2,4,6-Tribromophenol (TBP), an intermediate of brominated flame retardants, can easily release to environment and recalcitrant to degradation. Previously, Bacillus sp. GZT, a pure aerobic strain capable of simultaneously debrominating and mineralizing TBP, was successfully isolated by us. To further obtain a practical application and dig up its TBP degradation mechanism, a total of 46.7-fold purification of a novel dehalogenase with a final specific activity of 18.9 U mg−1 and a molecular mass of 63.4 kDa was achieved. Under optimal conditions (35 °C and 200 rpm), up to 80% degradation efficiencies were achieved within 120 min. Adding H2O2, NADPH, Mn2+ and Mg2+ promoted enzyme reaction effectively; while EDTA, methyl viologen, Ni2+, Cu2+, Ca2+ and Fe2+ strongly inhibited reaction activities. The debromination of TBP was catalyzed by the enzyme at a Km of 78 μM and a Vmax of 0.65 min−1 mg protein−1, which indicated that this dehalogenase could specifically eliminate TBP with a high efficiency and stability. Based on MALDI-TOF/TOF analysis, the dehalogenase shared 98% identity with peptide ABC transporter substrate-binding protein. One open reading frame (ORF) encoding this peptide was found in Strain GZT genome, subjected to clone and expressed in Escherichia coli (E. coli) to characterize the encoding gene. Result showed that this recombinant strain could also remove as similar amount of TBP as Bacillus sp. GZT under the identical condition. Based on these results, we suggest that this newly-isolated TBP dehalogenase highlights a new approach for remediating TBP pollution.

Extensive studies have been conducted on the environmental degradation of multiwall carbon nanotubes (MWCNTs), but primarily focused on the extent and rate of MWCNTs mineralization. Few studies have explored possible structural changes that may occur to MWCNTs during natural or engineered processes. We systematically examined MWCNTs in oxidative coupling reactions in the presence of a common contaminant tetrabromobisphenol A (TBBPA). MWCNTs was modified by the radicals of TBBPA resulting from peroxidase-mediated coupling reaction. Interactions between TBBPA radicals and MWCNTs were definitely confirmed by analyzing the characteristic mass spectrometry response of bromine in TBBPA and the structures of MWCNTs. After reaction with TBBPA radicals for 60 min, the content of bromine contained in MWCNTs was 6.84(±0.12)%, a quantity equivalent to a 501.65(±2.19) mg loading of TBBPA per gram MWCNTs. Modified MWCNTs had better stability and smaller sizes than that of MWCNTs and TBBPA-adsorbed MWCNTs. Assessment using zebrafish embryos revealed that the modified MWCNTs passed through the chorion and entered the embryo inducing acute toxicity, while the MWCNTs/TBBPA-adsorbed MWCNTs was trapped by chorion. These findings indicated that MWCNTs was modified in peroxidase-mediated coupling reactions, and suggested that such modifications may have an influence on the ecological risks of MWCNTs.

The fate of organic pollutants in the environment, especially the formation and stability of non-extractable (i.e., bound) residues (NERs) determines their environmental risk. Using ¹⁴C-tracers, we studied the fate of the carcinogen phenanthrene in active or sterilized oxic loamy soil in the absence and presence of the geophagous earthworm Metaphire guillelmi and characterized the NERs derived from phenanthrene. After incubation of ¹⁴C-phenanthrene in active soil for 28 days, 40 ± 3.1% of the initial amount was mineralized and 70.1 ± 1.9% was converted to NERs. Most of the NERs (>92%) were bound to soil humin. Silylation of the humin-bound residues released 45.3 ± 5.3% of these residues, which indicated that they were physically entrapped, whereas the remainder of the residues were chemically bound or biogenic. By contrast, in sterilized soil, only 43.4 ± 12.6% of the phenanthrene was converted to NERs and all of these residues were completely released upon silylation, which underlines the essential role of microbial activity in NER formation. The presence of M. guillelmi in active soil significantly inhibited phenanthrene mineralization (24.4 ± 2.6% mineralized), but NER formation was not significantly affected. Only a small amount of phenanthrene-derived residues (1.9–5.3% of the initial amount) accumulated in the earthworm body. When humin-bound residues were mixed with fresh soil, 33.9% (humin recovered from active soils) and 12.4% (humin recovered from sterilized soils) of the residues were mineralized after 75 days of incubation, respectively, which indicated a high bioavailability of NERs, albeit lower than the initial addition of phenanthrene. Our results indicated that many phenanthrene-derived NERs, especially those physically entrapped, are still bioavailable and may pose a toxic threat to soil organisms.

