The m-aminophenol (m-AP) is a widely used industrial chemical, which enters water, soils, and sediments with waste emissions. A common soil metal oxide, birnessite (δ-MnO2), was found to mediate the transformation of m-AP with fast rates under acidic conditions. Because of the highly complexity of the m-AP transformation, mechanism-based models were taken to fit the transformation kinetic process of m-AP. The results indicated that the transformation of m-AP with δ-MnO2 could be described by precursor complex formation rate-limiting model. The oxidative transformation of m-AP on the surface of δ-MnO2 was highly dependent on reactant concentrations, pH, temperature, and other co-solutes. The UV-VIS absorbance and mass spectra analysis indicated that the pathway leading to m-AP transformation may be the polymerization through the coupling reaction. The m-AP radicals were likely to be coupled by the covalent bonding between unsubstituted C2, C4 or C6 atoms in the m-AP aromatic rings to form oligomers as revealed by the results of activation energy and mass spectra. Furthermore, the toxicity assessment of the transformation productions indicated that the toxicity of m-AP to the E. coli K-12 could be reduced by MnO2 mediated transformation. The results are helpful for understanding the environmental behavior and potential risk of m-AP in natural environment.

In the present work, low-cost and efficient iron oxide nanoparticle incorporated on mesoporous biochar was prepared from effluent treatment plant (ETP) sludge collected from the textile industry. This sludge contains a higher amount of Fe due to the use of ferric chloride as a coagulant in the treatment of wastewater generated during the process. The raw sludge and prepared biochar was extensively examined by various sophisticated techniques like XRF, XRD, BET, TGA, XPS, RAMAN, FTIR, FESEM, TEM, and VSM. TEM and XRD analysis confirms the presence of iron oxide nanoparticles on mesoporous biochar. The prepared biochar was found to possess BET surface area of 91 m² g⁻¹. Several parameters like pH, dose, initial concentration, temperature and time were optimized for the adsorptive removal of ofloxacin (OFL) from aqueous solution. Biochar (named as BTSFe) achieved ≈96% removal efficiency of OFL with a maximum adsorption capacity (qₘ) of 19.74 mg g⁻¹ at optimum condition. π-π electron–donor-acceptor and H bonding were the major mechanisms responsible for the OFL adsorption. Kinetic and equilibrium thermodynamic study of showed that the adsorption of OFL was represented by the pseudo-second-order kinetics model, and the process was exothermic and spontaneous. Additionally, Redlich-Peterson and Freundlich isotherms best fitted the experimental data indicating multilayer adsorption phenomenon. Biochar was magnetically separated and thermally regenerated after each cycle for five times with a nominal overall decrease of ≈8% in removal efficiency. Leaching of iron during the adsorption process was also checked and found to be within the permissible limit. This study provides an alternative application of the textile industry sludge as an efficient, low-cost biochar for the removal of emerging pharmaceutical compounds.

Antibiotics in the environment usually co-exist with their transformation products with retained toxicity, raising concerns about environmental risks of their combined exposure. Herein, we reported a novel predictive approach for evaluating the individual and combined toxicity for photodegradation products of fluoroquinolone antibiotics (FQs). Quantitative structure-activity relationship (QSAR) models with promising predictive performance were constructed and validated using experimental data obtained with 13 FQs and 78 mixtures towards E. coli. A structural descriptor reflecting the interaction among FQ molecules and the target protein was employed in the QSAR models, which was obtained through molecular docking and thus provided a rational mechanistic explanation for these models. The predicted results indicated that the degradation products displayed varying degrees of changes compared to the parent FQs, while the combined toxicity of FQs and their degradation products was mostly additive. Furthermore, following UV irradiation the degradation products displayed elevated capacity of inducing resistance mutations in E. coli, though their overall toxicity was reduced. This result highlights the implications of antibiotic degradation products on resistance development in bacteria and stresses the importance of considering such impacts during environmental risk assessments of antibiotics.

A substantial increase in the usage of organophosphate esters (OPEs) as flame retardants and plasticizers in rubbers, textiles, upholstered furniture, lacquers, plastics, building materials and electronic equipment has resulted in their increasing concentrations in the environment over time. However, little is known about the concentrations and fate of OPEs and their metabolites (mOPEs) in biota, including chicken eggs. The aim of this study was to understand the spatial variation in the concentrations in chicken eggs and the partitioning between yolk and albumin. In total, 153 chicken eggs were purchased across Australia and analysed for 9 OPEs and 11 mOPE. Most of the compounds were found to be deposited in egg yolk, where diphenyl phosphate (DPHP, 3.8 ng/g wet weight, median) and tris(2-chloroisopropyl) phosphate (TCIPP, 1.8 ng/g wet weight, median) were predominant mOPE and OPE, respectively. Moreover, no spatial differences in concentrations of OPEs and mOPEs in eggs purchased from different locations were found in this study. Although comparable levels of ∑OPEs were detected in egg yolk and albumin, much higher concentrations of ∑mOPEs were found in yolk than albumin. Meanwhile, a negative correlation (R² = 0.964, p = 0.018) was found between the molecular mass of analytes and partitioning coefficient of Cyₒₗₖ/Cyₒₗₖ₊ₐₗbᵤₘᵢₙ (defined as chemical concentration in egg yolk divided by the sum of chemical concentrations in both yolk and albumin). These results indicate that n-octanol/water partition coefficients (log KOW) may not be a crucial factor in the distribution of OPEs and mOPEs between egg yolk and albumin, which is important in understanding distribution of emerging organic contaminants in biota.

