[Relationships Between Microplastic and Surrounding Soil in an E-Waste Zone of China].

Microplastic pollution is ubiquitous and has attracted significant public attention. Recent research on microplastic has focused on aquatic environments, but its impacts on soil ecosystems remain poorly understood, especially in e-waste dismantling zones. The objective of this study was to investigate the relationships between microplastic and surrounding soil in abandoned e-waste disassembling plots with different dismantling methods focusing on ecotoxicology and microbiology in Guiyu, Shantou District, Guangdong Province. The surface morphology of collected microplastics showed signs of aging and degradation, possibly due to their long-term exposure in the soil and the original disassembling methods. In addition, there were diverse metal elements at different surface positions of the same microplastic sample based on SEM-EDS analyses, indicating that some metal elements carried by microplastics are derived from the surrounding soil rather than being inherent to the microplastic. Moreover, seven heavy metals (Pb, Cd, Cr, As, Ba, Co, and Ni) inherent in microplastic were identified using ICP-OES, revealing that the concentrations varied in different sampling plots were typically higher than in the surrounding soil. In particular, the concentration of Ba in microplastic was 103 orders of magnitude higher than in soil. Indeed, Ba in the form of BaSO4 is widely used as a filler in numerous plastics. Furthermore, microplastic-associated microorganisms were examined using 16S rRNA sequencing, and the relationships between the top 50 genera of microplastic-bound bacteria and soil environmental factors were analyzed using the Spearman's rank correlation coefficient. Microorganisms primarily originated from the surroundings of microplastics; therefore, environmental factors could directly affect the microbial communities associated with this type of pollutant. Importantly, different dismantling methods were associated with distinct soil environmental factors, and their correlations with microplastic-associated microorganisms also varied.

Decontamination of dense nonaqueous-phase liquids in groundwater using pump-and-treat and in situ chemical oxidation processes: a field test.

Groundwater remediation is difficult because of the complexity of the treatment area and the presence of various pollutants, and it is difficult to achieve using a single process. A combined pump-and-treat (P&T) and in situ chemical oxidation (ISCO) system was used to remove dense nonaqueous-phase liquids (DNAPLs) from groundwater at the field scale in this study. The underground water pH, electrical conductivity, dissolved oxygen concentration, and SO4 2- concentration were used as indirect evidence of in situ chemical reactions. Groundwater remediation using the P&T-ISCO process using 1.5% sodium persulfate and 0.03% sodium hydroxide had a remarkable effect on DNAPLs, and the DNAPL diffusion distance was much higher under pumping conditions than under natural conditions. During groundwater remediation, the pollutant concentration positively correlated with the pH, electrical conductivity, and dissolved oxygen concentration and negatively correlated with the SO4 2- concentration. In summary, P&T-ISCO can effectively accelerate DNAPL degradation to give efficient groundwater remediation.

Degradation of trichloroethylene by photoelectrochemically activated persulfate.

Chlorine-containing organic compounds were discharged informally as a result of untreated industrial wastewater, which caused groundwater pollution. In this study, titanium dioxide nanotube arrays (TNAs) were modified with copper oxide to photoelectrochemical (PEC) active persulfate to degrade trichloroethylene (TCE). The SEM results show copper nano-particles with a cubic shape were successfully deposited on the surface of TNAs. The results of UV-vis analysis indicate the absorption wavelengths red-shift to 550-600 nm for better light utilization. CuO/TNAs were dominated by the anatase phase after sintering at 450 °C with significant visible light response. The chemical contents for the surface of CuO/TNAs are 23.7, 53.4, 18.4 and 4.4% for C, O, Ti and Cu, respectively. The photocurrent of CuO/TNAs is 1.89 times higher than that of TNAs-93 cm^2-1hr under 100 W Hg-lamp illuminations. This demonstrates the efficiency of light utilization of TNAs was improved by the modification with copper nanoparticles. The degradation rate of TCE in the anodic chamber is more effective than that in the cathodic chamber because of the synergistic effect of hydroxyl and sulfate radicals. The mechanism of TCE degradation via persulfate in the PEC system was proposed and discussed in detail.

