Yongrong Bian

Mercury reduction and complexation by natural organic matter in anoxic environments

Mercuric Hg(II) species form complexes with natural dissolved organic matter (DOM) such as humic acid (HA), and this binding is known to affect the chemical and biological transformation and cycling of mercury in aquatic environments. Dissolved elemental mercury, Hg(0), is also widely observed in sediments and water. However, reactions between Hg(0) and DOM have rarely been studied in anoxic environments. Here, under anoxic dark conditions we show strong interactions between reduced HA and Hg(0) through thiolate ligand-induced oxidative complexation with an estimated binding capacity of ~3.5 μmol Hg/g HA and a partitioning coefficient >106 mL/g. We further demonstrate that Hg(II) can be effectively reduced to Hg(0) in the presence of as little as 0.2 mg/L reduced HA, whereas production of Hg(0) is inhibited by complexation as HA concentration increases. This dual role played by DOM in the reduction and complexation of mercury is likely widespread in anoxic sediments and water and can be expected to significantly influence the mercury species transformations and biological uptake that leads to the formation of toxic methylmercury.

Effects of pH and metal ions on oxytetracycline sorption to maize-straw-derived biochar

Biochars produced from biomass residues have been recognized as effective sorbents to hydrophobic compounds, but knowledge on sorption of antibiotics to biochar and its mechanisms are still inadequate. Sorption of oxytetracycline (OTC) in aqueous solution to maize-straw-derived biochar, and the effect of pH and metal ions, was investigated in batch experiments, and the main sorption mechanisms were elucidated using FTIR and zeta potential measurements. The results showed that sorption of OTC on biochar was highly pH-dependant. The amount of sorbed OTC first increased and then decreased with increasing pH, and maximum sorption was achieved at pH 5.5. Cu(2+) enhanced the sorption of OTC, while Pb(2+) slightly reduced the sorption under acidic conditions. Other metal ions had no significant effect on the sorption of OTC to biochar. Surface complexation, through π-π interaction and metal bridging, was the most important sorption mechanism although cation exchange might have played a role.

Polycyclic aromatic hydrocarbons in soils in the vicinity of Nanjing, China

The occurrence and distribution of polycyclic aromatic hydrocarbons (PAHs) in vegetable soils from five vegetable fields (including: Liuhe, Xixia, Pukou, Jianye and Yuhua districts) in Nanjing outskirt were investigated with high performance liquid chromatography (HPLC) equipped with fluorescence detector. The total concentrations of 15 priority PAHs in 126 soil samples ranged from 21.91 to 533.84ng g(-1) dry weight, and the sum of seven carcinogenic PAHs concentrations varied from 1.48 to 236.19ng g(-1) dry weight. Statistical analysis of the PAHs concentrations showed that the highest PAHs concentration was observed in Liuhe, and the lowest PAHs concentrations were found in Xixia among the five districts. The ratios of fluoranthene to sum of fluoranthene and pyrene concentrations (Flt/(Flt+Pyr)) were more than 0.5 in 99% of vegetable soil samples, showing that the PAHs in soils were generally derived from straw and coal combustion sources. The results from principal component analysis (PCA) further indicated that extensive combustion activities affected the PAHs distribution in Nanjing vegetable soils.

Bioavailability assessment of hexachlorobenzene in soil as affected by wheat straw biochar.

Biochar incorporation with soil could increase sorption of organic contaminants, thereby reducing their bioavailability. In this study, the effects of wheat straw biochar on the sorption, dissipation and bioavailability of hexachlorobenzene (HCB), a typical persistent organic pollutant (POP), were investigated in laboratory experiments. We observed that HCB sorption by biochar was 42 times higher than that by soil and the sorption isotherm was linear for the concentration range studied. Biochar amendments reduced HCB dissipation, volatilization and earthworm (Eisenia foetida) uptake of HCB from soil. Hydroxypropyl-β-cyclodextrin extraction correlated better with the earthworm bioassay than butanol extraction of HCB in biochar-amended soil. The results of both chemical extraction and earthworm bioassay indicate that biochar amendment of soil resulted in a rapid reduction in the bioavailability of HCB, even for the 0.1% biochar application rate. This suggested that wheat straw biochar could potentially be used in immobilizing POPs in contaminated sites.

