Nanoscale zero-valent iron changes microbial co-occurrence pattern in pentachlorophenol-contaminated soil.

Nanoscale zero-valent iron (nZVI) is a prominent nanomaterial for the remediation of organochlorine-contaminated soil and groundwater. However, a knowledge gap regarding the effects of the coexistence of nZVI and pollutants on soil microorganisms remains. Here, we studied the effects of nZVI on the microbial community structure, co-occurrence network, and keystone taxa in pentachlorophenol (PCP, a typical organochlorine pesticide) contaminated soils. The addition of nZVI (1000 mg/kg) had no obvious recovery effect on the microbial community structure of PCP-contaminated soil, but enhanced the connection and lowered the modularity of the microbial network. These changes were mainly present in the bacterial network rather than in the fungal or archaeal network. Moreover, the addition of nZVI increased the number of keystone taxa in the PCP-contaminated soil from 29 to 76. These keystone taxa are related to the degradation of organochlorine pollutants, carbon metabolism, and nitrogen metabolism and may thus be helpful in recovering soil ecological functions. These findings provide new insights into the interaction among nanomaterials, microorganisms, and pollutants.

Biodegradation of tricresyl phosphates isomers by a novel microbial consortium and the toxicity evaluation of its major products.

A novel microbial consortium ZY1 capable of degrading tricresyl phosphates (TCPs) was isolated, it could quickly degrade 100% of 1 mg/L tri-o-cresyl phosphate (ToCP), tri-p-cresyl phosphate (TpCP) and tri-m-cresyl phosphate (TmCP) within 36, 24 and 12 h separately and intracellular enzymes occupied the dominated role in TCPs biodegradation. Additionally, triphenyl phosphate (TPHP), 2-ethylhexyl diphenyl phosphate (EHDPP), bisphenol-A bis (diphenyl phosphate) (BDP), tris (2-chloroethyl) phosphate (TCEP) and tris (1-chloro-2-propyl) phosphate (TCPP) could also be degraded by ZY1 and the aryl-phosphates was easier to be degraded. The TCPs reduction observed in freshwater and seawater indicated that high salinity might weak the degradability of ZY1. The detected degradation products suggested that TCPs was mainly metabolized though the hydrolysis and hydroxylation. Sequencing analysis presented that the degradation of TCPs relied on the cooperation between sphingobacterium, variovorax and flavobacterium. The cytochrome P450/NADPH-cytochrome P450 reductase and phosphatase were speculated might involve in TCPs degradation. Finally, toxicity evaluation study found that the toxicity of the diesters products was lower than their parent compound based on the generation of the intracellular reactive oxygen (ROS) and the apoptosis rate of A549 cell. Taken together, this research provided a new insight for the bioremediation of TCPs in actual environment.

Metabolomic analysis and oxidative stress response reveals the toxicity in Escherichia coli induced by organophosphate flame retardants tris(2-chloroethyl) phosphate and triphenyl phosphate.

Organophosphate flame retardants (OPFRs) are emerging environmental pollutants that are increasingly being used in consumer commodities. The adverse effects on biota induced by tris(2-chloroethyl) phosphate (TCEP) and triphenyl phosphate (TPHP) have become a growing concern. Unfortunately, toxic mechanisms at the molecular level for OPFRs in organisms are still lacking. Herein, Escherichia coli (E.coli) was exposed to TCEP and TPHP for 24 and 48 h to reveal oxidative stress response and molecular toxicity mechanisms. The results indicated that promotion of ROS overload occurred at higher dosages groups. The levels of SOD and CAT were significantly elevated along with the increase of MDA attributed to lipid peroxidation. Additionally, apoptosis rates increased, accompanied by a decline in membrane potential and Na+/K+-ATPase and Ca2+/Mg2+-ATPase contents, signifying that E. coli cytotoxicity induced by TCEP and TPHP was mediated by oxidative stress. Based on metabolomic analysis, different metabolic pathways were disrupted, including glycolysis/gluconeogenesis, pentose phosphate metabolism, purine metabolism, glutathione metabolism, amino acid biosynthesis, butanoate metabolism, alanine and aspartate metabolism. Most differentially expressed metabolites were downregulated, indicating an inhibitory effect on metabolic functions and key metabolic pathways. These findings generated new insights into the potential environmental risks of OPFRs in aquatic organisms.