Enhanced photoelectrochemical degradation of Ibuprofen and generation of hydrogen via BiOI-deposited TiO2 nanotube arrays.

This study employed BiOI-deposited TiO2 nanotube arrays (BiOI-TNTAs) electrode in a photoelectrochemical (PEC) system to oxidize Ibuprofen and generate hydrogen in the anodic and cathodic chamber, respectively. FESEM results revealed the diameter of TiO2 nanotubes was 90-110nm. According to the XRD analysis, the BiOI-TNTAs were dominated by the anatase phase and tetragonal structure of BiOI. XPS results confirmed the coexistence of BiOI in the BiOI-TNTAs associated with Bi (33.76%) and I (8.81%). UV-vis absorption spectra illustrated BiOI-TNTAs exhibit strong absorptions in the visible light region. The PEC method showed the best degradation efficiency for Ibuprofen is a rate constant of 3.21×10-2min-1. The results of the Nyquist plot revealed the recombination of photogenerated electron-hole pairs was inhibited as the bias potential was applied. Furthermore, the Bode plot demonstrated the lifetime (τel) of photoexcited electrons of BiOI-TNTAs was 1.8 and 4.1 times longer than that of BiOI-Ti and TNTAs, respectively. In the cathodic chamber, the amount of hydrogen generation reached 219.94µM/cm2 after 3h of reaction time.

[Heavy Metal Contamination in Farmland Soils at an E-waste Disassembling Site in Qingyuan, Guangdong, South China].

Crude e-waste dismantling activities have caused a series of environmental pollution problems, and the pollutants released from the dismantling activities would finally pose high risks to human health by means of the accumulation through food chains. To explore the contamination status of heavy metals to the surrounding farmland soils in Longtang and Shijiao Town, Qingyuan, Guangdong, China, 22 farmland soil samples were collected and analyzed for the contents, spatial distributions and chemical forms of 6 heavy metals (Pb, Cu, Cd, Zn, Cr and Ni). The results showed that the 6 heavy metals exhibited obvious accumulations when compared to the corresponding background values in Guangdong Province. According to farmland environmental quality evaluation standard for edible agricultural products HJ 332-2006, the pollution severity of heavy metals was evaluated by monomial pollution index and Nemerow synthetic pollution index methods, the results indicated that 72. 7% of the soil samples contained one or more kinds of heavy metals with higher concentrations than the corresponding standard values, Cd, Cu, Pb and Zn were the main metals in the polluted soils, and for the proportion of contaminated soil samples in all the 22 samples, Cd was the highest, followed by Cu, and finally Pb and Zn. Nemerow synthetic pollution index further revealed that 68. 2% of soil samples were contaminated, and among them 53. 3% of samples were heavily contaminated. Most of the heavy metals were well correlated with each other at the 0. 05 or 0. 01 level, which indicated that primitive e-waste recycling activities were an important source of the heavy metal contamination in Longtang and Shijiao Town. The contents of Cd, Pb, Cu and Zn in surface soils were higher than those of other soil layers, and the contents of these 4 metals in deep soils (20- 100 cm) did not show significant decreases with the increasing depths. The contents of Cr and Ni maintained constant, and exhibited no statistical differences with the sampling depths. Sequential leaching tests showed that the active fractions of Pb, Cu and Cd ranged from 36. 9% to 90. 6%, 39. 6% to 93. 9% and 43. 7% to 99. 6%, with mean values of 61. 3% 65. 3% and 80. 7%, respectively. The active fractions of these three metals in most samples accounted for more than half of their own total contents, which would cause a high ecological risk.

Removal of natural estrogens and their conjugates in municipal wastewater treatment plants: a critical review.

