This study systematically explored the effect of humic acid (HA) (as model of natural organic matter) on the kinetics, products and transformation pathway of triclosan (TCS) by laccase-catalyzed oxidation. It was found that TCS could be effectively transformed by laccase-catalysis, with the apparent second-order rate constant being 0.056 U⁻¹ mL min⁻¹. HA inhibited the removal rate of TCS. HA-induced inhibition was negatively correlated with HA concentration in the range of 0–10 mg L⁻¹ and pH-dependent from 3.5 to 9.5. FT-IR and ¹³C NMR spectra showed a decrease of aromatic hydroxyl (phenolic) groups and an increase of aromatic ether groups, indicating the cross-linking of HA via C-O-C and C-N-C bonds during enzyme-catalyzed oxidation. Ten principle oxidative products, including two quinone-like products (2-chlorohydroquinone, 2-chloro-5-(2,4-dichlodichlorophenoxy)-(1,4)benzoquinone), one chlorinated phenol (2,4-dichlorophenol (2,4-DCP)), three dimers, two trimmers and two tetramers, were detected by gas chromatograghy/mass spectrometry (GC-MS) and high performance liquid chromatography/quadrupole time-of-flight/mass spectrometry (HPLC/Q-TOF/MS). The presence of HA induced significantly lesser generation of self-polymers and enhanced cross-coupling between HA and self-polymers via C-O-C, C-N-C and C-C coupling pathways. A plausible transformation pathway was proposed as follows: TCS was initially oxidized to form reactive phenoxyl radicals, which self-coupled to each other subsequently by C-C and C-O pathway, yielding self-polymers. In addition, the scission of ether bond was also observed. The presence of HA can promote scission of ether bond and further oxidation of phenoxyl radicals, forming hydroxylated or quinone-like TCS. This study shed light on the behavior of TCS in natural environment and engineered processes, as well provided a perspective for the water/wastewater treatment using enzyme-catalyzed oxidation techniques.

The effects of ambient temperature on stroke death in China have been well addressed. However, few studies are focused on the attributable burden for the incident of different types of stroke due to ambient temperature, especially in Beijing, China. We purpose to assess the influence of ambient temperature on hospital stroke admissions in Beijing, China. Data on daily temperature, air pollution, and relative humidity measurements and stroke admissions in Beijing were obtained between 2013 and 2014. Distributed lag non-linear model was employed to determine the association between daily ambient temperature and stroke admissions. Relative risk (RR) with 95% confidence interval (CI) and Attribution fraction (AF) with 95% CI were calculated based on stroke subtype, gender and age group. A total number of 147, 624 stroke admitted cases (including hemorrhagic and ischemic types of stroke) were documented. A non-linear acute effect of cold temperature on ischemic and hemorrhagic stroke hospital admissions was evaluated. Compared with the 25th percentile of temperature (1.2 °C), the cumulative RR of extreme cold temperature (first percentile of temperature, −9.6 °C) was 1.51 (95% CI: 1.08–2.10) over lag 0–14 days for ischemic type and 1.28 (95% CI: 1.03–1.59) for hemorrhagic stroke over lag 0–3 days. Overall, 1.57% (95% CI: 0.06%–2.88%) of ischemic stroke and 1.90% (95% CI: 0.40%–3.41%) of hemorrhagic stroke was attributed to the extreme cold temperature over lag 0–7 days and lag 0–3 days, respectively. The cold temperature's impact on stroke admissions was found to be more obvious in male gender and the youth compared to female gender and the elderly. Exposure to extreme cold temperature is associated with increasing both ischemic and hemorrhagic stroke admissions in Beijing, China.

Antibiotics can effectively protect livestock from pathogen infection, but residual antibiotics in manure bring risks to ecosystems and public health. Here, we demonstrated that black soldier fly larvae (BSFL) could provide an environmentally friendly manure treatment based on their ability to effectively and rapidly degrade tetracycline (TC). Investigation of the biological mechanisms and degradation pathways of TC by BSFL indicated that nearly 97% of TC was degraded within 12 days in a non-sterile BSFL treatment system, which is up to 1.6-fold faster than that achieved by normal composting. Our results showed that rapid TC-degradation was largely carried out by the intestinal microbiota of the larvae, which doubled the TC-degradation rates compared to those achieved in sterile BSFL systems. This conclusion was further supported by highly-efficient TC-biodegradation both in vivo and in vitro by four larval intestinal isolates. Moreover, detailed microbiome analysis indicated that intestinal bacterial and fungal communities were modified along with significantly increased tet gene copy number in the gut, providing the means to tolerate and degrade TC. Through analysis of TC degradation in vitro, four possible biodegradation products, two hydrolysis products and three conceivable inactivation products were identified, which suggested TC degradation reactions including hydrolysis, oxygenation, deamination, demethylation, ring-cleavage, modification, etc. In conclusion, our studies suggested an estimation of the fate of TC antibiotics in manure treatment by BSFL colonized by gut microbes. These results may provide a strategy for accelerating the degradation of antibiotics by adjusting the intestinal microbiota of BSFL.

