[Show abstract][Hide abstract] ABSTRACT: It is hard to quantify the trace pollutants in the environment without the corresponding reference standards. Structure identifications of unknown organic pollutants are thus of great importance in environmental analysis. As for polybrominated diphenyl ethers (PBDE) with one substituent of methoxyl group, there are 837 congeners, but only 32 standards are commercially available. In this work, an effective method based on gas chromatography coupled with mass spectrometry (GC–MS) was proposed to predict the potential structures of methoxylated polybrominated diphenyl ethers (MeO-PBDEs). The mass fragmentation pattern using SIM mode not only provided the useful information on the substitution position of methoxyl group, the number of Br atoms, but also guaranteed the high sensitivity for trace analysis. Br distribution patterns of the unknown MeO-PBDEs were revealed by a linear regression model with dummy variables which described the retention time relationship between MeO-PBDEs and the corresponding PBDEs on different types of GC columns. This method was successfully used to identify three new MeO-PBDEs metabolites of BDE-28 as 4-MeO-BDE-22, 4’-MeO-BDE-25 and 4-MeO-BDE-31 in the pumpkins. Therefore, the newly developed structure prediction model based on GC–MS behavior is helpful in the evaluation of unknown PBDE metabolites in the environment.
[Show abstract][Hide abstract] ABSTRACT: Activated sludge is hard to be dewatered due to the highly water bounded in sludge flocs. This study investigated the hybrid treatment of microwave irradiation and acidification on sludge dewaterability as well as its mechanism. Results showed that the combined microwave-acid treatment (T = 100 °C, initial pH = 2.5) was effective for improving sludge dewaterability, e.g. capillary suction time (CST) decreased from 37.7 s to 9.2 s, bound water content decreased from 1.96 ± 0.19 g/g Dry Sludge (DS) to 0.88 ± 0.24 g/g DS. The treated sludge showed more fluidity and less thixotropy. Both MW heating temperature and pH played important roles in improving sludge dewaterability. Higher temperature was beneficial for sludge disintegration, but the released polymers resulted in highly negative zeta potential and deteriorated sludge dewaterability. The acidification was capable of reducing the negative zeta potential, increasing flocs size and finally improving sludge dewaterability. According to the analysis of molecule weight distribution and 3D-EEM, the fractions of polymers especially protein-like substances at molecule weight of 10(4)-10(5) Da were the key organics related to sludge dewaterability, but not the humic acid-like and fulvic acid-like substances.
[Show abstract][Hide abstract] ABSTRACT: Because of their significant impact on public health, waterborne pathogens, especially bacteria and viruses, are frequently monitored in surface water to assess microbial quality of water bodies. However, more than one billion people worldwide currently lack access to safe drinking water, and a diversity of waterborne outbreaks caused by pathogens is reported in nations at all levels of economic development. Spatio-temporal distribution of conventional pollutants and five pathogenic microorganisms were discussed for the Haihe River Basin. Land use and socio-economic assessments were coupled with comprehensive water quality monitoring. Physical, chemical, and biological parameters were measured at 20 different sites in the watershed for 1 year, including pH, temperature, conductivity, dissolved oxygen, turbidity, chemical oxygen demand, ammonia-N, total and fecal coliforms, E. coli, and Enterococcus. The results highlighted the high spatio-temporal variability in pathogen distribution at watershed scale: high concentration of somatic coliphages and fecal indicator bacteria in March and December and their very low concentration in June and September. All pathogens were positively correlated to urban/rural residential/industrial land and negatively correlated to other four land use types. Microbial pollution was greatly correlated with population density, urbanization rate, and percentage of the tertiary industry in the gross domestic product. In the future, river microbial risk control strategy should focus more on the effective management of secondary effluent of wastewater treatment plant and land around rivers.
No preview · Article · Dec 2015 · Environmental Science and Pollution Research
[Show abstract][Hide abstract] ABSTRACT: Microwave (MW) hybrid processes are able to disrupt the flocculent structure of complex waste activated sludge, and help promote the recovery of phosphorus as struvite. In this study, to optimize struvite yield, (1) the characteristics of matter released in MW-hybrid treatments were compared, including MW, MW-acid, MW-alkali, MW-H2O2, and MW-H2O2-alkali. The results showed that selective release of carbon, nitrogen, phosphorus, Ca2 +, and Mg2 + achieved by sludge pretreatment using MW-hybrid processes. MW-H2O2 is the recommended sludge pretreatment process for phosphorus recovery in the form of struvite. The ratio of Mg2 +:NH4+-N:PO43 −-P was 1.2:2.9:1 in the supernatant. (2) To clarify the effects of organic matter on struvite recovery, the composition and molecular weight distribution of organic matters were analyzed. Low molecular weight COD was found to facilitate the removal rate of NH4+-N and PO43-P via crystallization, and the amorphous struvite crystals (< 1 kDa) from the filtered solutions had high purity. Therefore, the present study reveals the necessity of taking into consideration the interference effect of high molecular weight organic matters during struvite crystallization from sewage sludge.