Divergent patterns of heavy metal accumulation in paddy fields affect the dietary safety of rice: a case study in Maoming City, China.

The objective of this work was to study the impact of large petrochemical plants and mining operations on the accumulation of heavy metals in farmland and rice, as well as assess their potential risks on human health. The contents of seven heavy metals, Cd, Pb, Cr, Ni, Co, Cu, and Mn, were monitored in a typical polluted paddy soil-rice system near a petrochemical plant and mining area in Maoming, China. The results showed that the content of Cd in the soil exceeds the standard rate by 100%, and the single factor pollution index of Cd was 5.12, which is considered heavy pollution. Excessive heavy metals can inhibit and poison the growth of rice plants. Rice plants can maintain a certain level of heavy metal content by reducing the absorption or interception in the root cells, leading to great differences in the distribution of different heavy metals in plant tissues. Cadmium, Cu, Co, and Mn are easily absorbed from the soil by rice roots, while other heavy metals are relatively difficult to absorb by rice roots. Cuprum, Cd, Co, Pb, and Cr were mainly accumulated in the root of rice, but Mn and Ni migrate to the above ground plant tissues quickly. The brown rice produced in the paddy fields in the study area was seriously polluted. The concentration of Cd, Pb, and Ni in brown rice exceeded the standard by 100%, and Cr in brown rice also exceeded the standard by 80%. If residents consume rice from the study area, their daily intake of Cr and Cd will be 1.02 and 3.24 times higher, respectively, than the standard limit recommended by the FAO/WHO. The irrigation streams were polluted due to the discharge of petrochemical plants and mining wastewater, causing the serious pollution of heavy metals in the surrounding paddy fields. The rice produced in this area poses a serious risk to consumers, and so this problem of pollution should be addressed.

Effect of a low-cost and highly efficient passivator synthesized by alkali-fused fly ash and swine manure on the leachability of heavy metals in a multi-metal contaminated soil.

Soil pollution, caused by heavy metals, is an environmental problem that requires an urgent solution in China. Chemical passivation is a technology that uses various passivators to reduce the availability of heavy metals in soil and realize the remediation of contaminated soil. In this study, we examined the effects of fly ash (FA), alkali-fused fly ash (AFFA), swine manure biochar (SB), and modifying biochar (MB) on the leachability of Cu, Zn, Pb, and Cd via soil culture experiments. The results showed that the addition of AFFA, SB, and MB significantly reduced the extractable contents of Cu, Pb, and Cd in the soil. AFFA and MB had the best passivation effect, followed by SB and FA. The passivation effect on Pb was the best, followed by that on Cu and Cd. AFFA modification significantly improved the passivation effect of MB on Cu, Pb, and Cd in composite contaminated soil. With the addition of 3% MB, the Pb, Cu, and Cd extracted by TCLP decreased by 95.7, 74.1, and 59.1%, respectively. Correlation analysis, Fourier transform infrared spectrometry, scanning electron microscopy, and energy-dispersive X-ray spectroscopy showed that the passivation mechanism is mainly due to an increase in the soil pH, silicate content, and cohesiveness. The soil culture experiments in this study proved that MB is a low-cost and highly efficient organic-inorganic composite passivator for multi-metal contaminated soils.

Phenanthrene degradation in soil using biochar hybrid modified bio-microcapsules: Determining the mechanism of action via comparative metagenomic analysis.