Nitrous oxide (N₂O) is a potent greenhouse gas and tends to accumulate as an intermediate in the process of bacteria denitrification. To achieve complete reduction of nitrogen oxide (NOₓ) in bacteria denitrification, the structural gene nosZ encoding nitrous oxide reductase (N₂OR) was cloned from Alcaligenes denitrificans strain TB (GenBank JQ044686). The recombinant plasmid containing the nosZ gene was built, and the expression of nosZ gene in Escherichia coli was determined. Results show that the nosZ gene consisting of 1917 nucleotides achieves heterologous expression successfully by codon optimization strategy under optimal conditions (pre-induction inoculum OD₆₀₀ of 0.67, final IPTG concentration of 0.5 mM, inducing time of 6 h, and inducing temperature of 28 °C). Determination result of gas chromatography confirms that N₂O degradation efficiency of recombinant E. coli is strengthened by at least 1.92 times compared with that of original strain TB when treated with N₂O as substrate. Moreover, N₂OR activity in recombinant strain is 2.09 times higher than that in wild strain TB, which validates the aforementioned result and implies that the recombinant E. coli BL21 (DE3)-pET28b-nosZ is a potential candidate to control N₂O accumulation and alleviate greenhouse effect. In addition, the N₂OR structure and the possible N₂O binding site in Alcaligenes sp. TB are predicted, which open an avenue for further research on the relationship between N₂OR activity and its structure.

The occurrence, eliminations, enantiomeric distribution and intra-day variations of five chiral pharmaceuticals (three beta-blockers and two antidepressants) were investigated in eight major WWTPs in Beijing, China. The results revealed that metoprolol (MTP) and venlafaxine (VFX) were of the highest concentrations among the five determined pharmaceuticals with mean concentrations of 803 ng L⁻¹ and 408 ng L⁻¹, respectively in influents, and 354 ng L⁻¹ and 165 ng L⁻¹ in effluents, respectively. Their removal efficiencies, intra-day concentration changes and enantiomeric profiles during wastewater treatment were further analyzed. Loads of these two chiral pharmaceuticals were also studied to reveal drug use pattern. A/A/O+MBR (anaerobic/anoxic/oxic + membrane bio-reactor) followed by joint disinfection treatment process exhibited the high removal efficiencies. No or weak enantioselectivity was observed in most WWTPs. However, obvious enantiomeric fraction (EF) changing of MTP was observed in WWTP3 employing A/A/O+MBR. Intra-day concentration fluctuations of MTP were smaller than VFX. A quick response to sudden rise influent concentration of MTP was observed in WWTP1 effluent but EF response lagged behind. Similar bihourly EF variations in influents and effluents were also observed in most WWTPs for MTP and VFX in consideration of hydraulic residence time (HRT).

China accounts for more than half of the world's vegetable production, and identifying the contribution of vegetable production to nitrous oxide (N₂O) emissions in China is therefore important. We performed a meta-analysis that included 153 field measurements of N₂O emissions from 21 field studies in China. Our goal was to quantify N₂O emissions and fertilizer nitrogen (N) based-emission factors (EFs) in Chinese vegetable systems and to clarify the effects of rates and types of N fertilizer in both open-field and greenhouse systems. The results indicated that the intensive vegetable systems in China had an average N₂O emission of 3.91 kg N₂O-N ha⁻¹ and an EF of 0.69%. Although the EF was lower than the IPCC default value of 1.0%, the average N₂O emission was generally greater than in other cropping systems due to greater input of N fertilizers. The EFs were similar in greenhouse vs. open-field systems but N₂O emissions were about 1.4 times greater in greenhouses. The EFs were not affected by N rate, but N₂O emissions for both open-field and greenhouse systems increased with N rate. The total and fertilizer-induced N₂O emissions, as well as EFs, were unaffected by the type of fertilizers in greenhouse system under same N rates. In addition to providing basic information about N₂O emissions from Chinese vegetable systems, the results suggest that N₂O emissions could be reduced without reducing yields by treating vegetable systems in China with a combination of synthetic N fertilizer and manure at optimized economic rates.

Urban agriculture plays an important role in sustainable food supply. However, because of the atmospheric pollution and soil contamination associated with urban areas, this activity may be of concern. In fact, contamination of soil with metals and the transference of contaminants to vegetables can represent health and safety risks associated with urban agriculture. The objective of this study was to evaluate the concentrations of selected trace metals (cadmium, copper and lead) in three lettuce cultivars produced in three different urban gardens in the metropolitan region of Belo Horizonte, Brazil and their respective soils. Samples of lettuce and soil were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) and graphite furnace atomic absorption spectrometry (AAS-GF), respectively, and their transfer coefficients were calculated. The methods were optimized and were fit for the purpose. Copper was the prevalent metal found in soils and lettuce, with an average of 27.9 ± 13.9 and 0.608 ± 0.157 mg kg⁻¹ respectively, followed by lead (19.4 ± 7.7 and 0.037 ± 0.039 mg kg⁻¹), and cadmium (0.16 ± 0.03 and 0.009 ± 0.005 mg kg⁻¹). Cadmium presented the largest transfer coefficients, ranging from 0.34 to 1.84 with an average of 0.92 ± 0.45, which may indicate a potential risk of accumulation in vegetables in the case of high soil contamination. A significant positive correlation was observed (p < 0.01) between cadmium in lettuce and in soil. Even though lead concentrations varied in the soils from the different urban areas, ranging from 11.88 to 30.01 mg kg⁻¹, no significant difference (p < 0.05) was found among the lettuce, probably due to its low mobility (transfer coefficient = 0.02). The copper and cadmium levels found in lettuce indicate safe lettuce production in the three urban gardens.

