Spatial variation, emissions, transport, and risk assessment of organophosphate esters in two large petrochemical complexes in southern China.

Organophosphate esters (OPEs) serve as significant flame retardants and plasticizers in various petrochemical downstream products. The petrochemical industry could be a potential source of atmospheric OPEs, but their emissions from this industry are poorly understood. The present study revealed the spatial variation, emission, and atmospheric transport of traditional and novel OPEs (TOPEs and NOPEs, respectively) in atmospheric particulate matter (PM) across Hainan and Guangdong petrochemical complexes (HNPC and GDPC, respectively) in southern China. The total concentrations of TOPEs ranged from 232 to 46,002 pg/m3 and from 200 to 20,347 pg/m3 in the HNPC and GDPC, respectively, which were substantially higher than those of NOPEs (HNPC: 23.5-147 pg/m3, GDPC: 13.9-465 pg/m3). Enterprises involved in the production of downstream petrochemical products presented relatively high concentrations of OPEs, indicating evident emissions of these pollutants in the petrochemical industry. The correlations of PM-bound OPEs in the atmosphere are determined mainly by their coaddition to industrial products or their coexistence in technical mixtures. The annual emissions of TOPEs and NOPEs in the HNPC were 42.6 kg and 0.34 kg, respectively, and those in the GDPC were 116 kg and 1.85 kg, respectively. OPEs from the HNPC can reach Vietnam, Cambodia, and Guangxi Province, China, and those from the GDPC can reach Guangxi Province and Hunan Province via atmospheric transmission after 24 h of emission. The OPE concentrations reaching the receptor regions were generally less than 3.20 pg/m3. Risk assessment revealed that OPE inhalation exposure on two petrochemical complexes likely poses minor risks for people living in the study areas, but the risk resulting from two chlorinated OPEs should be noted since they are close to the threshold values. This study has implications for enhancing control measures for OPE emissions to reduce health risks related to the petrochemical industry.

Mechanistic insights into tris(2-chloroisopropyl) phosphate biomineralization coupled with lead (II) biostabilization driven by denitrifying bacteria.

The ubiquity and persistence of organophosphate esters (OPEs) and heavy metal (HMs) pose global environmental risks. This study explored tris(2-chloroisopropyl)phosphate (TCPP) biomineralization coupled to lead (Pb2+) biostabilization driven by denitrifying bacteria (DNB). The domesticated DNB achieved synergistic bioremoval of TCPP and Pb2+ in the batch bioreactor (efficiency: 98 %).TCPP mineralized into PO43- and Cl-, and Pb2+ precipitated with PO43-. The TCPP-degrading/Pb2+-resistant DNB: Achromobacter, Pseudomonas, Citrobacter, and Stenotrophomonas, dominated the bacterial community, and synergized TCPP biomineralization and Pb2+ biostabilization. Metagenomics and metaproteomics revealed TCPP underwent dechlorination, hydrolysis, the TCA cycle-based dissimilation, and assimilation; Pb2+ was detoxified via bioprecipitation, bacterial membrane biosorption, EPS biocomplexation, and efflux out of cells. TCPP, as an initial donor, along with NO3-, as the terminal acceptor, formed a respiratory redox as the primary energy metabolism. Both TCPP and Pb2+ can stimulate phosphatase expression, which established the mutual enhancements between their bioconversions by catalyzing TCPP dephosphorylation and facilitating Pb2+ bioprecipitation. TCPP may alleviate the Pb2+-induced oxidative stress by aiding protein phosphorylation. 80 % of Pb2+ converted into crystalized pyromorphite. These results provide the mechanistic foundations and help develop greener strategies for synergistic bioremediation of OPEs and HMs.

Disposable Plastic Waste and Associated Antioxidants and Plasticizers Generated by Online Food Delivery Services in China: National Mass Inventories and Environmental Release.

China's online food delivery (OFD) services consume enormous amounts of disposable plastics. Here, we investigated and modeled the national mass inventories and environmental release of plastics and chemical additives in the plastic. The extra-tree regression identified six key descriptors in determining OFD sales in Chinese cities. Approximately 847 kt of OFD plastic waste was generated in 2021 (per capita 1.10 kg/yr in the megacities and 0.39 kg/yr in other cities). Various additives were extensively detected, with geomean concentrations of 140.96, 4.76, and 0.25 µg/g for ∑8antioxidants, ∑21phthalates, and bisphenol A (BPA), respectively. The estimated mass inventory of these additives in the OFD plastics was 164.7 t, of which 51.1 t was released into the atmosphere via incineration plants and 51.0 t was landfilled. The incineration also released 8.07 t of polycyclic aromatic hydrocarbons and 39.1 kt of particulate matter into the atmosphere. Takeout food may increase the dietary intake of phthalates and BPA by 30% to 50% and raise concerns about considerable exposure to antioxidant transformation products. This study provides profound environmental implications for plastic waste in the Chinese OFD industry. We call for a sustainable circular economy action plan for waste disposal, but mitigating the hazardous substance content and their emissions is urgent.