[Show abstract][Hide abstract] ABSTRACT: The stability of engineered nanomaterials in natural aquatic environment has drawn much attention over the past years. Silver sulfide nanoparticles (Ag2S-NPs) are generally assumed to be stable in natural environment due to their physicochemical property, however, it may vary depending on environmental conditions. Here, we investigated whether and how the environmentally relevant factors including light irradiation, solution pH, inorganic salts, dissolved organic matter (DOM) and dissolved oxygen (DO) individually and in combination influenced the stability of Ag2S-NPs in aquatic environment. We presented for the first time that transformation of Ag2S-NPs can indeed occur in the aqueous system with environmentally relevant concentration of Fe3+ under simulated solar irradiation and natural sunlight within short time (96 h), along with significant changes in morphology and dissolution. The photoinduced transformation of Ag2S-NPs in the presence of Fe3+ can be dramatically influenced by solution pH, Ca2+/Na+ and Cl-/SO42-, DOM and DO. Moreover, Ag2S-NPs dissolution increased within 28 h, followed rapid decline in the next 68 h, which may be a result of the reconstitution of small Ag2S-NPs. Taken together, this work is of importance to comprehensively evaluate the stability of Ag2S-NPs in aquatic environment, improving our understanding of their potential risks to human and environmental health.
No preview · Article · Nov 2015 · Environmental Science & Technology
[Show abstract][Hide abstract] ABSTRACT: Membrane fouling, including foulants and factors, was investigated during hydraulic retention time (HRT) optimization of a membrane bioreactor (MBR) that treated wastewater from the production of antibiotics. The results showed that HRT played an important role in membrane fouling. Trans-membrane pressure (TMP), membrane flux, and resistance were stable at -6 kPa, 76 L m(-2) h(-1) bar(-1), and 4.5 × 10(12) m(-1) when HRT was at 60, 48, and 36 h, respectively. Using Fourier transform infrared spectroscopy, foulants were identified as carbohydrates and proteins, which correlated with effluent organic matter and effluent chemical oxygen demand (COD) compounds. Therefore, membrane fouling trends would benefit from low supernatant COD (378 mg L(-1)) and a low membrane removal rate (26 %) at a HRT of 36 h. Serious membrane fouling at 72 and 24 h was related to soluble microbial products and extracellular polymeric substances in mixed liquor, respectively. Based on the TMP decrease and flux recovery after physical and chemical cleaning, irremovable fouling aggravation was related to extracellular polymeric substances' increase and soluble microbial products' decrease. According to changes in the specific oxygen uptake rate (SOUR) and mixed liquor suspended solids (MLSSs) during HRT optimization in this study, antibiotic production wastewater largely inhibited MLSS growth, which only increased from 4.5 to 5.0 g L(-1) when HRT was decreased from 72 to 24 h, but did not limit sludge activity. The results of a principal component analysis highlighted both proteins and carbohydrates in extracellular polymeric substances as the primary foulants. Membrane fouling associated with the first principal component was positively related to extracellular polymeric substances and negatively related to soluble microbial products. Principal component 2 was primarily related to proteins in the influent. Additional membrane fouling factors included biomass characteristics, operational conditions, and feed characteristics.
Full-text · Article · Nov 2015 · Environmental Science and Pollution Research
[Show abstract][Hide abstract] ABSTRACT: This study investigated the effects of residual H2O2 on hydrolysis-acidification and methanogenesis stages of anaerobic digestion after microwave-H2O2 (MW-H2O2) pretreatment of waste activated sludge (WAS). Results showed that high sludge solubilization at 35-45 % was achieved after pretreatment, while large amounts of residual H2O2 remained and refractory compounds were thus generated with high dosage of H2O2 (0.6 g H2O2/g total solids (TS), 1.0 g H2O2/g TS) pretreatment. The residual H2O2 not only inhibited hydrolysis-acidification stage mildly, such as hydrolase activity, but also had acute toxic effect on methanogens, resulting in long lag phase, low methane yield rate, and no increase of cumulative methane production during the 30-day BMP tests. When the low dosage of H2O2 at 0.2 g H2O2/g TS was used in MW-H2O2 pretreatment, sludge anaerobic digestion was significantly enhanced. The cumulative methane production increased by 29.02 %, but still with a lag phase of 1.0 day. With removing the residual H2O2 by catalase, the initial lag phase of hydrolysis-acidification stage decreased from 1.0 to 0.5 day.