Binding Constants of Mercury and Dissolved Organic Matter Determined by a Modified Ion Exchange Technique

Ion-exchange techniques have been widely used for determining the conditional stability constants (logK) between dissolved organic matter (DOM) and various metal ions in aqueous solution. An exception is mercuric ion, Hg2+, whose exceedingly strong binding with reduced sulfur or thiol-like functional groups in DOM makes the ion exchange reactions difficult. Using a Hg-selective thiol resin, we have developed a modified ion-exchange technique which overcomes this limitation. This technique allows not only the determination of binding constants between Hg2+ and DOM of varying origins, but also the discrimination of complexes with varying coordination numbers [i.e., 1:1 and 1:2 Hg:thiol-ligand (HgL) complexes]. Measured logK values of four selected DOM isolates varied slightly from 21.9 to 23.6 for 1:1 HgL complexes, and from 30.1 to 31.6 for 1:2 HgL(2) complexes. These results suggest similar binding modes that are likely occurring between Hg2+ and key thiolate functional groups in DOM particularly at a relatively low Hg to DOM ratio. Future studies should further elucidate the nature and precise stoichiometries of binding between Hg2+ and DOM at environmentally relevant concentrations.

PAHs biodegradation potential of indigenous consortia from agricultural soil and contaminated soil in two-liquid-phase bioreactor (TLPB)

Estimation of PAHs degradation potential of indigenous consortia is essential for remediation of polluted soils. In this study, the biodegradation of a mixture of 11 PAHs was compared using a long-term PAH-contaminated soil (CS) and an unpolluted agricultural soil (AS) as inocula in a two-liquid-phase bioreactor (TLPB). In the TLPB, silicone oil was used as the organic phase to increase the PAHs bioavailability. The microbial numbers were also determined during the biodegradation. The results demonstrated that naphthalene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene could be completely biodegraded in both soils within 4-50 days. With the exception of dibenzo(a,h)anthrancene, the other PAHs including benzo(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene and benzo(k)fluoranthene were degraded to different extents in both soils at the end of 170 days. Complete biodegradation of benzo(a)anthracene and benzo(b)fluoranthene only occurred in CS. During the process, microbial growth was highly correlated to the biodegradation of PAHs. Sequential utilization of PAHs showed a competitive-inhibition in the multi-substrate system. The half-life times of PAHs obtained here were much shorter than those reported previously in soils, indicating that indigenous microbes in both soils had high PAHs degradation potential, facilitated by TLPB.

Residual Characteristics of Organochlorine Pesticides in Lou Soils with Different Fertilization Modes

ABSTRACT Soil samples with three fertilization treatments (no fertilizer, corn straw and farm manure) collected from a Lou soil (Eum-orthic Anthrosol classfied using Chinese Soil Taxonomy) in northwestern China were analysed for residual levels and their characteristics of organochlorine pesticides (α-HCH, β-HCH, γ-HCH, δ-HCH, HCB, o, p′-DDT, p, p′-DDT, o, p′-DDE, p, p′-DDE, p, p′-DDD, α-endosulfan, dieldrin and endrin). Organochlorine pesticides (OCPs) were detected in all soil samples except δ-HCH and their total concentrations ranged from 159.31 ± 9.00 to 179.77 ± 2.58 ng g −1 with an order of HCHs > DDTs > (dieldrin + endrin) > HCB > α-endosulfan. Among all the compounds, γ-HCH had the highest concentration followed by p, p′-DDE. The residual levels of HCH isomers and DDT as well as their metabolites in soil with different fertilization treatments were in the order of γ-HCH > β-HCH ≈ α-HCH > δ-HCH and p, p′-DDE > p, p′-DDT > o, p′-DDT > p, p′-DDD ≈ o, p′-DDE, respectively. DDE/DDT ratios ranged from 1.59 ± 0.13 to 3.35 ± 0.16 and endrin/dieldrin ratios from 1.40 ± 0.06 to 9.20 ± 4.05, both indicating no new occurrence of these pesticides in these soils, while α-HCH/γ-HCH ratios of 0.04 indicated a new input of lindane (almost pure γ-HCH) in the past several years. The farm manure treatments showed lower DDT residues than samples without fertilizer. Also addition of corn straw and farm manure increased soil organic matter content and decreased the soil pH which could retard the degradation of DDT in the soil.

