Iodination of dissolved organic matter (DOM) initiated by manganese oxide may represent an important source of organoiodine compounds (OICs) for iodide-containing waters. Here, Suwannee River natural organic matter was selected as model DOM, the OICs formation in simulated freshwater samples from iodinated DOM induced by manganese oxide (δ-MnO2) was investigated at different pHs and concentrations of iodide and δ-MnO2 by using negative ion electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS). While no OIC was observed in DOM control samples without δ-MnO2, hundreds of OICs were detected in the presence of δ-MnO2, suggesting the enhanced role of δ-MnO2 played in DOM iodination. The relative abundance was defined as the value of dividing the peak intensity of OICs by the highest m/z peak intensity constantly occurred in each mass spectrum, and selected as a parameter for partly reflecting the real level of OICs. The relative abundance of most OICs were around or greater than 1%, and several OICs with higher relative abundance were identified as diiodo-5-hydroxy-4-cyclopentene-1,3-dione, diiodomethane and diiodoacetic acid. The numbers of the formed OICs increased with the increase concentrations of iodide/δ-MnO2 and the decrease of pH, and nearly all OICs formed at lower levels of iodide/δ-MnO2 and/or higher pH were overlapped by that at higher levels of iodide/δ-MnO2 and/or lower pH, indicating the reliability of FT-ICR MS analysis techniques and data processing method. The OICs were formed mainly from the iodination of typical lignin-like and tannin-like compounds, as well as the precursor compounds with higher relative abundance through substitution reactions. Our findings demonstrate that the OICs formation by δ-MnO2-initiated DOM iodination should receive more attention and the concentration, exact structure and toxicity of the OICs need to be further investigated.

Microplastic (MP) are environmental pollutants and have the potential to cause varying degrees of aquatic toxicity. In this study, the effects on gut microbiota of adult male zebrafish exposed for 14 days to 100 and 1000 μg/L of two sizes of polystyrene MP were evaluated. Both 0.5 and 50 μm-diameter spherical polystyrene MP increased the volume of mucus in the gut at a concentration of 1000 μg/L (about 1.456 × 10¹⁰ particles/L for 0.5 μm and 1.456 × 10⁴ particles/L for 50 μm). At the phylum level, the abundance of Bacteroidetes and Proteobacteria decreased significantly and the abundance of Firmicutes increased significantly in the gut after 14-day exposure to 1000 μg/L of both sizes of polystyrene MP. In addition, high throughput sequencing of the 16S rRNA gene V3-V4 region revealed a significant change in the richness and diversity of microbiota in the gut of polystyrene MP-exposed zebrafish. A more in depth analysis, at the genus level, revealed that a total of 29 gut microbes identified by operational taxonomic unit (OTU) analysis were significantly changed in both 0.5 and 50 μm-diameter polystyrene MP-treated groups. Moreover, it was observed that 0.5 μm polystyrene MP not only increased mRNA levels of IL1α, IL1β and IFN but also their protein levels in the gut, indicating that inflammation occurred after polystyrene MP exposure. Our findings suggest that polystyrene MP could induce microbiota dysbiosis and inflammation in the gut of adult zebrafish.

Nitrogen (N)-enriched leaching water may act as a source of indirect N₂O emission when it is discharged to agricultural drainage ditches. In this study, indirect N₂O emissions from an agricultural drainage ditch mainly receiving interflow water were measured using the static chamber-gas chromatography technique during 2012–2015 in the central Sichuan Basin in southwestern China. We found the drainage ditch was a source of indirect N₂O emissions contributing an inter-annual mean flux of 6.56 ± 1.12 μg N m⁻² h⁻¹ and a mean indirect N₂O emission factor (EF₅g) value of 0.03 ± 0.003%. The mean EF₅g value from literature review was 0.51%, which was higher than the default EF₅g value (0.25%) proposed by the Intergovernmental Panel on Climate Change (IPCC) in 2006. Our study demonstrated that, more in situ observations of N₂O emissions as regards N leaching are required, to account for the large variation in EF₅g values and to improve the accuracy and confidence of the default EF₅g value. Indirect N₂O emissions varied with season, higher emissions occurred in summer and autumn. These seasonal variations were related to drainage water NO₃⁻-N concentration, temperature, and precipitation. Our results showed that intensive precipitation increased NO₃⁻-N concentrations and N₂O emissions, and when combined with warmer water temperatures, these may have increased the denitrification rate that led to the higher summer and autumn N₂O emissions in the studied agricultural drainage ditch.