Promotion of plant capacity for accumulation of heavy metals (HMs) is one of the key strategies in enhancing phytoremediation in contaminated soils. Here we report that, Rhodococcus qingshengii, an abscisic acid (ABA)-catabolizing bacteria, clearly boosts levels of Cd, Zn, and Ni in wild-type Arabidopsis by 47, 24, and 30%, respectively, but no increase in Cu was noted, when compared with non-inoculated Arabidopsis plants in contaminated growth substrate. Furthermore, when compared with wild-type plants, R.qingshengii-induced increases in Cd, Zn, and Ni concentrations were more pronounced in abi1/hab1/abi2 (ABA-sensitive mutant) strains of Arabidopsis, whereas little effect was observed in snrk2.2/2.3 (ABA insensitive mutant). This demonstrates that metabolizing ABA might be indispensable for R. qingshengii to improve metal accumulation in plants. Bacterial inoculation significantly elevated the expression of Cd, Zn, and Ni-related transporters; whereas the transcript levels of Cu transporters remained unchanged. This result may be a reasonable explanation for why the uptake of Cd, Zn, and Ni in plants was stimulated by bacterial inoculation, while no effect was observed on Cu levels. From our results, we clearly demonstrate that R. qingshengii can increase the accumulation of Cd, Zn, and Ni in plants via an ABA-mediated HM transporters-associated mechanism. Metabolizing ABA in the plants by ABA-catabolizing bacterial inoculation might be an alternative strategy to improve phytoremediation efficiency in HMs contaminated soil.

Technologies for cleaner production of rice in cadmium (Cd) contaminated field are being explored worldwide. In order to investigate the inhibition mechanism of phosphate on Cd transport in soil-plant system, controlled experiments were performed in this study. Experimental results showed that Cd levels in roots, flag leaves, rachises and grains of rice plants (Oryza sativa L.) were significantly reduced by supplement of 0.5–2.5 g kg⁻¹ calcium magnesium phosphate fertilizer (CMP). Path coefficient analysis revealed that phosphorous had significant negative direct effect on Cd, but positive indirect effect on essential and non-essential amino acids. Applying 2.5 g kg⁻¹ CMP made the Cd concentration decreased by 45.7% while free essential and non-essential amino acids increased by 28.0–28.6% in grains. Levels of the branched-chain amino acids in grains were much higher than other essential amino acids, and increased with the amount of CMP fertilization. After application of CMP, pH of soil solution and thickness of the iron plaque around roots increased significantly. Spectra from X-ray photoelectron spectrometer (XPS) showed that content of N, P and Fe increased apparently, C, O and Ca had no change, while S decreased by 74.2% in roots after application of 2.5 g kg⁻¹ CMP. Meanwhile, Cd concentration in protoplasts of root cells decreased by 39.5–80.1% with the increase of CMP. These results indicate that application of CMP can effectively inhibit Cd accumulation in root protoplasts by promoting iron plaque formation on the root surface, reduce Cd concentration and increase free amino acids in rice grains.

We present here spectroscopic compositional analysis of brown carbon (BrC) and humic-like substances (HULIS) in the Indian context under varying conditions of source emissions and atmospheric processing. To this end, we study bulk water-soluble organic matter (WSOM), neutral- and acidic-HULIS (HULIS-n and HULIS-a), and high-polarity (HP)-WSOM collected in the eastern Indo-Gangetic Plain (IGP) with respect to UV–Vis, fluorescence, FT-IR, ¹H NMR and ¹³C characteristics under three aerosol regimes: photochemistry-dominated summer, aged biomass burning (BB)-dominated post-monsoon, and fresh BB-dominated winter. Absorption coefficients (bₐbₛ_₃₆₅ ₙₘ; Mm⁻¹) of WSOM and HULIS fractions increase by a factor of 2–9 during winter as compared to summer, with HULIS-n dominating total HULIS + HP-WSOM absorption (73–81%). Fluorophores in HULIS-n appear to contain near-similar levels of aromatic and unsaturated aliphatic conjugation across seasons, while HULIS-a exhibits distinctively smaller-chain structures in summer and post-monsoon. FT-IR spectra reveals, among others, strong signatures of aromatic phenols in winter WSOM suggesting a BB-related origin. ¹H NMR-based source attribution coupled with back trajectory analysis indicate the presence of secondary and BB-related organic aerosol (SOA and BBOA) in the post-monsoon and winter, and marine-derived OA (MOA) in the summer, which is supported by ¹³C measurements. Overall, these observations uncover a complex interplay of emissions and atmospheric processing of carbonaceous aerosols in the IGP.