Oxytetracycline (OTC) is one of the most used antibiotics in aquaculture. The main concern related to its use is the bacterial resistance, when ineffective treatments are applied for its removal or inactivation. OTC photo-degradation has been suggested as an efficient complementary process to conventional methods used in intensive fish production (e.g.: ozonation). Despite this, and knowing that the complete mineralization of OTC is difficult, few studies have examined the antibacterial activity of OTC photoproducts. Thus, the main aim of this work is to assess whether the OTC photoproducts retain the antibacterial activity of its parent compound (OTC) after its irradiation, using simulated sunlight. For that, three Gram-negative bacteria (Escherichia coli, Vibrio sp. and Aeromonas sp.) and different synthetic and natural aqueous matrices (phosphate buffered solutions at different salinities, 0 and 21‰, and three different samples from marine aquaculture industries) were tested. The microbiological assays were made using the well-diffusion method before and after OTC has been exposed to sunlight. The results revealed a clear effect of simulated sunlight, resulting on the decrease or elimination of the antibacterial activity for all strains and in all aqueous matrices due to OTC photo-degradation. For E. coli, it was also observed that the antibacterial activity of OTC is lower in the presence of sea-salts, as demonstrated by comparison of halos in aqueous matrices containing or not sea-salts.

Bromide is a conservative tracer that is often applied with non-conservative solutes such as pesticides to estimate their retardation in the soil. It has been applied in concentrations of up to 250 g Br L−1, levels at which the growth of single-celled organisms can be inhibited. Bromide applications may therefore affect the biodegradation of non-conservative solutes in soil.The present study investigated the effect of potassium bromide (KBr) on the mineralisation of three pesticides – glyphosate, MCPA and metribuzin – in four agricultural A-horizon soils. KBr was added to soil microcosms at concentrations of 0, 0.5, 2.5 and 5 g Br− L−1 in the soil solution. The study concluded that KBr had a negative effect on pesticide mineralisation. The inhibitory effect varied depending on the KBr concentration, the type of pesticide and the type of soil. Furthermore, 16 S amplicon sequencing revealed that the KBr treatment generally reduced the abundance of bacteroidetes and proteobacteria on both an RNA and DNA level.Therefore, in order to reduce the effect of KBr on the soil bacterial community and consequently also on xenobiotic degradation, it is recommended that KBr be applied in a concentration that does not exceed 0.5 g Br− L−1 in the soil water.

To constrain organic matter compositions and origins, elemental (TOC, TN, C/N) and stable carbon (δ13C) and nitrogen isotope (δ15N) compositions are measured for surface sediments collected from muddy deposit along the Zhejiang coast, East China Sea. The results showed that the TOC, TN, C/N, δ13C, and δ15N were 0.19–0.67%, 0.03–0.09%, 6.76–9.22, −23.43 to −20.26‰, and 3.93–5.27‰, respectively. The δ13C values showed that the mixing inputs of terrigenous and marine organic matter generally dominated sedimentary organic matter in the west part, and the sedimentary organic matters were mainly influenced by the marine organic matter in the east part of the study area. A stable carbon isotope two end member mixing model estimates ~38% terrestrial -derived and ~62% marine-derived inputs to sedimentary organic matter. Microbial mineralization strongly controls δ15N values, and therefore cannot be used to identify the provenance of organic matter for the Zhenjiang coast.

The main goal of this study was to determine the concentrations of trace elements in the mineralogically contrasting shells of two Arctic bivalves: Chlamys islandica and Ciliatocardium ciliatum. Aragonite shells seem to be more susceptible to the binding of metal ions, which is most likely a result of their crystal lattice structure. We suggest that less biologically controlled aragonite mineralization tends to incorporate more metal impurities into the crystal lattice in waters with a lower pH, where metal ions are more available. Higher concentrations of impurities may further increase the lattice distortion causing lower crystal lattice stability and higher susceptibility to dissolution. Calcitic shells seem to be less prone to bind metal ions than aragonite shells most likely because under strict biological control, the uptake of ions from ambient seawater is more selective; thus, the final crystal lattice is less contaminated by other metals and is more resistant to dissolution.

