Effect of Cu2+ on the Laccase-Inducted Formation of Non-Extractable Residues of Tetrabromobisphenol A in Humic Acids.

We used 14 C-radiolabelling to study the non-extractable residues (NERs) formation of tetrabromobisphenol A (TBBPA) in a humic acid (HA) suspension under catalysis of laccase in the presence of copper. When entering the suspension after TBBPA adsorbing to HA supramolecular associates, Cu2+ at low concentrations (even without toxicity to laccase) significantly reduced the amount and first-order kinetic constant of the NER formation, while Cu2+ had no significant effect on the formation after it was complexed with HA. The inhibition effect of Cu2+ on the NER formation is explained to be attributed to the prevention of laccase-induced oxidation of TBBPA in the voids of HA associates by complexation of Cu2+ with periphery molecules of the associates. The results provide insights into varying effects of heavy metals on the environmental fate of organic contaminants and suggest that co-existing heavy metals could increase their environmental risk by reducing their NER formation.

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.

Fate of Tetrabromobisphenol A (TBBPA) and Formation of Ester- and Ether-Linked Bound Residues in an Oxic Sandy Soil.

Bound-residue formation is a major dissipation process of most organic xenobiotics in soil. However, both the formation and nature of bound residues of tetrabromobisphenol A (TBBPA) in soil are unclear. Using a 14C-tracer, we studied the fate of TBBPA in an oxic soil during 143 days of incubation. TBBPA dissipated with a half-life of 14.7 days; at the end of incubation, 19.6% mineralized and 66.5% formed bound residues. Eight extractable metabolites were detected, including TBBPA methyl ethers, single-ring bromophenols, and their methyl ethers. Bound residues (mostly bound to humin) rapidly formed during the first 35 days. The amount of those humin-bound residues then quickly decreased, whereas total bound residues decreased slowly. By contrast, residues bound to humic acids and fulvic acids increased continuously until a plateau was reached. Ester- and ether-linked residues accounted for 9.6-27.0% of total bound residues during the incubation, with ester linkages being predominant. Residues bound via ester linkages consisted of TBBPA, TBBPA monomethyl ether, and an unknown polar compound. Our results indicated that bound-residue formation is the major pathway of TBBPA dissipation in oxic soil and provide first insights into the chemical structure of the reversibly ester-linked bound residues of TBBPA and its metabolites.

Enhanced transformation of tetrabromobisphenol a by nitrifiers in nitrifying activated sludge.

The fate of the most commonly used brominated flame retardant, tetrabromobisphenol A (TBBPA), in wastewater treatment plants is obscure. Using a (14)C-tracer, we studied TBBPA transformation in nitrifying activated sludge (NAS). During the 31-day incubation, TBBPA transformation (half-life 10.3 days) was accompanied by mineralization (17% of initial TBBPA). Twelve metabolites, including those with single benzene ring, O-methyl TBBPA ether, and nitro compounds, were identified. When allylthiourea was added to the sludge to completely inhibit nitrification, TBBPA transformation was significantly reduced (half-life 28.9 days), formation of the polar and single-ring metabolites stopped, but O-methylation was not significantly affected. Abiotic experiments confirmed the generation of mono- and dinitro-brominated forms of bisphenol A in NAS by the abiotic nitration of TBBPA by nitrite, a product of ammonia-oxidizing microorganisms (AOMs). Three biotic (type II ipso-substitution, oxidative skeletal cleavage, and O-methylation) and one abiotic (nitro-debromination) pathways were proposed for TBBPA transformation in NAS. Apart from O-methylation, AOMs were involved in three other pathways. Our results are the first to provide information about the complex metabolism of TBBPA in NAS, and they are consistent with a determining role for nitrifiers in TBBPA degradation by initiating its cleavage into single-ring metabolites that are substrates for the growth of heterotrophic bacteria.

Degradation and metabolism of tetrabromobisphenol A (TBBPA) in submerged soil and soil-plant systems.