This article reviews studies focusing on the removal performance of natural estrogens in municipal wastewater treatment plants (WWTPs). Key factors influencing removal include: sludge retention time (SRT), aeration, temperature, mixed liquor suspended solids (MLSS), and substrate concentration. Batch studies show that natural estrogens should biodegrade well; however, batch observations do not always agree with observations from full-scale municipal WWTPs. To explain this discrepancy, deconjugation kinetics of estrogen conjugates in lab-scale studies were examined and compared. Most estrogen conjugates with slow deconjugation rates are unlikely to be easily removed; others could be cleaved in WWTP settings. Nevertheless, some estrogens cleaved from their conjugates may be found in treated effluent, because deconjugation requires several hours or longer, and there is insufficient rest time for the biodegradation of the cleaved natural estrogens in the WWTP. Therefore, WWTP removals of natural estrogens are likely to be underestimated when estrogen conjugates are present in raw wastewater. This review suggests that biodeconjugation of estrogen conjugates should be enhanced to more effectively remove natural estrogens in WWTPs.

Estimated human excretion rates of natural estrogens calculated from their concentrations in raw municipal wastewater and its application.

Natural estrogens are important endocrine disrupting compounds (EDCs), which may pose adverse effects on our environment. To avoid time-consuming sample preparation and chemical analysis, estimation of their concentrations in municipal wastewater based on their human urine/feces excretion rates has been generally adopted. However, the data of excretion rates available are very limited and show significant difference among countries. In the context of increasing reporting on the concentrations of natural estrogens in municipal wastewater around the world, this study presented a simple method to estimate their human excretion rates based on the concentrations of natural estrogens in raw sewage. The estimated human excretion rates of natural estrogens among ten countries were obtained, which totally covered over 33 million population. Among these, Brazilians had the largest excretion rates with estrone (E1) and 17ß-estradiol (E2) as 236.9 and 60 µg/day/P, respectively, while Iran had the lowest value of 2 µg/day/P for E1 and 0.5 µg/day/P for E2. The average estimated human excretion rates of E1, E2, and estriol (E3) are 17.3, 6.4, and 39.7 µg/day/P, respectively. When the estimated human excretion rates obtained were applied for prediction, the predicted results showed better accuracies than those based on human urinary/feces excretion rates. The method in this study is simple, cost-effective and time-saving, which may be widely applied.

Do we underestimate the concentration of estriol in raw municipal wastewater?

The main source of natural estrogens to municipal wastewater is human excretions via urine or feces, thus their concentrations in raw wastewater should show positive linear relationship with their human excretions. This study mainly focused on their concentration relationship in raw wastewater. Based on comparison between chemical analyses and predictions through human excretion rates, the observed concentrations of estriol (E 3) in municipal wastewater were found to be noticeably lower than the predicted values. The main cause for the disparity is that substantial conjugated E 3 also exists in raw wastewater. This work suggested that monitoring both E 3 and its conjugates is necessary to get more accurate E 3 removal performance of wastewater treatment plants (WWTPs).

[Using flow cytometry to explore the changes of Sphingomonas sp. GY2B bacterial surface characteristics in the process of degrading phenanthrene].

The first step of biodegradation is the contact of microorganism and pollutants, in order to examine the influence of phenanthrene on Sphingomonas sp. GY2B's surface properties during its degrading process, the bacteria was cultivated at different conditions, and detected by flow cytometry combined with fluorescent dyes for its surface changes. The results indicated that, the membrane structure had been certainly damaged during the degrading process, leading to an increased membrane permeability. Moreover, the destruction of bacteria membrane integrity became more serious with a higher pollutant concentration. At the concentration of 300 mg x L(-1), the ratio of stained bacterial cells/unstained cells was 12.44 after cultured for 60 h, while at 100 mg x L(-1) and 1.2 mg x L(-1), the ratios were 1.95 and 1.11, respectively. The results of fourier transform infrared (FT-IR) absorbance spectroscopy detection, the discrimination of death, injured and intact cells, and Zeta potential detection further verified the bacterial cell surface permeability changes. Flow cytometry combined with fluorescent dye propidium iodide was used to monitor the changes of bacterial membrane integrity on single-cell level which exhibited a good potential for exploring the changes of bacterial surface properties during the degrading progress and more deeply for investigating the degradation mechanism.

Bioaccumulation characterization of cadmium by growing Bacillus cereus RC-1 and its mechanism.