Pb0 flue gas biosorption in denitrifying MBfR: Characteristics and binding ability of extracellular polymeric substances.

Pb0 in flue gas which is ubiquitous in the environment, poses a certain threat to human and ecology, but the study on EPS-dependent stabilization of lead to remove Pb0 from flue gas remains insufficient. In this investigation, the characteristics and heavy metals-binding ability of four EPS fractions were evaluated. The EPS were extracted from denitrifying membrane biofilm reactor (MBfR) and divided into slime EPS (S-EPS), loosely-bound EPS (LB-EPS), tightly-bound EPS (TB-EPS) and EPS in circulating flow (Y-EPS). The S, LB, TB-EPS related to Pb stabilization on biofilm need more attention. Compared to Pb-S-EPS (0.013 mg g-1) and Pb-LB-EPS (0.13 mg g-1), the Pb-TB-EPS (0.26 mg g-1) was mainly stable form of vapor Pb0, since TB-EPS's higher content (30.67-82.44 mg g-1 VSS), proteins (13.47-36.32 mg g-1 VSS) and polysaccharides (9.37-32.48 mg g-1 VSS) concentration. Particularly, proteins related ligands were more effective in S, LB, TB-EPS dependent adsorption of Pb, complexing with hydrophobic acid ligands further strengthened in TB-EPS adsorption. The Pb-EPS complex formed via binding with functional groups (such as O-H, N-H, C-H and CC) on EPS, also facilitated by loose structure of proteins. This study enlightens the researchers on the bio-treatment and EPS-dependent biosorption of Pb0 in flue gas in denitrifying MBfR.

Lead removal in flue gas from sludge incineration by denitrification: Insights from metagenomics and metaproteomics.

Flue gas lead emission during sludge incineration damages to human health and ecological environment seriously. Therefore, a denitrifying bio-trickling filter (DNBTF) for lead removal in flue gas from sludge incineration was investigated. Lead removal efficiency was up to 90.7% in 60 days' operation. Lead speciation in biofilms of DNBTF consists of 84.27% residue lead, 15.18% organic bound lead, and less than 1% exchangeable and reducible lead. Lead resistant bacteria and lead resistant-denitrifying bacteria accounted for 85.04% and 58.25%, respectively. Lead resistant microorganisms(Pseudomonas, Azoarcus, Stappia, Pararhodobacter, Paracoccus, Azospirillum, Hyphomonas, Rhodobacter, Polymorphum, Brevunimonas, Stenotrophomonas) could resist the toxicity of Pb2+ in flue gas by transport protein and binding protein, and detoxify Pb2+ in flue gas by extracellular polymeric substances (EPS) adsorption, protein binding and precipitation under the action of resistance genes, such as pbrAB, golT, troABCD, znuABC, czcABCD, pcoB, copA, as shown by integrated metagenomic and metaproteomic analyses. The biofilm was characterized by FTIR, XRD, 3D-EEM, and SEM-EDS. XRD and SEM-EDS spectra indicated the formation of pyromorphite from bioconversion of lead in flue gas. Lead-containing flue gas was bio-stabilized in the form of pyromorphite and HA-Pb via complexation of humic acids in extracellular polymeric substances (EPS), biosorption and biodeposition. This provides a new way of sludge incineration flue gas lead removal using a denitrifying biotricking filter.

Investigation of the effects of high cervical spinal cord electrical stimulation on improving neurological dysfunction and its potential mechanism in rats with traumatic brain injury.