Quantitative structure–toxicity relationship study of lethal concentration to tadpole (Bufo vulgaris formosus) for organophosphorous pesticides

In the present study more than 1,000 structural parameters of 41 organophosphorus pesticides (OPs) were calculated using the software ChemOffice 8.03 and Dragon 2.1. Then, with multivariate linear regression and best subset regression analyses, different equations were derived to calculate the lethal toxicity, LC(50), for these 41 organophosphorous pesticides found in tadpoles (Bufo vulgaris formosus). An equation was developed for all selected OPs, especially those with relatively low toxicity levels (LC(50)>4.5mM) that accounted for 89.09% of the variability in the toxic effect. The equation indicated that the main contributions to OPs toxicity with tadpoles were the electrostatic contribution qH(+) (maximum net positive H atomic charge), spatial autocorrelation (MATS7 m) and hydrophobicity (lgK(ow)), with the two former being the most important parameters. For OPs with high toxicity, however, different structural parameters were introduced. The following equation was developed with LC(50)<4.5mM. These equations implied that with different levels of toxicity there could have different mechanisms in the tadpole. Furthermore, the results showed that molecular structural parameters had a particular value in modeling chemical reactivity within a homologous series of compounds.

Novel Biochar-Plant Tandem Approach for Remediating Hexachlorobenzene Contaminated Soils: Proof-of-Concept and New Insight into the Rhizosphere

Volatilization of semi/volatile persistent organic pollutants (POPs) from soils is a major source of global POPs emission. This proof-of-concept study investigated a novel biochar-plant tandem approach to effectively immobilize and then degrade POPs in soils using hexachlorobenzene (HCB) as a model POP and ryegrass (Lolium perenne L.) as a model plant growing in soils amended with wheat straw biochar. HCB dissipation was significantly enhanced in the rhizosphere and near rhizosphere soils, with the greatest dissipation in the 2 mm near rhizosphere. This enhanced HCB dissipation likely resulted from (i) increased bioavailability of immobilized HCB and (ii) enhanced microbial activities, both of which were induced by ryegrass root exudates. As a major component of ryegrass root exudates, oxalic acid suppressed HCB sorption to biochar and stimulated HCB desorption from biochar and biochar-amended soils, thus increasing the bioavailability of HCB. High-throughput sequencing results revealed that the 2 mm near rhizosphere soil showed the lowest bacterial diversity due to the increased abundance of some genera (e.g., Azohydromonas, Pseudomonas, Fluviicola, and Sporocytophaga). These bacteria were likely responsible for the enhanced degradation of HCB as their abundance was exponentially correlated with HCB dissipation. The results from this study suggest that the biochar-plant tandem approach could be an effective strategy for remediating soils contaminated with semi/volatile organic contaminants.

Use of Organic Solvents to Extract Organochlorine Pesticides (OCPs) from Aged Contaminated Soils

Abstract Problems associated with organochlorine pesticide (OCP)-contaminated sites in China have received wide attention. To solve such problems, innovative ex-situ methods of site remediation are urgently needed. We investigated the feasibility of the extraction method with different organic solvents, ethanol, 1-propanol, and three fractions of petroleum ether, using a soil collected from Wujiang (WJ), China, a region with long-term contamination of dichlorodiphenyltrichloroethanes (DDTs). We evaluated different influential factors, including organic solvent concentration, washing time, mixing speed, solution-to-soil ratio, and washing temperature, on the removal of DDTs from the WJ soil. A set of relatively better parameters were selected for extraction with 100 mL L −1 petroleum ether (60–90 °C): washing time of 180 min, mixing speed of 100 r min −1 , solution-to-soil ratio of 10:1, and washing temperature of 50 °C. These selected parameters were also applied on three other seriously OCP-polluted soils. Results demonstrated their broad-spectrum effectiveness and excellent OCP extraction performance on the contaminated soils with different characteristics.