was removed, indicating that the degraded metabolites existed in solution. To further degrade the metabolites, nanoscale zero-valent iron (nZVI) was used as heterogeneous catalyst for Fenton-like oxidation of the metabolites after biodegradation lasting 40h. Results showed that the total the removal COD increased from 36.4% to 91.6% at pH 3.0, 1.0gL(-1) nZVI, 10.0mML(-1) H2O2 and temperature of 35°C. Scanning electron microscopy (SEM) showed the aggregation and corrosion of nZVI. X-ray diffraction (XRD) confirmed the existence of Fe(0) and the presence of iron oxide (Fe(II)) and iron oxohydroxide (Fe(III)). A possible degradation pathway was proposed since two naphthalene metabolites (1-Naphthalenol and 1,4-Naphthalenedione) were detected by GC-MS., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Soil plays a significant role in controlling the potential bioavailability of contaminants in the environment. In this study, eleven soils were used to investigate the relationship between soil properties and relative bioavailability (RB) of lead (Pb). To minimise the effect of source of Pb on in vivo bioavailability, uncontaminated study soils were spiked with 1500 mg Pb/kg soil and aged for 10-12 months prior to investigating the relationships between soil properties and in vivo RB of Pb using swine model. The biological responses to oral administration of Pb in aqueous phase or as spiked soils were compared by applying a two-compartment pharmacokinetic model to blood Pb concentration. The study revealed that RB of Pb from aged soils ranged from 30±9% to 83±7%. The very different RB of Pb in these soils was attributed to variations in the soils' physico-chemical properties. This was established using sorption studies showing: firstly, Freundlich partition coefficients that ranged from 21 to 234; and secondly, a strongly significant (R(2)=0.94, P<0.001) exponential relationship between RB and Freundlich partition coefficient (Kd). This simple exponential model can be used to predict relative bioavailability of Pb in contaminated soils. To the best of our knowledge, this is the first such model derived using sorption partition coefficient to predict the relative bioavailability of Pb., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Nitrate contamination in drinking water is a major threat to public health. This study investigated the efficiency of denitrification of aqueous solutions in the co-presence of synthesized nanoscale zero-valent iron (nZVI; diameter: 20-80 nm) and a previously isolated Paracoccus sp. strain YF1. Various influencing factors were studied, such as oxygen, pH, temperature, and anaerobic corrosion products (Fe(2+), Fe(3+) and Fe3O4). With slight toxicity to the strain, nZVI promoted denitrification efficiency by providing additional electron sources under aerobic conditions. For example, 50 mg L(-1) nZVI increased the nitrate removal efficiency from 66.9% to 85.2%. However, a high concentration of nZVI could lead to increased production of Fe(2+), a toxic ion which could compromise the removal efficiency. Kinetic studies suggest that denitrification by both free cells, and nZVI-amended cells fitted well to the zero-order model. Temperature and pH are the major factors affecting nitrate removal and cell growth, with or without the presence of nZVI. In this study, nitrate removal and cell growth increased in the pH range of 6.5-8.0, and temperature range of 25-35 °C. These conditions favor the growth of the strain, which dominated denitrification in all scenarios involved. As for anaerobic corrosion products, compared with Fe(2+) and Fe(3+), Fe3O4 promoted denitrification by serving as an electron donor. Finally, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) confirmed attachments of nZVI on the surface of the cell, and the formation of iron oxides. This study indicated that, as an electron donor source with minimal cellular toxicity, nZVI could be used to promote denitrification efficiency under biotic conditions., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Despite bimetallic Fe/Ni nanoparticles have been extensively used to remediate groundwater, they have not been used for the catalytic degradation of amoxicillin (AMX). In this study, bentonite-supported bimetallic Fe/Ni (B-Fe/Ni) nanoparticles were used to degrade AMX in aqueous solution. More than 94% of AMX was removed using B-Fe/Ni, while only 84% was removed by Fe/Ni at an initial concentration of 60 mg L(-1) within 60 min due to bentonite serving as the support mechanism, leading to a decrease in aggregation of Fe/Ni nanoparticles, which was confirmed by scanning electron microscopy (SEM). The formation of iron oxides in the B-Fe/Ni after reaction with AMX was confirmed by X-ray diffraction (XRD). The main factors controlling the degradation of AMX such as the initial pH of the solution, dosage of B-Fe/Ni, initial AMX concentration, and the reaction temperature were discussed. The possible degradation mechanism was proposed, which was based on the analysis of degraded products by liquid chromatography-mass spectrometry (LC-MS)., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

A new minimal medium was formulated considering the limitations of the existing media for testing heavy metal sensitivity to bacteria. Toxicity of cadmium and copper to three bacteria was investigated in the new medium and compared with three other media commonly used to study the effect of the toxic metals. Based on speciation data arrived at using ion-selective electrodes, the available free-metal concentration in solution was highest in the MES-buffered medium. This finding was strongly supported by the estimated EC(50) values for the metals tested based on the toxicity bioassays. The free-ionic cadmium and copper concentrations in the medium provide more accurate determination of metal concentrations that affects the bacteria, than with most of other existing media. This will avoid doubts on other media and misleading conclusions relevant to the toxicity of heavy metals to bacteria and provides a better option for the study of metal-bacteria interactions., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

This study presents the first systematic information on the degradation patterns of clandestine drug laboratory chemicals in soil. The persistence of five compounds - parent drugs (methamphetamine, 3,4-methylenedioxymethamphetamine (MDMA)), precursor (pseudoephedrine), and synthetic by-products N-formylmethylamphetamine and 1-benzyl-3-methylnaphthalene) - were investigated in laboratory scale for 1 year in three different South Australian soils both under non-sterile and sterile conditions. The results of the degradation study indicated that 1-benzyl-3-methylnaphthalene and methamphetamine persist for a long time in soil compared to MDMA and pseudoephedrine; N-formylmethylamphetamine exhibits intermediate persistence. The role of biotic versus abiotic soil processes on the degradation of target compounds was also varied significantly for different soils as well as with the progress in incubation period. The degradation of methamphetamine and 1-benzyl-3-methylnaphthalene can be considered as predominantly biotic as no measureable changes in concentrations were recorded in the sterile soils within a 1 year period. The results of the present work will help forensic and environmental scientists to precisely determine the environmental impact of chemicals associated with clandestine drug manufacturing laboratories., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The acute toxicity of an organophosphorous pesticide, fenamiphos and its metabolites, fenamiphos sulfoxide, fenamiphos sulfone, fenamiphos phenol, fenamiphos sulfoxide phenol and fenamiphos sulfone phenol, to a cladoceran, Daphnia carinata was studied in both cladoceran culture medium and natural water collected from a local river. The toxicity followed the order: fenamiphos>fenamiphos sulfone>fenamiphos sulfoxide. The hydrolysis products of fenamiphos, F. sulfoxide (FSO) and F. sulfone (FSO(2)) (F. phenol, FSO phenol and FSO(2) phenol) were not toxic to D. carinata up to 500microgl(-1) water, suggesting hydrolysis reaction leads to detoxification. Also the toxicity was reduced in natural water compared to the cladoceran culture medium due to microbial mediated degradation of toxicants in the natural water. Fenamiphos and its metabolites were stable in both cladoceran water and filter-sterilised natural water while these compounds showed degradation in unfiltered natural water implicating the microbial role in degradation of these compounds. To our knowledge this is the first study on acute toxicity of fenamiphos metabolites to cladoceran and this study suggests that the organophosphate pesticides are highly toxic to fresh water invertebrates and therefore pollution with these compounds may adversely affect the natural ecosystems.