Contamination by tetrabromobisphenol A (TBBPA), the most widely used brominated flame retardant, is a matter of environmental concern. Here, we investigated the fate and metabolites of (14)C-TBBPA in a submerged soil with an anoxic-oxic interface and planted or not with rice (Oryza sativa) and reed (Phragmites australis) seedlings. In unplanted soil, TBBPA dissipation (half-life 20.8 days) was accompanied by mineralization (11.5% of initial TBBPA) and the substantial formation (60.8%) of bound residues. Twelve metabolites (10 in unplanted soil and 7 in planted soil) were formed via four interconnected pathways: oxidative skeletal cleavage, O-methylation, type II ipso-substitution, and reductive debromination. The presence of the seedlings strongly reduced (14)C-TBBPA mineralization and bound-residue formation and stimulated debromination and O-methylation. Considerable radioactivity accumulated in rice (21.3%) and reed (33.1%) seedlings, mainly on or in the roots. While TBBPA dissipation was hardly affected by the rice seedlings, it was strongly enhanced by the reed seedlings, greatly reducing the half-life (11.4 days) and increasing monomethyl TBBPA formation (11.3%). The impact of the interconnected aerobic and anaerobic transformation of TBBPA and wetland plants on the profile and dynamics of the metabolites should be considered in phytoremediation strategies and environmental risk assessments of TBBPA in submerged soils.

Size-segregated characteristics of water-soluble oxidative potential in urban Xiamen: Potential driving factors and implications for human health.

Oxidative potential (OP), defined as the ability of particulate matter (PM) to generate reactive oxygen species (ROS), has been considered as a potential health-related metric for PM. Particles with different sizes have different OP and deposition efficiencies in the respiratory tract and pose different health risks. In this study, size-segregated PM samples were collected at a coastal urban site in Xiamen, a port city in southeastern China, between August 2020 and September 2021. The water-soluble constituents, including inorganic ions, elements and organic carbon, were determined. Total volume-normalized OP based on the dithiothreitol assay was highest in spring (0.241 ± 0.033 nmol min-1 m-3) and lowest in summer (0.073 ± 0.006 nmol min-1 m-3). OP had a biomodal distribution with peaks at 0.25-0.44 µm and 1.0-1.4 µm in spring, summer, and winter and a unimodal pattern with peak at 0.25-0.44 µm in fall, which were different from the patterns of redox-active species. Variations in the seasonality of fine and coarse mode OP and their correlations with water-soluble constituents showed that the size distribution patterns of OP could be attributed to the combined effects of the size distributions of transition metals and redox-active organics and the interactions between them which varied with emissions, meteorological conditions and atmospheric processes. Respiratory tract deposition model indicated that the deposited OP and the toxic elements accounted for 47.9 % and 36.8 % of their measured concentrations, respectively. The highest OP doses and the excess lifetime carcinogenic risk (ELCR) were found in the head airway (>70 %). However, the size distributions of OP deposition and ELCR in the respiratory tract were different, with 63.9 % and 49.4 % of deposited ELCR and OP, respectively, coming from PM2.5. Therefore, attention must be paid to coarse particles from non-exhaust emissions and road dust resuspension.

Impacts of distorted local chemical coordination on electrochemical performance in hydrated vanadium pentoxide.

Modulating and elevating the operating voltage of a given cathode is a significant challenge to enhance the energy density of secondary batteries without sacrificing power output. The chemical coordination strongly influences the energy levels of d-orbitals of redox cations in cathode materials, which tie to their operating voltage. In contrast to concentrated studies on enhancing the specific capacity, in this study, we choose bi-layered hydrated vanadium pentoxide as the model to modulate the d-orbital energy levels through local chemical coordination manipulation, achieving a higher operating voltage in rechargeable aqueous zinc ion batteries. Here we show that, by employing X-ray absorption spectroscopy (XAS) and pair distribution function (PDF) techniques, we can analyze the distortion of [VO6] octahedra and extract chemical bond information, deciphering the correlation between the chemical coordination and operating voltage in cathode materials. The fundamentals could guide the designing and developing RAZIBs with higher energy and power density.

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.

[Atmospheric NH3 Emission Inventory and Its Tempo-spatial Changes in Xiamen-Zhangzhou-Quanzhou Region from 2015 to 2020].

