Yongfeng Wang

Degradation, metabolism, and bound-residue formation and release of Tetrabromobisphenol A in soil during sequential anoxic-oxic incubation.

Tetrabromobisphenol A (TBBPA) is one of the most commonly used flame retardants and has become an environmental contaminant worldwide. We studied the fate of (14)C-labeled TBBPA in soil under static anoxic (195 days) and sequential anoxic (125 days)-oxic (70 days) conditions. During anoxic incubation, TBBPA dissipated with a half-life of 36 days, yielding four debromination metabolites: bisphenol A (BPA) and mono-, di-, and tribrominated BPA. At the end of anoxic incubation, all four brominated BPAs completely disappeared, leaving BPA (54% of initial TBBPA) as the sole detectable organic metabolite. TBBPA dissipation was accompanied by trace mineralization (<1.3%) and substantial bound-residue formation (35%), probably owing to chemical binding to soil organic matter. Subsequent oxic incubation was effective in degrading accumulated BPA (half-life 11 days) through mineralization (6%) and bound-residue formation (62%). However, 42% of the anoxically formed bound residues was released as TBBPA and lower brominated BPAs, which were then persistent during oxic incubation. Our results provide the first evidence for release of bound residues during alteration of the redox environment and indicate that sequential anoxic-oxic incubation approaches-considered effective in remediation of environments containing halogenated xenobiotics-do not completely remove xenobiotics from environmental matrices.

Effects of the geophagous earthworm Metaphire guillelmi on sorption, mineralization, and bound-residue formation of 4-nonylphenol in an agricultural soil

Effects of earthworms on fate of nonylphenol (NP) are obscure. Using (14)C-4-NP111 as a representative, we studied the fate of 4-NP in an agricultural soil with or without the earthworm Metaphire guillelmi and in fresh cast of the earthworm. Sorption of 4-NP on the cast (Kd 1564) was significantly higher than on the parent soil (Kd 1474). Mineralization of 4-NP was significantly lower in the cast (13.2%) and the soil with earthworms (10.4%) than in the earthworm-free soil (16.0%). One nitro metabolite of 4-NP111 (2-nitro-4-NP111) was identified in the soil and cast, and the presence of the earthworm significantly decreased its amounts. The presence of earthworm also significantly decreased formation of bound residues of 4-NP in the soil. Our results demonstrate that earthworms could significantly change the fate of 4-NP, underlining that earthworm effects should be considered when evaluating behavior and risk of 4-NP in soil.

Effects of biochar and the geophagous earthworm Metaphire guillelmi on fate of 14C-catechol in an agricultural soil

Both biochar and earthworms can exert influence on behaviors of soil-borne monomeric phenols in soil; however, little was known about the combined effects of biochar and earthworm activities on fate of these chemicals in soil. Using (14)C-catechol as a representative, the mineralization, transformation and residue distribution of phenolic humus monomer in soil amended with different amounts of biochar (0%, 0.05%, 0.5%, and 5%) without/with the geophagous earthworm Metaphire guillelmi were investigated. The results showed biochar at amendment rate <0.5% did not affect (14)C-catechol mineralization, whereas 5% biochar amendment significantly inhibited the mineralization. Earthworms did not affect the mineralization of (14)C-catechol in soil amended with <0.5% biochar, but significantly enhanced the mineralization in 5% biochar amended soil when they were present in soil for 9 d. When earthworms were removed from the soil, the mineralization of (14)C-catechol was significantly lower than that of in earthworm-free soil indicating that (14)C-catecholic residues were stabilized during their passage through earthworm gut. The assimilation of (14)C by earthworms was low (1.2%), and was significantly enhanced by biochar amendment, which was attributed to the release of biochar-associated (14)C-catecholic residues during gut passage of earthworm.

Formation, characterization, and mineralization of bound residues of tetrabromobisphenol A (TBBPA) in silty clay soil under oxic conditions