The knowledge of gene-chemical interaction can be used to derive toxicological mechanism of chemical pollutants, therefore, it might be useful to discriminate chemicals with different mechanisms. In this study, three narcotic chemicals (4-chlorophenol (4-CP), 3, 4-dichloroaniline (DCA) and 2, 2, 2-trichloroethanol (TCE)) and three specific acting chemicals (triclosan (TCS), clarithromycin (CLARY), sulfamethoxazole (SMX)) were assessed by Escherichia coli (E. coli) genome-wide knockout screening. 66, 97, 88, 144, 198 and 180 initial robust hits were identified by exposure to 4-CP, DCA, TCE, TCS, CLARY and SMX with two replicates at the concentration of IC50, respectively. The average fold change values of responsive mutants to the three narcotic chemicals were smaller than the three specific acting chemicals. The common gene ontology (GO) term of biological process enriched by the three narcotic chemicals was “response to external stimulus” (GO: 0009605). Other GO terms like “lipopolysaccharide biosynthetic process” (induced by 4-CP) and “purine nucleotide biosynthetic process” (induced by DCA) were also influenced by the narcotic chemicals. The toxic target of three known specific acting chemicals could be validated by GSEA of responsive genes. Four genes (flhC, fliN, fliH and flhD) might serve as potential biomarkers to distinguish narcotic chemicals and specific acting chemicals. The E. coli functional genomic approach presented here has shown great potential not only for the molecular mechanistic screening of chemicals, rather it can discriminate chemicals based on their mode-of-action.

High arsenic (As) concentrations in the soil, water and plant systems can pose a direct health risk to humans and ecosystems. Phosphate (Pi) ions strongly influence As availability in soil, its uptake and toxicity to plants. Better understanding of As(V)-Pi interactions in soils and plants will facilitate a potential remediation strategy for As contaminated soils, reducing As uptake by crop plants and toxicity to human populations via manipulation of soil Pi content. However, the As(V)-Pi interactions in soil-plant systems are complex, leading to contradictory findings among different studies. Therefore, this review investigates the role of soil type, soil properties, minerals, Pi levels in soil and plant, Pi transporters, mycorrhizal association and microbial activities on As-Pi interactions in soils and hydroponics, and uptake by plants, elucidate the key mechanisms, identify key knowledge gaps and recommend new research directions. Although Pi suppresses As uptake by plants in hydroponic systems, in soils it could either increase or decrease As availability and toxicity to plants depending on the soil types, properties and charge characteristics. In soil, As(V) availability is typically increased by the addition of Pi. At the root surface, the Pi transport system has high affinity for Pi over As(V). However, Pi concentration in plant influences the As transport from roots to shoots. Mycorrhizal association may reduce As uptake via a physiological shift to the mycorrhizal uptake pathway, which has a greater affinity for Pi over As(V) than the root epidermal uptake pathway.

This study presents the particle size distribution and respiratory deposition estimates of airborne perfluoroalkyl acids (PFAAs) during the haze period. Size-segregated haze aerosols were collected from an urban location in Shanghai using an eight-stage air sampler. The samples were analyzed for eight PFAAs using ultra-high-performance liquid chromatography tandem triple quadrupole mass spectrometry. The quantification results showed that the concentrations of particle-bound Σ 8PFAAs ranged from 0.26 to 1.90 ng m⁻³ (mean: 1.44 ng m⁻³). All of the measured PFAAs particle size distributions had a bimodal mode that peaked respectively in accumulation size range (0.4 < Dp < 2.1 μm) and coarse size ranges (Dp > 2.1 μm), but the width of each distribution somewhat varied by compound. The emission source, molecular weight, and volatility of the PFAAs were important factors influencing the size distribution of particle-bound PFAAs. Of these compounds, PFUnDA presented a strong accumulation in the fine size range (average 75% associated with particles <2.1 μm), followed by PFOA (69%) and PFDA (64%). The human risk assessment of PFOS via inhalation was addressed and followed the same pattern as the size distribution, with a 2-fold higher risk for the fine particle fraction compared to the coarse particle fraction at urban sites. Approximately 30.3–82.0% of PFAA deposition (∑PFAA: 72.5%) in the alveolar region was associated with particles <2.1 μm, although the contribution of fine particles to the total PFAAs concentration in urban air was only 28–57% (∑8PFAAs: 48%). These results suggested that fine particles are significant contributors to the deposition of PFAAs in the alveolar region of the lung.