Based on the district and county activity level data of different types of atmospheric ammonia (NH3) emission sources in the Xiamen-Zhangzhou-Quanzhou (XZQ) Region and the modified emission factors, an ammonia emission inventory with a spatial resolution of 1 km×1 km in 2017 was established. In addition, the annual variations in NH3 emission from 2015 to 2020 in this region were analyzed. The results showed that the emission of NH3 in the XZQ Region in 2017 was 27.40 kt with livestock and poultry breeding, farmland ecosystem, human emission, fuel combustion, and waste treatment accounting for 42.48%, 22.04%, 14.71%, 7.08%, and 5.69% of the total emission, respectively. The order of emission density of NH3 was Xiamen (1.94 t·km-2)>Quanzhou (1.07 t·km-2)>Zhangzhou (0.95 t·km-2). High values of emission density were mainly concentrated in the coastal urban areas with a concentrated population and the inland township areas with developed livestock and poultry breeding and planting industries. The monthly variation in NH3 emissions was consistent with the pattern of temperature change, with high values in summer. Due to the different economic structure and development level in different cities, NH3 emissions in Quanzhou City showed a decline from 2015 to 2020, whereas there were fluctuations in the trends of ammonia emissions in Xiamen and Zhangzhou cities. The relationship between NH3 emission intensity and per capita GDP was significantly negative.

Isomer-specific degradation of branched and linear 4-nonylphenol isomers in an oxic soil.

Using (14)C- and (13)C-ring-labeling, degradation of five p-nonylphenol (4-NP) isomers including four branched (4-NP(38), 4-NP(65), 4-NP(111), and 4-NP(112)) and one linear (4-NP(1)) isomers in a rice paddy soil was studied under oxic conditions. Degradation followed an availability-adjusted first-order kinetics with the decreasing order of half-life 4-NP(111) (10.3 days) > 4-NP(112) (8.4 days) > 4-NP(65) (5.8 days) > 4-NP(38) (2.1 days) > 4-NP(1) (1.4 days), which is in agreement with the order of their reported estrogenicities. One metabolite of 4-NP(111) with less polarity than the parent compound occurred rapidly and remained stable in the soil. At the end of incubation (58 days), bound residues of 4-NP(111) amounted to 54% of the initially applied radioactivity and resided almost exclusively in the humin fraction of soil organic matter, in which chemically humin-bound residues increased over incubation. Our results indicate an increase of specific estrogenicity of the remaining 4-NPs in soil as a result of the isomer-specific degradation and therefore underline the importance of understanding the individual fate (including degradation, metabolism, and bound-residue formation) of isomers for risk assessment of 4-NPs in soil. 4-NP(1) should not be used as a representative of 4-NPs for studies on their environmental behavior.

Degradation behaviors of Isopropylphenazone and Aminopyrine and their genetic toxicity variations during UV/chloramine treatment.

Combination of ultraviolet and chloramine (i.e., UV/chloramine) treatment has been attracting increasingly attention in recent years due to its high efficiency in removing trace organic contaminants. This study investigated the degradation behaviors of two pyrazolone pharmaceuticals (i.e., Isopropyl phenazone (PRP) and Aminopyrine (AMP)) and their genetic toxicity variations during UV/chloramine treatment. The results showed that chloramine could hardly degrade PRP and AMP, while UV/chloramine greatly increased the observed first-order rate constant (kobs) of PRP and AMP degradation. The quenching and probe experiments illustrated that the reactive chlorine species (RCS) contributed dominantly to PRP removal, and hydroxyl radical (HO•) was the major contributor to the degradation of AMP, while the reactive amine radicals (RNS) could hardly degrade them. The overall degradation rates of PRP and AMP decreased as pH increased from 6.5 to 10. The kobs of PRP and AMP increased along with NH2Cl dosage increasing and reached a plateau at higher concentrations (0.2-0.5 mM). The present background carbonate (HCO3-, 1-10 mM), chloride (Cl-, 1-10 mM) and natural organic matter (NOM, 5-10 mg-C L-1) exhibited inhibition impacts on PRP and AMP degradation. In addition, the intermediates/products of PRP and AMP were identified and their general degradation pathways were proposed to be hydroxylation, deacetylation, and dephenylization. Specifically, Cl-substitution was inferred during PRP degradation, while demethylation in tertiary amine group was only observed in AMP degradation. These mechanisms including the main reactive sites of PRP and AMP were further confirmed by the frontier orbitals calculation. Moreover, the results of the genetic toxicity according to the micronucleus test of Viciafaba root tip indicated that UV/chloramine treatment could partially reduce the genetic toxicity of PRP and AMP.