The nature and stability of bound residues (BRs) derived from the widely used brominated flame retardant tetrabromobisphenol A (TBBPA) in fine-textured soil is unknown. We incubated 14C-labeled TBBPA in silty clay rice paddy soil for 93days under oxic conditions. TBBPA dissipated with a first-order kinetic constant kd of 0.0474±0.0017day-1 (t1/2 14.6±0.3days) and mineralized with a km of 0.0011±0.00002day-1. At the end of the incubation, four metabolites, including two methylation products (TBBPA monomethyl and dimethyl ether), accounted for 7.9±0.1% of the initial TBBPA. The BRs continuously increased in amount to a maximum of 80.1±3.6%. About 86.3±0.9% of the BRs localized in the humin fraction and 55.9±1.5% was hydrolyzable with strong alkali (SAH-BRs), which represents reversible BRs. Together with results previously reported for coarse-textured soil, these results indicate that the absolute amounts of both BRs and SAH-BRs of TBBPA as well as the relative contribution of SAH-BRs to total BRs in fine-textured soil are markedly higher than in coarse-textured soil. When BRs-containing soil was incubated with fresh soil for 231days, 9.2±0.3% was mineralized (km 0.00047±0.00002day-1) and SAH-BRs decreased to 34.1±1.1%, accompanied by transformation into other BR forms. These indicate that BRs are bioavailable in the soil. Amendment with rice root exudates did not effectively affect the mineralization, release, and distribution of BRs, suggesting that bioavailability of BRs but not microbial activity limits the degradation of BRs in the silty clay soil. This study provides first insights into the nature and stability of TBBPA-derived BRs in fine-textured soil under oxic conditions and indicates the significant role of reversible BRs in the environmental risk of TBBPA.

Fate and metabolism of the brominated flame retardant tetrabromobisphenol A (TBBPA) in rice cell suspension culture.

Tetrabromobisphenol A (TBBPA) is the brominated flame retardant with the highest production volume and its bioaccumulation in environment has caused both human health and environmental concerns, however the fate and metabolism of TBBPA in plants is unknown. We studied the fate, metabolites, and transformation of (14)C-labeled TBBPA in rice cell suspension culture. During the incubation for 14 days, TBBPA degradation occurred continuously in the culture, accompanied by formation of one anisolic metabolite [2,6-dibromo-4-(2-(2-hydroxy)-propyl)-anisole] (DBHPA) (50% of the degraded TBBPA) and cellular debris-bound residues (46.4%) as well as mineralization (3.6%). The cells continuously accumulated TBBPA in the cytoplasm, while a small amount of DBHPA (2.1% of the initially applied TBBPA) was detectable inside the cells only at the end of incubation. The majority of the accumulated residues in the cells was attributed to the cellular debris-bound residues, accounting for 70-79% of the accumulation after the first incubation day. About 5.4% of the accumulation was associated with cell organelles, which contributed 7.5% to the cellular debris-bound residues. Based on the fate and metabolism of TBBPA in the rice cell suspension culture, a type II ipso-substitution pathway was proposed to describe the initial step for TBBPA degradation in the culture and balance the fate of TBBPA in the cells. To the best of our knowledge, our study provides for the first time the insights into the fate and metabolism of TBBPA in plants and points out the potential role of type II ipso-hydroxylation substitution in degradation of alkylphenols in plants. Further studies are required to reveal the mechanisms for the bound-residue formation (e.g., binding of residues to specific cell wall components), nature of the binding, and toxicological effects of the bound residues and DBHPA.

Stimulation of Tetrabromobisphenol A Binding to Soil Humic Substances by Birnessite and the Chemical Structure of the Bound Residues

Studies have shown the main fate of the flame retardant tetrabromobisphenol A (TBBPA) in soils is the formation of bound residues, and mechanisms on it are less-understood. This study investigated the effect of birnessite (δ-MnO2), a naturally occurring oxidant in soils, on the formation of bound residues. (14)C-labeled TBBPA was used to investigate the pH dependency of TBBPA bound-residue formation to two soil humic acids (HAs), Elliott soil HA and Steinkreuz soil HA, in the presence of δ-MnO2. The binding of TBBPA and its transformation products to both HAs was markedly increased (3- to 17-fold) at all pH values in the presence of δ-MnO2. More bound residues were formed with the more aromatic Elliott soil HA than with Steinkreuz soil HA. Gel-permeation chromatography revealed a uniform distribution of the bound residues within Steinkreuz soil HA and a nonuniform distribution within Elliott soil HA. (13)C NMR spectroscopy of (13)C-TBBPA residues bound to (13)C-depleted HA suggested that in the presence of δ-MnO2, binding occurred via ester and ether and other types of covalent bonds besides HA sequestration. The insights gained in this study contribute to an understanding of the formation of TBBPA bound residues facilitated by δ-MnO2.