In an effort to explore the protective mechanism of growing Bacillus cereus RC-1 against the toxicity of different Cd(II) concentrations, bacterial growth, cadmium consumption, surface interactions and intra- and extra-cellular Cd(II) contents were examined. Cellular morphology and growth were evidently affected by the initial metal concentrations above 20 mg L(-1), according to the analysis of SEM, AFM, TEM and UV spectrophotometer. Surface complexation and electrostatic attraction played an important role in the different Cd(II) concentrations, as determined by the FTIR and Zeta potential analysis. Intracellular accumulation was the predominant mechanism in culture with lower metal concentrations (below 20 mg L(-1)), but was overshadowed by extracellular adsorption at higher concentrations. This suggested that the growing cells might employ one dominant mechanism at lower concentrations and then shift to another at higher concentrations. These results suggest options could be exploited for bioremediation of aqueous solution in which the Cd(II) concentration is less than 20 mg L(-1).

Determination of decabrominated diphenyl ether in soils by Soxhlet extraction and high performance liquid chromatography.

This study described the development of a method based on Soxhlet extraction combining high performance liquid chromatography (Soxhlet-HPLC) for the accurate detection of BDE-209 in soils. The solvent effect of working standard solutions in HPLC was discussed. Results showed that 1:1 of methanol and acetone was the optimal condition which could totally dissolve the BDE-209 in environmental samples and avoid the decrease of the peak area and the peak deformation difference of BDE-209 in HPLC. The preliminary experiment was conducted on the configured grassland (1 µ g/g) to validate the method feasibility. The method produced reliable reproducibility, simulated soils (n = 4) RSD 1.0%, and was further verified by the analysis e-waste contaminated soils, RSD range 5.9-11.4%. The contamination level of BDE-209 in burning site was consistent with the previous study of Longtang town but lower than Guiyu town, and higher concentration of BDE-209 in paddy field mainly resulted from the long-standing disassembling area nearby. This accurate and fast method was successfully developed to extract and analyze BDE-209 in soil samples, showing its potential use for replacing GC to determinate BDE-209 in soil samples.

Biosorption of Cd(II) by live and dead cells of Bacillus cereus RC-1 isolated from cadmium-contaminated soil.

The present study investigated the biosorption capacity of live and dead cells of Bacillus cereus RC-1 for Cd(II). The biosorption characteristics were investigated as a function of initial pH, contact time, and initial cadmium concentration. Equilibrium biosorption was modeled using Langmuir, Freundlich and Redlich-Peterson isotherm equations. It was found that the maximum biosorption capacities calculated from Langmuir isotherm were 31.95 mg/g and 24.01 mg/g for dead cells and live cells, respectively. The kinetics of the biosorption was better described by pseudo-second order kinetic model. Desorption efficiency of biosorbents was investigated at various pH values. These results indicated that dead cells have higher Cd(II) biosorption capacity than live cells. Furthermore, zeta potential, transmission electron microscopy (TEM), scanning electron microscopy (SEM) coupled with energy dispersive X-ray (EDX), and Fourier transform infrared spectroscopy (FTIR) studies were carried out to understand the differences in the Cd(II) biosorption behavior for the both biosorbents. The bioaccumulation of Cd(II) by B. cereus RC-1 was found to depend largely on extracellular biosorption rather than intracellular accumulation. Based on the above studies, dead biomass appears to be a more efficient biosorbent for the removal of Cd(II) from aqueous solution.

Removal of chromium (VI) from electroplating wastewater using an anion exchanger derived from rice straw.

An anion exchanger from rice straw was used to remove Cr (VI) from synthetic wastewater and electroplating effluent. The exchanger was characterized using Fourier transform infrared (FTIR) spectrum and scanning electron microscopy (SEM), and it was found that the quaternary amino group and hydroxyl group are the main functional groups on the fibrous surface of the exchanger. The effect of contact time, initial concentration and pH on the removal of Cr (VI), and adsorption isotherms at different temperature, was investigated. The results showed that the removal of Cr (VI) was very rapid and was significantly affected by the initial pH of the solution. Although acidic conditions (pH = 2-6) facilitated Cr (VI) adsorption, the exchanger was effective in neutral solution and even under weak base conditions. The equilibrium data fitted well with Langmuir adsorption model, and the maximum Cr (VI) adsorption capacities at pH 6.4 were 0.35, 0.36 and 0.38 mmol/g for 15, 25 and 35 degrees C, respectively. The exchanger was finally tested with real electroplating wastewater, and at sorbent dosage of 10 g/L, the removal efficiencies for Cr (VI) and total Cr were 99.4% and 97.8%, respectively. In addition, the positive relationship between adsorbed Cr (VI) and desorbed Cl- suggested that Cr (VI) was mainly removed by ion exchange with chlorine.