To explore the effects of high cervical spinal cord electrical stimulation (cSCS) on the recovery of neurological function and its possible mechanism in rats with traumatic brain injury (TBI). 72 rats were randomly divided into: (1) a sham group; (2) a traumatic brain injury (TBI) group; (3) a TBI+cSCS group; (4) a LY294002+TBI+cSCS group. The degree of neurological dysfunction was evaluated by modified Neurological severity score (mNSS). The pathological changes of the brain tissue in the injured area were observed by HE staining, and the apoptosis of neuron cells were observed by TUNEL staining. The expressions of BDNF and VEGFmRNA were detected by polymerase chain reaction (PCR), and the expressions of p-AKT, AKT, Bcl-2, Bax and caspase-3 proteins were detected by western blot. Compared with that of the TBI and LY294002+TBI+cSCS groups, the mNSS of the TBI+cSCS group were significantly lower on day 3 and 7 ( P <0.05). Compared with that in the TBI and LY294002+TBI+cSCS groups, the apoptosis of neuron cells in the TBI+cSCS group decreased significantly ( P < 0.05). Compared with the TBI and LY294002+TBI+cSCS group, the expression of Bcl-2 protein increased and the expressions of Bax and Caspase-3 proteins decreased in the TBI+cSCS group ( P < 0.05). Compared with that in the TBI and LY294002+TBI+cSCS groups, the intensity of p-Akt/Akt in the TBI+cSCS group increased ( P < 0.05). We found that cSCS had a protective effect on neuron cells after craniocerebral injury and could improve neurological dysfunction in rats, the mechanism of which might be that cSCS made the PI3K/Akt pathway more active after TBI.

Coupled catalytic-biodegradation of toluene over manganese oxide-coated catalytic membranes.

Volatile organic compounds (VOCs) harm human health and the ecological environment. This work demonstrated manganese oxide catalytic membrane coupled to biodegradation of toluene in a catalytic membrane biofilm rector (CMBfR). Toluene removal efficiency in CMBfR was up to 91% in a 200-day operation. Manganese oxide combined to membrane biofilm reactor could promote degradation of toluene. Manganese oxide catalysts were characterized by XRD, Raman, XPS, and FT-IR. Raman and XPS spectra verified the existence of Mn defects, adsorbed oxygen species, and the oxygen vacancy, which was catalytic of toluene on the Mn oxides coated membranes significantly. Pseudomonas, Hydrogenophaga, Flavobacterium, Bacillus, Clostridium and Prosthecobacter were the dominant bacteria of toluene degradation. Mn oxides catalysis could degrade toluene into intermediate products; these products were entered into the biological phase eventually metabolized to CO2 and H2O. These results show that the catalytic membrane biofilm reactor is achievable and opens new possibilities for applying the catalytic membrane biofilm reactor to VOCs treatment.

Hyperbaric oxygen via mediating SIRT1-induced deacetylation of HMGB1 improved cReperfusion inj/reperfusion injury.

Ischemic stroke leads to severe neurological dysfunction in adults. Hyperbaric oxygen (HBO) induces tolerance to cReperfusion inj/reperfusion (I/R) injury. Therefore, our aims were to investigate whether SIRT1 participates in regulatingin the neuro-protective effect of HBO in a cerebral I/R model and its mechanism. Mice N2a cells were used to construct an oxygen deprivation/reperfusion (OGD/R) model to simulate in vitro brain I/R injury and to evaluate the role of HBO in OGD/R stimulated cells. Cell proliferation was detected using MTT, and apoptosis was determined by flow cytometry. ELISA was used to measure the concentration of TNF-α, IL-1ß and IL-6 related inflammatory factors. RT-qPCR and western blot assays were performed to test the expression of SIRT1. Immunoprecipitation was used to detect acetylation of HMGB1. Expression of SIRT1 was obviously reduced after OGD/R treatment in N2a cells, while SIRT1 was obviously enhanced in HBO treated cells. Moreover, knockdown of SIRT1 induced neuro-inflammation damage in cells and HBO effectively improved the inflammatory response in OGD/R treated cells by affecting SIRT1 levels. Furthermore, HBO induced the deacetylation of HMGB1 via regulating SIRT1. Interestingly, HBO via regulating the SIRT1-induced HMGB1 deacetylation and suppressing MMP-9 improved ischemic brain injury. HBO regulated ischemic brain injury via regulation of SIRT1-induced HMGB1 deacetylation, making it a potential treatment for ischemic brain injury treatment.

Biological treatments of mercury and nitrogen oxides in flue gas: biochemical foundations, technological potentials, and recent advances.

Nitrogen oxides (NOx) and mercury (Hg) are commonly found coexistent pollutants in combustion flue gas. Ever-increasing emission of atmospheric Hg and NOx has caused considerable environmental risks. Traditional flue gas demercuration and denitration techniques have many socioeconomic, technological and environmental drawbacks. Biotechnologies can be a promising and prospective alternative strategy. This article discusses theoretical foundation (biochemistry and genomic basis) and technical potentials (Hg0 bio-oxidation coupled to denitrification) of bioremoval of Hg and NOx in flue gas and summarized recent experimental and technological advances. Finally, several specific technical perspectives have been put forward to better guide future researches.