A strategy involving biochar (BC) hybrid modification was developed to promote the bioremediation effect of degrading bacteria immobilized in layer-by-layer assembly (LBL) microcapsules for the treatment of phenanthrene (PHE) polluted soil. A taxonomic and functional metagenomic approach was used to investigate changes in the microbial community structures and functional gene compositions in the PHE-polluted soil during the bioremediation process. Biofortification with an initial PHE concentration of 100 mg kg-1 dry soil in soils using the BC (3%) hybrid LBL bio-microcapsule (BC-LBL, 2.0 g kg-1 dry soil, 107 colony forming unite cell g-1 dry soil) was faster; further, a higher PHE degradation efficiency (80.5% after 25 d) was achieved when compared with that by the LBL agent (66.2% after 25 d) used. Sphingomonas, Streptomyces, Gemmatirosa, Ramlibacter, Flavisolibacter, Phycicoccus, Micromonospora, Acidobacter, Mycobacterium and Gemmatimonas were more abundant in BC-LBL treatment than those in LBL one. Functional gene annotation results showed that more gene number with BC-LBL treatment than those with LBL one. More abundant functions in the former were primarily related to the growth, reproduction, metabolism, and transportation of bacteria. BC hybridization promoting PHE degradation by microencapsulated bacteria may be due to the strong adsorption property of BC, which results in the enrichment of the nutrients that needed for bacterial growth and reproduction, as well as enhancing the mass transfer performance of PHE to BC-LBL; Meanwhile, BC could also stimulate and improve the metabolism and membrane transportation of the degrading bacteria, and finally improving the degradation function.

Rapidly photocatalytic mineralization of typical veterinary drugs with the SnO2/SnIn4S8 composite.

Considering the high environmental risk, the remediation of veterinary drug pollutants aroused numerous concerning. In this paper, a novel photocatlyst, SnO2/SnIn4S8, was fabricated by in situ precipitation and hydrothermal method and then employed to simulate photocatalytic degradation of olaquindox under visible light. The SEM, TEM, XRD, XPS and electrochemical results clearly showed that the n-type heterojunction between SnO2 and SnIn4S8 was successfully constructed, which greatly reduce the recombination of the photogenic electron and holes, leading to the improvement of photocalytic performance and stability (recycled over 10 times). Besides, the SnO2/SnIn4S8 composite also exhibited good ability to mineralize the olaquindox. Under the optimal condition (pH of 3, 1 g L-1 of 30 wt% SnO2/SnIn4S8 and 10 mg L-1 of initial olaquindox concentration), the olaquindox could be fully and rapidly degraded in 25 min, and completely mineralized in 2 h (99.3 ± 1.7%). LC-QTOF-MS analysis evidently displayed 10 intermediates during the olaquindox degradation. In addition, with the attack of the reactive oxygen species (h+, •OH and •O2-), olaquindox could be effectively decomposed via deoxygenation, hydroxylation and carboxylation reactions. Importantly, compared to photodegradation, the photocatalytic process was an ideal way to eliminate the olaquindox form water because it could avoid the accumulation of toxic byproducts.

Bacterial communities and functional genes stimulated during phenanthrene degradation in soil by bio-microcapsules.

In this study, a taxonomic and functional metagenomic method was used to investigate the difference produced between degrading bacteria immobilized in layer-by-layer assembly (LBL) microcapsules or not during the bioremediation of a soil polluted with phenanthrene (PHE). Bioaugmentation with LBL microcapsule immobilized degrading bacteria could result in different changes of native microbial communities, shifting the functional gene constructions of polluted soils. The LBL treatment enhanced PHE degradation (initial concentration of 100 mg kg-1 dry soil) by 60% after 25 d compared to the free bacteria (FB). The enhancing effect of PHE degradation produced by the LBL treatment was found to be significantly associated with some crucial phyla (e.g., Bacteroides, Gemmatimonadetes and Acidobacteria) and genera including Streptomyces, Ramlibacter, Mycobacterium, Phycicoccus, Gemmatirosa, Flavisolibacter, Micromonospora, Acid_Candidatus_Koribacter and Gemmatimonas. The main differences of functional metagenomics between LBL and FB treatments were observed in higher levels in metabolism of aromatic hydrocarbons and its related functions or enzymes in the former, e.g., membrane transport systems, binding, substrate transporter, cleavage enzymes, dehydrogenation, oxidase, esterase and glycosidase, greatly favoring PHE mineralization. Therefore, our results provide useful findings on understanding of how immobilization strategies can influence the taxonomic and functional gene composition in soils, as well as polycyclic aromatic hydrocarbons (PAH) degradation.