Dissolved sulfide, iron (Fe), and phosphorus (P) concentrations in sediments of the East China Sea were simultaneously measured in situ by diffusive gradients in thin films (DGT) technique. The results, by combination with solid-phase Fe speciation, were used to characterize the interplays of Fe, S and P. Diverse distributions of dissolved sulfide among the sites are attributable to highly dynamic diagenetic regimes and varying availability of labile organic carbon (OC). The DGT technique provided high-resolution evidence for coexistence of microbial iron reduction (MIR) and sulfate reduction in localized zones, and for Fe-coupled P mobilization. Measured Fe2+/P ratios suggest that Fe2+ reoxidatiion at the oxic zones can serve as an efficient scavenger of P. Empirical estimation indicates that MIR plays an important role in anaerobic OC mineralization in the sediments, which is a combined result of low availability of labile OC, high reactive Fe content, and unsteady diagenetic regimes.

This work studies the degradation of safranin T (SF, a recalcitrant pollutant) by an electrochemical process and three photochemical advanced oxidation technologies (TiO₂ photocatalysis, UV/H₂O₂, and photo-Fenton). The degradation routes of each process were elucidated initially. Based on the mineralization extent, improvement of the treated solutions’ biodegradability, and energy consumption, the most suitable process was identified. Interestingly, in the electrochemical system, safranin T was efficiently eliminated through electrogenerated HOCl. In contrast, the popular photo-Fenton process was unable to degrade SF. Moreover, the pollutant was refractory to highly energetic UV₂₅₄ irradiation. Meanwhile, the UV/H₂O₂ and TiO₂ photocatalysis processes removed SF slowly. Interestingly, the electrochemical system produced biodegradable solutions. Furthermore, the electrical energy consumption (EC) for the 100% removal of SF showed that the electrochemical process only spent 0.04 and 0.06% of the EC needed by TiO₂ photocatalysis and UV/H₂O₂, respectively. Therefore, the fast SF degradation, the high biodegradability intensification, and the very low energy consumption evidenced the relative advantages of the electrochemical process for the remediation of water containing safranin T. Finally, to obtain a deeper understanding of SF degradation by the electrochemical system, an analysis of structural transformations was made. It was found that the electrogenerated HOCl initially attacked the central azine and the aromatic amines on SF. Subsequently, aliphatic compounds were formed, which due to their biodegradable character could be completely eliminated by a conventional biological system or discharged into natural media.

The efficiency of the following systems: photolysis (UV-C only), photocatalysis with titanium-dioxide (UV-C/TiO₂), photocatalysis with granular-activated carbon (UV-C/GAC), and by adsorption on GAC, was assessed under different initial contaminant concentrations, i.e., 0.1–100 mg L⁻¹. The experiments were conducted in a batch photocatalytic reactor (1.9 L and 32 W UV power). It was found that UV-C/TiO₂ and UV-C/GAC systems showed fairly equal removal efficiencies under lower MNZ concentrations (0.1–5 mg L⁻¹) compared to higher concentrations at similar catalyst loading of 2.5 g L⁻¹. A decline in removal rate (based on first-order reaction) was observed with respect to increase in initial MNZ concentration in all systems. MNZ removal by adsorption on GAC was much lesser compared to UV-C only, UV-C/TiO₂, and UV-C/GAC systems. The adsorption data well correlated with the Freundlich model indicated that the adsorption was on the heterogeneous surface of the catalyst. The effectiveness of the systems were evaluated by calculating electrical energy consumed per order (E EO). The lowest E EO value was found to be for UV-C/TiO₂ (0.03 kWh m⁻³ order⁻¹) for the degradation of 0.1 mg L⁻¹ of MNZ compared to UV-C/GAC (0.06 kWh m⁻³ order⁻¹), UV-C only (0.15 kWh m⁻³ order⁻¹), and adsorption (0.44 kWh m⁻³ order⁻¹). The total organic carbon and nitrogen ion analyses have confirmed the mineralization of MNZ via aliphatic carboxylic acid compounds in the photocatalytic system. Overall, the photocatalytic system seems to be an energy-efficient treatment option for the removal of MNZ and similar other micropollutants.