Identify specific gene pairs for subarachnoid hemorrhage based on wavelet analysis and genetic algorithm.

Subarachnoid hemorrhage (SAH) is a fatal stroke caused by bleeding in the brain. SAH can be caused by a ruptured aneurysm or head injury. One-third of patients will survive and recover. One-third will survive with disability; one-third will die. The focus of treatment is to stop bleeding, restore normal blood flow, and prevent vasospasm. Treatment for SAH varies, depending on the bleeding's underlying cause and the extent of damage to the brain. Treatment may include lifesaving measures, symptom relief, repair of the bleeding vessel, and complication prevention. However, the useful diagnostic biomarkers of SAH are still limited due to the instability of gene marker expression. To overcome this limitation, we developed a new protocol pairing genes and screened significant gene pairs based on the feature selection algorithm. A classifier was constructed with the selected gene pairs and achieved a high performance.

Adjuvant treatment with Angong Niuhuang pills in treating traumatic brain damage: a meta-analysis of randomized controlled trials.

BACKGROUND: The Angong Niuhuang pill (ANP) has been widely used in the adjuvant treatment of patients with traumatic brain injury (TBI). However, the efficacy and adverse reactions of this drug are controversial. In this study, it was aimed to evaluate the effectiveness and safety of ANP on patients with TBI by a systematic review and meta-analysis of randomized controlled trials (RCTs). METHODS: PubMed, Embase, Cochrane Library, Chinese Biomedicine Database (CBM), China National Knowledge Infrastructure (CNKI), Chinese Scientific Journals Database (VIP), and Wangfang databases were systematically searched from their establishment until June 2020. RCTs of ANP treating TBI were enrolled. Odds risk (OR) was used to assess the total effective rate and safety and mean difference (MD) and 95% confidence interval (CI) were used to assess the quantitative data. Tthe included literature's quality was evaluated by RevMan 5.3. The sensitivity and publication bias was evaluated by Stata 16.0. RESULTS: Twelve studies were identified in this systematic review, including 1,568 participants. The metaanalysis results suggested that ANP combined with routine treatment obviously improved the postoperative GCS [MD =1.97, 95% CI (1.22, 2.72), P<0.01] and GOS [OR =2.28, 95% CI (1.60, 3.22), P<0.01] of patients with TBI. ANP also increased Mg2+ concentration and decreased pulmonary infection. In addition, ANP significantly reduced NSE, gastrointestinal bleeding, and liver and kidney function damage. CONCLUSIONS: Based on limited evidence, ANP adjuvant therapy may have a clinical benefit in improving the prognosis of patients with TBI and reducing the associated complications. At the same time, more studies with larger sample sizes and high quality are required to determine the safety and effectiveness of ANP adjuvant therapy.

Mercury oxidation coupled to autotrophic denitrifying branched sulfur oxidation and sulfur disproportionation for simultaneous removal of Hg0 and NO.

Coupling elemental mercury (Hg0) oxidation, autotrophic denitrifying sulfur oxidation, and sulfur disproportionation offers technological potential for simultaneous Hg0 and nitric oxide (NO) removal. This study shed light on simultaneous demercuration and denitration of flue gas by a sulfur-oxidizing membrane biofilm reactor (MBfR). Removal efficiency of Hg0 and NO attained 92% and 83%, respectively in long-term operation. Taxonomic and metagenomic study revealed that a tremendous variety of Hg0-oxidizing bacteria (MOB) (Thiobacillus, Truepera, etc.), denitrifying/sulfur-oxidizing bacteria (DSOB) (Thioalkalivibrio, Thauera, etc.), sulfur-disproportionating bacteria (SDB) (Desulfobulbus, Desulfomicrobium, etc.), and multi-functional bacteria (Halothiobacillus, Thiobacillus, etc.) significantly increased in abundance during growth under feeding of Hg0 and NO in simulated flue gas. The comprehensive employment of sequential chemical extraction processes, inductive coupled mass spectrometry, X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy coupled to energy disperse spectroscopy confirmed that Hg0 was finally biologically oxidized to crystallized metacinnabar (ß-HgS) extracellular micromolecular particles. Our findings provided mechanistic insights that MOB, DSOB, and multi-functional bacteria synergistically bio-oxidized Hg0 as the initial electron donor to Hg2+ and denitrified NO as the terminal electron acceptor to N2. SDB disproportionated S0 branched from S2O32- into S2- and SO42-, and ß-HgS formation from Hg2+ and disproportionation-derived S2-, thermodynamically favored Hg0 bio-oxidation. This novel biotechnique can be a cost-effective and environmentally friendly alternative to flue gas Hg0 and NO treatment. KEY POINTS: • Combination of Hg0 bio-oxidation and autotrophic denitrifying sulfur oxidation achieved simultaneous Hg0 and NO removal. • Thiosulfate disproportionation reinforced Hg0 bio-oxidation for Hg0 removal. • Mercury-oxidizing bacteria, denitrifying/sulfur-oxidizing bacteria, and sulfur-disproportionating bacteria synergistically accomplished Hg0 and NO removal.