Synthesis and characterization of 14C‐labelled sulfate conjugates of steroid oestrogens

Steroid oestrogens are typical endocrine-disrupting compounds in the environment and are excreted from the human and animals mainly as conjugates, including sulfate and glucuronide salts. The oestrogen conjugates are largely biologically inactive, but they can be de-conjugated and release free oestrogens, which usually exhibit strong oestrogenicity. Therefore, it is important to study the fate of oestrogen conjugates in the environment. However, because of the complexity of environmental matrixes, time-consuming pre-treatments of samples are usually required to reduce the interference of the matrixes. (14)C radioisotope can trace target substances and their degradation products at low concentrations in complex environmental samples and is therefore essential in such studies. We synthesized three oestrogen sulfates with (14)C-labelling at the ring, i.e. [3-(14)C]-estrone-3-sulfate ammonium salt, [3-(14)C]-17β-estradiol-17-sulfate ammonium salt, and [3-(14)C]-17β-estradiol-3,17-disulfate diammonium salt with radiochemical purities of >98% by sulfation of [3-(14)C]-labelled estrone and 17β-estradiol in dry pyridine with SO3 -triethylamine at room temperature or 90-95 °C, followed by hydrolysis with KOH-methanol solution and purification by preparative thin-layer chromatography on silica gel using an ammonia-containing eluent. The products were characterized by mass spectrometry and (13)C and (1)H nuclear magnetic resonance spectroscopy, using their corresponding non-labelled compounds. The (14)C-labelled oestrogen conjugates provide possibilities for studying their fate in soil and sediment environments as well as in the animal manure.

Effects of Cu 2+ and humic acids on degradation and fate of TBBPA in pure culture of Pseudomonas sp. strain CDT

Soil contamination with tetrabromobisphenol A (TBBPA) has caused great concerns; however, the presence of heavy metals and soil organic matter on the biodegradation of TBBPA is still unclear. We isolated Pseudomonas sp. strain CDT, a TBBPA-degrading bacterium, from activated sludge and incubated it with 14C-labeled TBBPA for 87 days in the absence and presence of Cu2+ and humic acids (HA). TBBPA was degraded to organic-solvent extractable (59.4%±2.2%) and non-extractable (25.1%±1.3%) metabolites, mineralized to CO2 (4.8%±0.8%), and assimilated into cells (10.6%±0.9%) at the end of incubation. When Cu2+ was present, the transformation of extractable metabolites into non-extractable metabolites and mineralization were inhibited, possibly due to the toxicity of Cu2+ to cells. HA significantly inhibited both dissipation and mineralization of TBBPA and altered the fate of TBBPA in the culture by formation of HA-bound residues that amounted to 22.1%±3.7% of the transformed TBBPA. The inhibition from HA was attributed to adsorption of TBBPA and formation of bound residues with HA via reaction of reactive metabolites with HA molecules, which decreased bioavailability of TBBPA and metabolites in the culture. When Cu2+ and HA were both present, Cu2+ significantly promoted the HA inhibition on TBBPA dissipation but not on metabolite degradation. The results provide insights into individual and interactive effects of Cu2+ and soil organic matter on the biotransformation of TBBPA and indicate that soil organic matter plays an essential role in determining the fate of organic pollutants in soil and mitigating heavy metal toxicity.

Transformation of tetrabromobisphenol A by Rhodococcus jostii RHA1: Effects of heavy metals

Tetrabromobisphenol A (TBBPA) is one of the most widely used brominated flame retardants in the world but it is also a pollutant of global concern. In the present study, we studied the transformation of 14C-labeled TBBPA by a polychlorinated-biphenyl-degrading bacterium, Rhodococcus jostii RHA1 (RHA1), under oxic conditions. During the 5-day incubation, TBBPA was biotransformed rapidly first to its monomethyl ether MeO-TBBPA and then to its more hydrophobic but less toxic dimethyl ether diMeO-TBBPA. The biotransformation followed pseudo-first-order decay kinetics, with a half-life of TBBPA of 0.32 days and only 0.6% of the initially added amount being mineralized. Considering the frequent co-occurrence of TBBPA with heavy metals in the natural environment, we also investigated the effects of three heavy metals (Cd, Cu, and Fe) on the transformation of TBBPA by strain RHA1. While TBBPA transformation was not significantly altered by Cd, it was accelerated by Cu and Fe, presumably due to the effects of these two essential metals on O-methyltransferase activity. Overall, the present study showed that RHA1 is an effective transformer of TBBPA and that certain essential metals, including Cu and Fe, promote the transformation.