[Distribution of Different Phosphorus Species in Water and Sediments from Gaocun to Lijin Reaches of the Yellow River].

The Yellow River is the second longest river in China, which plays a very important role in the transportation of nutrients at the regional and even global scale. Water and sediment samples were collected at five sites located at the Gaocun to Lijin reaches along the Yellow River and the distribution characteristics of different phosphorus species were analyzed. The concentration of suspended particulate matter (SPM) in water ranged from 1.89 to 2.67 g·L-1 with an average of 2.26 g·L-1 in May and from 0.43 to 1.79 g·L-1 with an average of 1.21 g·L-1 in September. It almost had the same variation rule as the water flux, which reflects the influence of water flux on SPM transportation. The concentration of total phosphorus (TP) in water ranged from 0.05 to 2.31 mg·L-1 in May and from 0.03 to 0.1 mg·L-1 in September. Particulate phosphorus (PP) was the dominant TP species in both months, and TP and PP were significantly correlated (P<0.01), which implied that phosphorus loss in soil from Gaocun to Lijin reaches is still serious. Water runoff was positively correlated with TP and PP (P<0.05), but negatively correlated with total dissolved phosphorus (TDP) and dissolved inorganic phosphorus (DIP) (P<0.05, P<0.01, respectively). Increasing water runoff obviously increased the dilution of TDP and DIP. The concentration of SPM was negatively correlated with DIP (P<0.01), the adsorption of SPM on phosphorus was mainly the adsorption of DIP. The permanganate index in water was higher in fall suggesting more serious organic pollution and it was positively correlated with DIP (P<0.01). The phosphorus content in sediments was quite low in both months; the total phosphorus (TP) content in sediments ranged from 284.23 to 569.58 mg·kg-1 in May and from 287.97 to 355.39 mg·kg-1 in September. Calcium-bound phosphate (Ca-P) was the dominant species of inorganic phosphorus (IP). The labile organic phosphorus (L-OP) content was significantly correlated with runoff, SPM concentration, and permanganate index (P<0.01,P<0.05,P<0.01, respectively). The organic phosphorus (OP) content was significantly higher at the Lijin site in May, likely caused by the rainfall-runoff from the mining area around Lijin. The energy-based production activities from the Gaocun to Lijin reaches should also be further investigated.

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.

Effects of biochar on the transformation and earthworm bioaccumulation of organic pollutants in soil.

Little is known about the effects of biochar on the fate and behavior of micropollutants in soil, especially in the presence of soil macrofauna. Using a 14C-tracer, we studied the fate of 2,4-dichlorophenol and phenanthrene, after 30 days in soil in the presence of a biochar (0-5%, dry weight) produced from China fir at 400 °C and/or the earthworm Metaphire guillelmi. Application of the biochar significantly reduced the degradation and mineralization of both pollutants and strongly increased the accumulation of their metabolites in soil. The earthworm had no significant effects on the degradation of parent molecules of the pollutants but it significantly reduced the mineralization of the pollutants independent of the presence of the biochar. Although at an application rate of <1% the biochar strongly sorbed both pollutants, it did not significantly decrease the bioaccumulation of free dichlorophenol and phenanthrene and their metabolites by the earthworm. Our results demonstrate the complex effects of biochar on the fate, transformation, and earthworm bioaccumulation of organic pollutants in soil. They show that biochar application may not be an appropriate strategy for treating soil contaminated with hydrophobic organic pollutants and underline the importance of soil-feeding earthworms in risk assessments of biochar effects on soil remediation.

Degradation and bound-residue formation of nonylphenol in red soil and the effects of ammonium.