Contamination of soil with heavy metals seriously harms the growth of crops. Silicon fertilizer is known to promote growth of crops and alleviate heavy metals stresses in vegetables. However, little is known about the effects of silicon fertilizer on pakchoi vegetable growth and soil microbial community in soil contaminated with multiple heavy metals. In order to elucidate this question, current study was designed to analyze the impact of different silicon fertilizer doses on the growth of pakchoi, heavy metals accumulation in pakchoi, and diversity and composition of bacterial community in heavy metals contaminated soil. Results of the study showed that, silicon fertilizer application significantly improved the yield of pakchoi and reduced the content of heavy metals in pakchoi. Moreover, the silicon fertilizer led to the heterogeneity of bacterial community structure in soil. Linear discriminant analysis (LDA) effect size (LEfSe) test showed the change of soil bacterial community structures under the higher silicon fertilizer doses (0.8–3.2%). Similarly, soil bacteria associated with heavy metal resistance and carbon/nitrogen metabolism showed a more active response to medium fertilizer dose (0.8% w/w). In addition, Mantel test and Redundancy analysis (RDA) showed that both the soil bacterial community structures and pakchoi growth were significantly correlated with soil EC, available K and pH. Study suggested that the application of silicon fertilizer provided richer bacteria associated with heavy metal resistance and plant growth, and more favorable soil physicochemical environment for the growth of pakchoi under multiple heavy metal contamination, and the impact was dependent on fertilizing dose.

Benzotriazole ultraviolet stabilizers (BUVSs) are widely used additives in industrial materials and personal care products that protect products from ultraviolet damage. Due to their high production volume and potential to bioaccumulate, BUVSs are an environmental pollutant of concern. In this study, juvenile zebrafish (Danio rerio) were exposed to 4 BUVSs (UV-234, UV-326, UV-329, and UV-P) at 10 and 100 μg/L for 28 d. BUVSs induced hepatic vacuolization and nuclei pyknosis in the liver following 100 μg/L UV-234 and UV-329 exposure. Transcriptomic analysis in the liver uncovered pathways related to inflammation that were affected by BUVSs. Based upon these data, we measured the expression levels of 9 genes involved in AHR-IL17/IL22 pathway in zebrafish larvae exposed to each BUVSs at one dose of either 10 or 100 μg/L for 6 days in a second set experiment. Transcript levels of interleukins il17a and il22 were decreased, while il6 mRNA was increased with exposure to UV-234, UV-329, and UV-P. No change to targeted transcripts was observed with UV-326 treatments. Moreover, cyp1a1 and ahr2 levels were increased in larvae treated with 100 μg/L UV-329 or UV-P. Consistent with expression data, protein abundance of IL22 was decreased by 29% with exposure to 100 μg/L UV-P. Taken together, these results demonstrate that exposure to different benzotriazole congeners may be associated with immunotoxicity in zebrafish through the AHR-IL17/IL22 pathway, and this may be associated with hepatic damage with prolonged exposures. This study provides new insight into unique pathways perturbed by specific BUVSs congeners.

Soil contamination in urban environment by trace metals is of public concerns. For better risk assessment, it is important to determine their background concentrations in urban soils. For this study, we determined the background concentrations of 9 trace metals including As, Ba, Cd, Co, Cu, Ni, Pb, Se, and Zn in 214 urban soils in Florida from two large cities (Orlando and Tampa) and 4 small cities (Clay County, Ocala, Pensacola and West Palm Beach). The objectives were to determine: 1) total concentrations of trace metals in urban soils in cities of different size; 2) compare background concentrations to Florida Soil Cleanup Target Levels (FSCTLs); and 3) determine their distribution and variability in urban soils via multivariate statistical analysis. Elemental concentrations in urban soils were variable, with Pb being the highest in 5 cities (165–552 mg kg⁻¹) and Zn being the highest concentration in Tampa (1,000 mg kg⁻¹). Besides, the As and Pb concentrations in some soils exceeded the FSCTL for residential sites at 2.1 mg kg⁻¹ As and 400 mg kg⁻¹ Pb. Among the cities, Clay County and Orlando had the lowest concentrations for most elements, with Cd, Co, and As being the lowest while Ba, Pb and Zn being the highest. Among all values, geometric means were the lowest while 95th percentile was the highest for all metals. Most 95th percentile values were 2–3 folds higher than the GM data, with Pb presenting the greatest difference, being 4 times greater than GM value (58.9 vs. 13.6 mg kg⁻¹). Still they were lower than FSCTL, with As exceeding FSCTL for residential sites at 2.1 mg kg⁻¹. In addition, the linear discriminate analysis showed distinct separation among the cities: Ocala (Ba & Ni) and Pensacola (As & Pb) were distinctly different from each other and from other cities with higher metal concentrations. The large variations among elemental concentrations showed the importance to establish proper background concentrations of trace metals in urban soils.