Synthesis of silica-composited biochars from alkali-fused fly ash and agricultural wastes for enhanced adsorption of methylene blue.

Two types of silica-composited biochars were prepared by mixing swine manure or rice straw with alkali-fused fly ash (AFFA) followed by pyrolysis. A 10% (w/w) AFFA modification improved the specific surface area, pore volume, and average pore size of the biochars. Certain surface oxygen-containing functional groups (i.e., -OH and CO) in the biochars were protected, and silicon-oxygen bonds (i.e., O-Si-O and OSi) were strengthened considerably by AFFA modifications during high-temperature pyrolysis. The adsorption capacity of biochar for methylene blue (MB) was enhanced after AFFA modification, and a modified biochar with the highest adsorption capacity was prepared at a pyrolysis temperature of 700 °C, pyrolysis holding time of 2 h, and an AFFA proportion of 10%. The MB adsorption capacity of the modified biochars significantly increased when the pH of the solution increased (from 3 to 13). The adsorption data were well described by a pseudo-second-order model and Langmuir isotherms. The maximum MB adsorption capacities of the modified swine manure and rice straw biochars were 143.76 mg/g and 131.58 mg/g, respectively. The adsorption capacities of the AFFA-modified biochars were 10.7-112.3% higher than those of the unmodified biochars. The enhanced MB adsorption capacities of the former appear to be attributed to their increased specific surface areas, increased porosities, strong oxygen-containing functional groups, and high contents of exchangeable sodium ions. These results indicate that industrial and agricultural wastes can be reused to produce novel silica-composited biochars with high MB removal capacity. Accordingly, these biochars could be effectively used to treat wastewater and thus to mitigate solid waste disposal-related problems.

Contamination of pyrethroids in agricultural soils from the Yangtze River Delta, China.

This study focused on contamination levels and spatial distributions of four common pyrethroids found in agricultural soils of the Yangtze River Delta (YRD), China. Pyrethroids were detected in 241 soil samples (88.8% detection rate) with total concentrations ranging from  cypermethrin (1.10 ng/g) > deltamethrin (0.89 ng/g) > cyhalothrin (0.20 ng/g). The highest concentration of fenpropathrin was recorded as 37.6 ng/g. The highest detection rate of 63.9% was found for cyhalothrin. A distinct pattern of spatial distribution was observed where high concentrations of pyrethroids were detected in sites around Taihu Lake. Potential sources of pyrethroids in agricultural soils from the YRD region include pyrethroids used for pest control and wastewater irrigation in the region. Redundancy and correlation analyses show that the soil TOC values have played a significant role in the behavior of pyrethroids in agricultural soils of the YRD region. Potential ecological risks of pyrethroids in agricultural soils of the YRD region are low. Cypermethrin and cyhalothrin showed potential toxic effects on the ecological conditions of agricultural soils in 4.6% and 2.9% of the sampling sites, respectively. Further studies should pay more attention to the potential human health risks posed by pyrethroids in agricultural soils for the protection of soil quality and food safety.

Acidity and metallic elements release from AMD-affected river sediments: Effect of AMD standstill and dilution.