This study characterized the effect of the metal(loid)-resistant bacteria Ralstonia eutropha Q2-8 and Exiguobacterium aurantiacum Q3-11 on Cd and As accumulation in wheat grown in Cd- and As-polluted soils (1 mg kg−1 of Cd + 40 mg kg−1 of As and 2 mg kg−1 of Cd + 60 mg kg−1 of As). The influence of strains Q2-8 and Q3-11 on water-soluble Cd and As and NH4+concentration and pH in the soil filtrate were also analyzed. Inoculation with these strains significantly reduced wheat plant Cd (12–32%) and As (9–29%) uptake and available Cd (15–28%) and As (22–38%) contents in rhizosphere soils compared to the controls. Furthermore, these strains significantly increased the relative abundances of the arsM bacterial As metabolism gene and of Fe- and Mn-oxidizing Leptothrix species in rhizosphere soils. Notably, these strains significantly reduced water-soluble Cd and As concentrations and increased pH and NH4+ concentration in the soil filtrate. These results suggest that these strains increased soil pH and the abundance of genes possibly involved in metal(loid) unavailability, resulting in reduced wheat Cd and As accumulation and highlight the possibility of using bacteria for in situ remediation and safe production of wheat or other food crops in metal(loid)-polluted soils.

Polybrominated diphenyl ethers (PBDEs) undergo debromination when they were exposed in zerovalent metal or bimetallic systems. Yet their debromination pathways and mechanisms in these systems were not well understood. Here we reported the debromination pathways of three BDE congeners (BDE-21, 25 and 29) by nano-zerovalent iron (n-ZVI). All these BDE congeners have three bromine substituents that were located in ortho-, meta- and para-positions. Results demonstrated that BDE-21, 25 and 29 preferentially debrominate meta-, ortho- and para-bromines, respectively, suggesting that bromine substituent at each position (i.e. ortho-, meta- or para-) of PBDEs can be preferentially removed. Singly occupied molecular orbitals of BDE anions are well correlated with their actual debromination pathways, which successfully explain why these BDE congeners exhibit certain debromination pathways in n-ZVI system. In addition, microscale zerovalent zinc (m-ZVZ), iron-based bimetals (Fe/Ag and Fe/Pd) were also used to debrominate PBDEs, with BDE-21 as target pollutant. We found that the debromination pathways of BDE-21 in m-ZVZ and Fe/Ag systems are the same to those in n-ZVI system, but were partially different from those in Fe/Pd systems. The debromination of BDE-21 in Pd-H2 system as well as the solvent kinetic isotope effect in single metal and bimetallic systems suggests that H atom transfer is the dominant mechanism in Fe/Pd system, while e-transfer is still the dominant mechanism in Fe/Ag system.

This article has been retracted: please see Elsevier Policy on Article Withdrawal (https://www.elsevier.com/about/our-business/policies/article-withdrawal).This article has been retracted at the request of the authors due to the results of a detailed investigation of the data quality conducted by the Central Analytical Laboratory (CAL) after relocation to the University of Wisconsin (UW) – Wisconsin State Laboratory of Hygiene. Using a subset of the 30 samples with the highest bromide ion (Br-) concentrations, the CAL at UW found 6 samples that could not be verified or were incorrect. Because the extent of the incorrect data is unknown, the NADP Executive Committee voted unanimously in May 2019 to discontinue public access to these data, and they decided to sequester all Br- data prior to June 2018. These issues were not obvious to the authors when the paper was written.The authors apologize for the inconvenience caused.

Reliable detection and attribution of changes in nitrogen (N) runoff from croplands are essential for designing efficient, sustainable N management strategies for future. Despite the recognition that excess N runoff poses a risk of aquatic eutrophication, large-scale, spatially detailed N runoff trends and their drivers remain poorly understood in China. Based on data comprising 535 site-years from 100 sites across China's croplands, we developed a data-driven upscaling model and a new simplified attribution approach to detect and attribute N runoff trends during the period of 1990–2012. Our results show that N runoff has increased by 46% for rice paddy fields and 31% for upland areas since 1990. However, we acknowledge that the upscaling model is subject to large uncertainties (20% and 40% as coefficient of variation of N runoff, respectively). At national scale, increased fertilizer application was identified as the most likely driver of the N runoff trend, while decreased irrigation levels offset to some extent the impact of fertilization increases. In southern China, the increasing trend of upland N runoff can be attributed to the growth in N runoff rates. Our results suggested that increased SOM led to the N runoff rate growth for uplands, but led to a decline for rice paddy fields. In combination, these results imply that improving management approaches for both N fertilizer use and irrigation is urgently required for mitigating agricultural N runoff in China.