[Interrelationships of rhamnolipids, hydrophobic substrate and degrading bacteria].

The effect of rhamnolipids on pyrene degradation by Pseudomonas sp. GP3A was investigated to explore the interrelationships of biosurfactant, hydrophobic substrate and degrading bacteria. The cell surface hydrophobicity, lipopolysaccharide, hydrogen bond, bacterial biomass and pyrene degradation were determined. The results showed that the apparent solubility of pyrene was enhanced significantly when the concentration of rhamnolipids was higher than critical micelle concentration (CMC) of 60 mg x L(-1). Biosurfactant can increase the cell surface hydrophobicity by releasing the component of the cell wall-lipopolysaccharide; With the increase of cell surface hydrophobicity from 12% to 55%, bacterial biomass increased from 4.4 x 10(6) CFU x mL(-1) to 1.2 x 10(7) CFU x mL(-1), corresponding with the increase of pyrene degradation from 16% to 44%. Meanwhile, hydrogen bond was formed between biosurfactant and bacteria, which was beneficial to hydrophobic substrate degradation. The half-life of pyrene was shorten significantly. The average residual rate of pyrene in 10 days was 81% without rhamnolipids, but decreased to 57%, 41%, 33% and 26%, respectively with the addition of 20, 50, 200 and 500 mg x L(-1) of rhamnolipids.

The effects of nutrient amendment on biodegradation and cytochrome P450 activity of an n-alkane degrading strain of Burkholderia sp. GS3C.

The promotion of hexadecane biodegradation activity by an n-alkane degrading strain of Burkholderia cepacia (GS3C) with yeast extract amendment was studied using various carbon, nitrogen, vitamin, and amino acid amendments. Cytochrome P450 monooxygenase enzymes play a very important role and are especially required to introduce oxygen in n-alkane degradation. These enzymes from GS3C were located and detected using amino acid amendments. It was shown that biodegradation activity was promoted with amino acids amendments. However, only specific amino acids (L-phenylalanine, L-glutamic acid, L-proline, L-lysine, L-valine and L-leucine) have biodegradation promoting ability for GS3C. Cell protein concentration and cytochrome P450 activity were promoted significantly with the addition of L-phenylalanine and yeast extract. Furthermore, a significant positive linear relationship between cytochrome P450 activity and biodegradation efficiency of GS3C was observed. The results indicate that amino acid is the primary factor of nutrient amendment in promoting hexadecane biodegradation by influencing cytochrome P450 activity in GS3C.

Dechlorination pathways of diverse chlorinated aromatic pollutants conducted by Dehalococcoides sp. strain CBDB1.

Dechlorination of chlorinated aromatic pollutants (CAPs) has become a major issue in recent decades. This paper reported a theoretical indicator for predicting the reductive dechlorination pathways of polychlorinated dibenzo-p-dioxins (PCDDs), chlorobenzenes and chlorophenols transformed by Dehalococcoides sp. strain CBDB1. Density functional theory (DFT) calculations were carried out at the B3LYP/6-31G(d) level for all related CAPs and Mulliken atomic charges on chlorine atoms (Q(Cl(n))) were adopted as the probe of the dechlorination reaction activity. Q(Cl(n)) can consistently indicate the main dechlorination daughter products of PCDDs, chlorobenzenes and chlorophenols conducted by strain CBDB1. The dechlorination reaction favors elimination of the chlorine atoms having greater Q(Cl(n)) values. The chlorine atom with the greatest Q(Cl(n)) value tends preferentially to be eliminated, whereas the chlorine atom with the smallest Q(Cl()(n)()) value tends unlikely to be eliminated or does not react at all. For a series of compounds having similar structure, the maximal Q(Cl(n)) of each molecular can be used to predict the possibility of its daughter product(s). In addition, the difference (Q(Cl(n))) between the maximal Q(Cl(n)) and the next maximal Q(Cl(n)) of the same molecule can be used to assess the possibility of formation of multiple dechlorination products.