Bio-oxidation of Elemental Mercury into Mercury Sulfide and Humic Acid-Bound Mercury by Sulfate Reduction for Hg0 Removal in Flue Gas.

Bioconversion of elemental mercury (Hg0) into immobile, nontoxic, and less bioavailable species is of vital environmental significance. Here, we investigated bioconversion of Hg0 in a sulfate-reducing membrane biofilm reactor (MBfR). The MBfR achieved effective Hg0 removal by sulfate bioreduction. 16 S rDNA sequencing and metagenomic sequencing revealed that diverse groups of mercury-oxidizing/sulfate-reducing bacteria (Desulfobulbus, Desulfuromonas, Desulfomicrobium, etc.) utilized Hg0 as the initial electron donor and sulfate as the terminal electron acceptor to form the overall redox. These microorganisms coupled Hg0 bio-oxidation to sulfate bioreduction. Analysis on mercury speciation in biofilm by sequential extraction processes (SEPs) and inductively coupled mass spectrometry (ICP-MS) and by mercury temperature programmed desorption (Hg-TPD) showed that mercury sulfide (HgS) and humic acid-bound mercury (HA-Hg) were two major products of Hg0 bio-oxidation. With HgS and HA-Hg comprehensively characterized by X-ray diffraction (XRD), excitation-emission matrix spectra (EEM), scanning electron microscopy-energy disperse spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR), it was proposed that biologically oxidized mercury (Hg2+) further reacted with biogenic sulfides to form cubically crystallized metacinnabar (ß-HgS) extracellular particles. Hg2+ was also complexed with functional groups -SH, -OH, -NH-, and -COO- in humic acids from extracellular polymeric substances (EPS) to form HA-Hg. HA-Hg may further react with biogenic sulfides to form HgS. Bioconversion of Hg0 into HgS was therefore achieved and can be a feasible biotechnique for flue gas demercuration.

Nitrification/denitrification shaped the mercury-oxidizing microbial community for simultaneous Hg0 and NO removal.

A denitrifying/nitrifying membrane biofilm reactor for simultaneous removal of Hg0 and NO was investigated. Hg0 and NO removal efficiency attained 94.5% and 86%, respectively. The mercury-oxidizing microbial community was significantly shaped by nitrification/denitrification after the supply of gaseous Hg0and NO continuously. Dominant genera Rhodanobacter and Nitrosomonas participated in Hg0 oxidation, nitrification and denitrification simultaneously. Hg0 oxidizing bacteria (Gallionella, Rhodanobacter, Ottowia, Nitrosomonas and etc.), nitrifying bacteria (Nitrosomonas, Rhodanobacter, Diaphorobacte and etc.) and denitrifying bacteria (Nitrosomonas, Rhodanobacter, Castellaniella and etc.) co-existed in the MBfR, as shown by metagenomic sequencing. X-ray photoelectron spectroscopy (XPS) and high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) confirmed the formation of a mercuric species (Hg2+) from mercury bio-oxidation. Mechanism of mercury oxidation can be described as the bacterial oxidation of Hg0 in which Hg0 serves as electron donor, NO serves as electron donor in nitrification and electron acceptor in denitrification, oxygen serves as electron acceptor.

Downregulation of PCDH9 predicts prognosis for patients with glioma.

Recent evidence has indicated that biological markers are essential in estimating the prognosis of patients with gliomas. The aim of this study was to determine the status and clinical significance of a novel tumor suppressor, PCDH9 (protocadherin 9) in glioma using tissue microarrays and immunohistochemistry. Normal brain tissue showed strong positive immunostaining for PCDH9, but this was downregulated in the primary cerebral glial tumor samples (51.7%). Loss of PCDH9 expression was associated significantly with a higher histological grade. Survival analysis demonstrated that patients with PCDH9-negative tumors had significantly shorter survival times than those with PCDH9-positive tumors and that PCDH9 was an independent prognostic factor. Our results suggest that PCDH9 might function as a tumor suppressor during cancer development and progression and could be regarded as a useful biomarker for predicting the outcome of patients with cerebral glial tumors.