Fate of nonylphenol (NP) in soils and the effects of nitrogen fertilizers are unclear. Using (14)C-tracer, we studied the aerobic and anaerobic degradation of 4-NP111 in a paddy red soil amended without and with ammonium chloride. Under oxic conditions, 4-NP111 had a half-life of 16.1 ± 1.6 days and minor mineralization (3.84 ± 0.02%), forming no extractable metabolite but abundant bound residues (60.9 ± 1.7%, mostly bound to humin) after 49 days of incubation. The ammonium amendment (8 mmol/kg soil) significantly inhibited the degradation (half-life of 68.0 ± 7.7 days), mineralization (2.0 ± 1.1%), and bound-residue formation (23.7 ± 0.2%). Under anoxic conditions, 4-NP111 did not degrade during 49 days of incubation and the ammonium amendment (40 mmol/kg soil) did not affect its persistence. Our results demonstrate that bound-residue formation was a major mechanism for NP dissipation in the red soil under oxic conditions and that chemical nitrogen fertilizer at average field application rate may already considerably increase NP recalcitrance in agricultural soils.

Fate and metabolism of tetrabromobisphenol A in soil slurries without and with the amendment with the alkylphenol degrading bacterium Sphingomonas sp. strain TTNP3.

Transformation of ring-(14)C-labelled tetrabromobisphenol-A (TBBPA) was studied in an oxic soil slurry with and without amendment with Sphingomonas sp. strain TTNP3, a bacterium degrading bisphenol-A. TBBPA degradation was accompanied by mineralization and formation of metabolites and bound-residues. The biotransformation was stimulated in the slurry bio-augmented with strain TTNP3, via a mechanism of metabolic compensation, although this strain did not grow on TBBPA. In the absence and presence of strain TTNP3, six and nine metabolites, respectively, were identified. The initial O-methylation metabolite (TBBPA-monomethyl ether) and hydroxytribromobisphenol-A were detected only when strain TTNP3 was present. Four primary metabolic pathways of TBBPA in the slurries are proposed: oxidative skeletal rearrangements, O-methylation, ipso-substitution, and reductive debromination. Our study provides for the first time the information about the complex metabolism of TBBPA in oxic soil and suggests that type II ipso-substitution could play a significant role in the fate of alkylphenol derivatives in the environment.

Inhibitory effects of carbon nanotubes on the degradation of 14C-2,4-dichlorophenol in soil.

Concerns on the potential risks of engineered nanoparticles to the environment are increasing; however, little is known about the effects of carbon nanotubes (CNTs) on the environmental fate of hydrophobic organic pollutants in soil. We incubated radioactive labeled 2,4-dichlorophenol ((14)C-2,4-DCP) in a soil in the presence of various concentrations (0, 2, 20, and 2000 mg kg(-1) dry soil) of single-walled (SWCNTs) and multi-walled (MWCNTs) carbon nanotubes, and determined the mineralization, degradation, and residue distribution of 2,4-DCP in the soil. CNTs were added to the soil either after the spiking of (14)C-2,4-DCP or together with (14)C-2,4-DCP as a mixture. CNTs at the concentration of 2000 mg kg(-1) significantly (P<0.05) inhibited the mineralization of (14)C-2,4-DCP and induced a 2.3- to 3.9-fold increase in the amounts of the non-degraded (14)C-2,4-DCP in the soil after 90 d of incubation. Pre-adsorption of (14)C-2,4-DCP on CNTs showed stronger inhibitory effects on the degradation of (14)C-2,4-DCP, already significant with CNTs at 20 mg kg(-1). In general, SWCNTs had a higher effect on the degradation and residue distribution of 2,4-DCP in the soil than MWCNTs. The inhibitory effects are supposed to be owing to limited activities of soil endogenous microorganisms, potential toxicities of CNTs to the microorganisms, and reduced bioavailability of 2,4-DCP in the presence of CNTs, even though a desorption hysteresis of 2,4-DCP on CNTs was not observed. Our results indicate that CNTs have more significant impacts on the environmental fate of the hydrophobic pollutants entering soil together with CNTs via strong sorption than the pollutants already present in soil.