In acid mine drainage (AMD) polluted rivers, considerable fraction of potential toxic elements are temporarily sequestered by sediments. There are two main potential environmental hazards associated with the sediments, acidity liberation and re-mobilization of metallic elements, during environmental conditions change. The effects of AMD standstill and water dilution on metallic elements migration were assessed in an AMD standstill test and a dialysis experiment. Maintaining AMD standstill, often occurring in AMD damming process, could induce the occurrence of iron secondary minerals precipitation along with attenuation of dissolved elements and a decrease in water pH value. Both field sediments and lab precipitates were confirmed as being dominant with schwertmannite which was the most important source and sink for acidity and metallic elements. The mechanism of cation heavy metals scavenging implied by FTIR results mostly depended on the exchanging of H+ from surface hydroxyl groups (-OH) in schwertmannite-rich sediments. For arsenic oxyanion, its adsorption included surface complexation with iron hydroxyl groups at the mineral surface, as well as anion exchange of SO42- present in the structure. The quantities of acidity release differed significantly from 20 to 3714 mol H+/t depending on the iron hydroxyl minerals type and their contents in the corresponding sediments in 35 d dialysis, with the release rate well fitted by the second order model. Slight degree of phase transformation in schwertmannite dominant sediment had resulted in a high risk of metallic element release during the 35 d dilution duration. The significant risk of metallic elements release was ranked in the order of Cd > Mn > Zn > Pb, and with more than 89% of Cd released from FS6 and 82% from LPS1. Relatively, Cu and As in sediments were much more stable. Overall, damming was an effective and low cost pretreatment strategy for AMD pollution control. Knowledge of the characteristics of iron secondary minerals in river sediments is essential premise for both comprehensive assessment of site contamination status and effective remediation strategy decision.

Contamination of pyrethroids and atrazine in greenhouse and open-field agricultural soils in China.

A national-scale survey was conducted to assess the levels and distribution of two extensively used pesticides (pyrethroids and atrazine) in greenhouse and open-field soils in 20 provinces across China. Concentrations between 1.30 and 113 ng/g and 0.51-85.4 ng/g for the total pyrethroids (PYs) and of LOD-137 ng/g and LOD-134 ng/g for atrazine were found in greenhouse and open-field soils, respectively. Higher contaminations were found in the greenhouse than in the open fields. The levels of total pyrethroids in 80% of the greenhouses and of atrazine in 60% of the greenhouses were significantly higher than those in the nearby open-field soils (p < 0.05), respectively. The contamination of PYs and atrazine was generally more serious in the northern provinces of China, such as Heilongjiang, Jilin, Liaoning, Beijing, and Hebei. Pearson correlation analysis revealed that the contamination of PYs was significantly correlated with the soil total organic carbon (TOC) value in both greenhouse and open-field soils. Canonical correspondence analysis (CCA) showed that PYs might have an impact on the microbial alpha diversity, while cyhalothrin and cypermethrin may be the key factors affecting the microbial community in the greenhouse and open-field soils. The soil samples containing pesticide residues showed distinct taxonomic and functional communities, where an increased diversity and abundance of microorganisms able to degrade pesticides was observed with high-level PYs contamination. These findings provide useful information for evaluating PYs and atrazine pollution and for contamination management in greenhouse agriculture.

Mechanism of enhancing pyrene-degradation ability of bacteria by layer-by-layer assembly bio-microcapsules materials.

The mechanism of improving pyrene (PYR)-degrading ability of bacteria CP13 in Layer-by-layer (LBL) assembly chitosan/alginate (CHI/ALG) bio-microcapsules was investigated. Flow cytometry analysis showed that LBL microcapsules could effectively slow down the increasing rate of bacterial cell membrane permeability and the decreasing rate of the membrane potential, so as to reduce the death rate and number of the cells, which could protect the degrading bacteria. The results of Fluorescence spectrum, circular dichroism (CD) spectrum and laser light scattering (LLS) analysis revealed that the other possible mechanism for LBL microcapsules to promote bacterial degradation were following: CHI could enter the secondary structure of the protein of the extracellular polymeric substances (EPS) from CP13 and combined with EPS to generate a stable ground material, which had larger molecular weight (3.76×106 g mol-1) than the original EPS (2.52×106 g mol-1). The combination of CHI and EPS resulted in the decrease of the density of EPS from 1.18 to 0.72 g L-1, suggesting that CHI can loosen the EPS configurations, improving the capture ability of bacteria for PYR as well as the mass transfer of PYR from the extracellular to intracellular, thus eventually promoting the bacteria degrade performance.

Bioremediation of PAH-contaminated farmland: field experiment.