Source samples including crustal dust, cement dust, coal combustion were sampled and ambient samples of PM₂.₅ and PM₁₀ were synchronously collected in Hefei from April to December 2014. The size distributions of the markers in the measured source profiles were incorporated into ME-2 solution to develop a new method, called the SDABB model (an advanced ABB three-way factor analysis model incorporating size distribution information). The performance of this model was investigated using three-way synthetic and ambient dataset. For the synthetic tests, the size distributions of markers estimated by the SDABB model were more consistent with true condition. The AAEs between estimated and observed contributions of the SDABB ranged from 15.2% to 29.0% for PM₁₀ and 19.9%–31.6% for PM₂.₅, which is lower than those of PMF2. For the ambient PM, six source categories were identified by SDABB for both sizes, although the profiles were different. The source contributions were sulphate (33.33% and 24.53%), nitrate and SOC (22.33% and 18.16%), coal combustion (19.01% and 18.23%), vehicular exhaust (12.99% and 12.07%), crustal dust (10.69% and 19.40%) and cement dust (1.65% and 5.39%) for PM₂.₅ and PM₁₀ respectively. In addition, the estimated ratios of Al, Si, Ti and Fe in CRD were 0.76, 0.84, 1.10 and 0.85; those of Al and Si in CC were 0.42 and 0.66; Ca and Si in CD were 0.95 and 1.10; NO₃⁻ and NH₄⁺ in nitrate were 1.11 and 1.01; and SO₄²⁻ and NH₄⁺ in sulphate were 0.96 and 1.16. These modeled ratios were consistent with the measured ratios. The size distribution of contributions also came close to reality. Thus, the advanced SDABB three-way model can better capture the characteristics of sources between sizes by effectively incorporating the size distributions of the markers as physical constraints.

The urbanization and industrialization of cities around the coastal region of the Bohai Sea have produced large amounts of sewage sludge from sewage treatment plants. Research on the biodegradation of nonylphenol (NP) and the influencing factors of such biodegradation during sewage sludge composting is important to control pollution caused by land application of sewage sludge. The present study investigated the effect of aeration on NP biodegradation and the microbe community during aerobic composting under two intermittent aeration treatments in a full-scale plant of sewage sludge, sawdust, and returned compost at a ratio of 6:3:1. The results showed that 65% of NP was biodegraded and that Bacillus was the dominant bacterial species in the mesophilic phase. The amount of NP biodegraded in the mesophilic phase was 68.3%, which accounted for 64.6% of the total amount of biodegraded NP. The amount of NP biodegraded under high-volume aeration was 19.6% higher than that under low-volume aeration. Bacillus was dominant for 60.9% of the composting period under high-volume aeration, compared to 22.7% dominance under low-volume aeration. In the thermophilic phase, high-volume aeration promoted the biodegradation of NP and Bacillus remained the dominant bacterial species. In the cooling and stable phases, the contents of NP underwent insignificant change while different dominant bacteria were observed in the two treatments. NP was mostly biodegraded by Bacillus, and the rate of biodegradation was significantly correlated with the abundance of Bacillus (r = 0.63, p < 0.05). Under aeration, Bacillus remained the dominant bacteria, especially in the thermal phase; this phenomenon possibly increased the biodegradation efficiency of NP. High-volume aeration accelerated the activity and prolonged the survival of Bacillus. The risk of organic pollution could be decreased prior to sewage sludge reuse in soil by adjusting the ventilation strategies of aerobic compost measurements.

The last decades have seen the increasing prevalence of thyroid disorders. These augmentations could be the consequence of the increasing contamination of the environment by chemicals that may disrupt the thyroid function. Indeed, in vitro studies have shown that many chemicals contaminating our environment and highlighted in human serum, are able to interfere with the thyroid function. Given the crucial importance of thyroid hormones on neurodevelopment in fetus and newborns, the influence of these pollutants on newborn thyroid homeostasis is a major health concern. Unfortunately, the overall evidence for a deleterious influence of environmental pollutants on thyroid remains poorly studied. Therefore, we assessed the contamination by polychlorinated biphenyls (PCBs), organochlorine pesticides and perfluorinated compounds (PFC) in 221 cord blood samples collected in Belgium between 2013 and 2016. Our results showed that compared to previous studies performed on newborns recruited in Belgium during the two last decades, the present pollutant contamination is declining. Multivariate statistical analyses pointed out a decrease of thyroid stimulating hormone (TSH) level in male newborns with detectable level of 4,4′- dichlorodiphenyldichloroethylene (4,4′-DDE) in comparison with those with no detectable level (p = 0.025). We also highlighted a negative association between perfluorononanoic acid (PFNA) concentration and TSH in male newborns (p = 0.018). Logistic regression showed increased odds ratio for presentation of hypothyroid in mother for each one unit augmentation of log natural concentration of PFOA (OR = 2.30, [1.18–4.5]) and PFOS (OR = 2.03 [1.08–3.83]). Our findings showed that the residual contamination by PFCs and organochlorine pollutants in cord blood are correlated with thyroid hormone in the newborns and the risk of hypothyroid in mothers.