Rules of thumb for assessing reductive dechlorination pathways of PCDDs in specific systems.

This paper reports a theoretical validation and proposition of the reductive dechlorination pathways for polychlorinated dibenzo-p-dioxin (PCDD) congeners. Density functional theory (DFT) calculations were carried out at the B3LYP/6-31G(d) level for all PCDDs and Mulliken atomic charges on chlorine atoms were adopted as the probe of the dechlorination reaction activity. The experimentally substantiated dechlorination pathways of 1,2,3,4-tetrachlorodibenzo-p-dioxin (1,2,3,4-TCDD) and its daughter products in the presence of zero-valent zinc were validated and the complete pathway of dechlorination of octachlorodibenzo-p-dioxin (OCDD) was proposed. The proposed pathways were found to be consistent with anaerobic biotransformation of several PCDD congeners. Four rules of thumb arrived from this study include (1) the chlorine atoms in the longitudinal (1,4,6,9) positions are removed in preference to the chlorine atoms on lateral (2,3,7,8) positions; (2) the chlorine atom that has more neighboring chlorine atoms at ortho-, meta- and para-positions is to be eliminated; (3) reductive dechlorination prefers to take place on the benzene ring having more chlorine substitutions; and (4) a chlorine atom on the side of the longitudinal symmetry axis containing more chlorine atoms is preferentially eliminated. These rules of thumb can be conveniently used for rapidly predicting the major dechlorination pathway for a given PCDD in specific systems.

Rapid degradation of phenanthrene by using Sphingomonas sp. GY2B immobilized in calcium alginate gel beads.

The strain Sphingomonas sp. GY2B is a high efficient phenanthrene-degrading strain isolated from crude oil contaminated soils that displays a broad-spectrum degradation ability towards PAHs and related aromatic compounds. This paper reports embedding immobilization of strain GY2B in calcium alginate gel beads and the rapid degradation of phenanthrene by the embedded strains. Results showed that embedded immobilized strains had high degradation percentages both in mineral salts medium (MSM) and 80% artificial seawater (AS) media, and had higher phenanthrene degradation efficiency than the free strains. More than 90% phenanthrene (100 mg x L(-1)) was degraded within 36 h, and the phenanthrene degradation percentages were >99.8% after 72 h for immobilized strains. 80% AS had significant negative effect on the phenanthrene degradation rate (PDR) of strain GY2B during the linear-decreasing stage of incubation and preadsorption of cells onto rice straw could improve the PDR of embedded strain GY2B. The immobilization of strain GY2B possesses a good potential for application in the treatment of industrial wastewater containing phenanthrene and other related aromatic compounds.

Modeling and prediction of photolysis half-lives of polycyclic aromatic hydrocarbons in aerosols by quantum chemical descriptors.

Quantitative structure-property relationship (QSPR) modeling is a powerful approach for predicting environmental fate parameters of organic pollutants with their structure descriptors. This study reports QSPR models for photolysis half-lives of polycyclic aromatic hydrocarbons (PAHs) in aerosols. Quantum chemical descriptors computed with density functional theory at B3LYP/6-31G(d) level and partial least squares (PLS) analysis with optimizing procedure were used for generating QSPR models. The correlation coefficient of the optimal model was 0.993, and the fitting results showed this optimal model had high fitting precision and good predictability. The predicted photolysis half-lives by the optimal model are very close to those observed. The PLS assistant analysis indicated that PAHs with large electronic spatial extent tend to be photolyzed faster, while PAHs with high molecular total energy and small Mulliken atomic charges on the most negative carbon atom tend to be photolyzed slower in aerosols.