The agricultural soil contaminated by polycyclic aromatic hydrocarbons (PAHs) is gradually emerging and becoming serious in China with the rapid development of economy. To reduce the risk of PAHs in agricultural soil and guarantee the food safety, the biological agent that Mycobacterium gilvum immobilized on modified peanut shell powder enhanced remediation of polycyclic aromatic hydrocarbon-contaminated vegetable farmland was investigated under the conditions of the field experiment. The results indicated that adding biological agent could promote PAH degradation in the soil, especially high-ring PAHs. The degradation rates of PAHs in the soil could be further improved to 16.5-43.5 %, respectively, compared with the soil without the biological agent. Adding the biological agent could significantly improve soil dehydrogenase activity and microbial diversity. It also could reduce the enrichment of PAHs in mustard planted in the polluted field, which indicated that the biological treatments might be less ecological risk. The work suggested that adding the biological agent might be a promising in situ bioremediation strategy for PAH-contaminated farmland field.

Pyrene biodegradation with layer-by-layer assembly bio-microcapsules.

Biotechnology is considered as a promising technology for the removal of polycyclic aromatic hydrocarbons from the environment. Free bacteria are often sensitive to some biotic and abiotic factors in the environment to the extent that their ability to effect biodegradation of organic pollutants, such as polycyclic aromatic hydrocarbons, is hampered. Consequently, it is imperative to carry out investigations into biological systems that will obviate or aid tolerance of bacteria to harsh environmental conditions. Chitosan/alginate bio-microcapsules produced using layer-by-layer (LBL) assembly method were tested for pyrene (PYR) biodegradation under harsh environmental conditions. Morphology observation indicated that the flake bio-microcapsules could be successfully prepared through LBL assembly method. Surface analysis showed that the bio-microcapsules had large fractions of mesopores. The results of the biodegradation experiments revealed that the 95% of 10mgL-1 PYR could be removed by the bacteria encapsulated chitosan/alginate bio-microcapsules in 3 days, which was higher than that of the free bacteria (59%). Compared to the free cells, the bacteria encapsulated chitosan/alginate bio-microcapsules produced 1-6 times higher PYR biodegradation rates at a high initial PYR concentration (50mgL-1) and extremely low pH values (pH =3) or temperatures (10°C or 40°C), as well as high salt stress. The results indicated that bacteria in microcapsules treatment gained a much higher tolerance to environmental stress and LBL bio-microcapsule could be promising candidate for remediating the organic pollutants.

A novel direct equipartition ray design (EquRay) procedure for toxicity interaction between ionic liquid and dichlorvos.

BACKGROUND, AIM AND SCOPE: Pollutants always co-exist in the environment. Determining and characterizing the interaction among chemicals is an important issue. Experimental designs (ED) play an important role in evaluating the interactions. The main aim of our study is to provide the test and analysis of the toxicity interaction with a novel ED method. MATERIALS AND METHODS: A novel direct equipartition ray design (EquRay) procedure was proposed to effectively and systematically determine the toxicities of binary mixtures on Vibrio qinghaiensis sp.-Q67. Here, one component is ionic liquid, 1-butyl-2,3-dimethylimidazolium chloride (IL1), 1-butylpyridinium bromide (IL2) or N-hexylpyridinium bis(trifluoromethylsulfonyl)imide (IL3), and another is dichlorvos (DIC). The toxicity interaction was evaluated by comparing experiment and additive model together with three-dimension deviation response surface (DRS) analysis. RESULT: Selecting CA as a reference model, the binary mixtures exerted less than additive (antagonism). Most of the deviations occurred in the centre portion of the DRS where the dCA (deviation from CA) values are between -15% and -26% for IL1-DIC and IL2-DIC mixtures and -10% and -15% for IL3 and DIC. Selecting IA as a additive model, IL1-DIC and IL2-DIC mixtures exhibited less than additive (antagonism) while IL3-DIC displayed an addition action and the absolute values of dIAs (deviation from IA) were less than 10%. CONCLUSION: A novel EquRay procedure was developed in this study and the EquRay can provide us with the information about the toxicity interaction between binary mixture components (such as DIC and IL) in different concentration regions across different mixture ratios.