Full-text · Article · Nov 2015 · Environmental Science and Pollution Research
[Show abstract][Hide abstract] ABSTRACT: The effects of microwave pretreatment (MW) on co-digestion of food waste (FW) and sewage sludge (SS) have never been investigated. In this study, a series of mesophilic biochemical methane potential (BMP) tests were conducted to determine the optimized ratio of FW and SS based on MW, and the evolution of bacterial and archaeal community was investigated through high-throughput sequencing method. Results showed that the optimized ratio was 3:2 for co-digestion of FW and SS based on MW, and the methane production was 316.24 and 338.44mLCH4/gVSadded for MW-FW and MW-SS, respectively. The MW-SS was superior for methane production compared to MW-FW, in which accumulation of propionic acid led to the inhibition of methanogenesis. Proteiniborus and Parabacteroides were responsible for proteins and polysaccharides degradation for all, respectively, while Bacteroides only dominated in co-digestion. Methanosphaera dominated in MW-FW at the active methane production phase, while it was Methanosarcina in MW-SS and mono-SS.
Full-text · Article · Oct 2015 · Bioresource Technology
[Show abstract][Hide abstract] ABSTRACT: Short-chain chlorinated paraffins (SCCPs) are a group of n-alkanes with carbon chain length of 10-13. In this work, paired indoor/outdoor samples of organic films on window glass surfaces from urban buildings in Beijing, China, were collected to measure the concentrations and congener distributions of SCCPs. The total SCCP levels ranged from 337 ng/m(2) to 114 μg/m(2), with total organic carbon (TOC) normalized concentrations of 365 μg/m(2)-365 mg/m(2). Overall, the concentrations of SCCPs on the interior films were higher than the concentrations on the exterior films, suggesting an important indoor environmental exposure of SCCPs to the general public. A significant linear relationship was found between the SCCP concentrations and TOC, with a correlation coefficient of R = 0.34 (p < 0.01). A film-air partitioning model suggests that the indoor gas-phase SCCPs are related to their corresponding window film levels.
[Show abstract][Hide abstract] ABSTRACT: Polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) were extensively investigated in the sediment samples collected from seven major river basins around China. The concentrations were in the range of 0.05-6.15 × 10(4) ng g(-1) dry weight (dw), 0.29-21.7 ng g(-1) dw and 0.01-6.49 ng g(-1) dw for PBDEs, PCBs and PCDD/Fs, respectively. The concentrations showed wide variations among different river basins, while the congener profiles in all the sediments were generally characterized by only a few compounds, such as BDE-209, -99 and -47, CB-11 and -28, OCDD and OCDF, etc. The spatial analysis identified a decreasing trend of these persistent organic pollutants (POPs) from south to north China, consistent with regional industrialization. However, relatively higher level of POPs was also observed in the upstream of Yellow River Basin. The present study gives insight into the spatial occurrence of the three POPs in the major river basins in China.
[Show abstract][Hide abstract] ABSTRACT: Temporal trends of short- (SCCPs) and medium-chain chlorinated paraffins (MCCPs) were examined in blubber samples of 50 finless porpoises (Neophocaena phocaenoides) and 25 Indo-Pacific humpback dolphins (Sousa chinensis) collected from the South China Sea between 2004 and 2014. Elevated levels of SCCPs and MCCPs were detected in all blubber samples of two cetacean species. Concentrations of SCCPs ranged from 280 to 3,900 ng g-1 dry weight (d.w.) in porpoises and from 430 to 9,100 ng g-1 d.w. in dolphins, while concentrations of MCCPs ranged from 320 to 8,600 ng g-1 d.w. in porpoises and 530 to 23,000 ng g-1 d.w. in dolphins. Significantly higher concentrations were present in dolphins than porpoises due to their exposure levels in their living habitats. Strongly linear correlations existed between SCCPs and MCCPs, but there were no significant concentration differences between the genders of both cetacean species in the same sampling year. Significantly temporal increasing trends of SCCPs and MCCPs have been observed in both porpoise and dolphin samples over the past decade, which reflect the influence of histories of production and usage on the bioaccumulation of CPs in marine mammals in China. An apparent temporal shift trend from SCCPs to MCCPs was also observed in CP accumulation profiles. Complex environmental fractionation from localized sources in the study region via atmospheric transport, oceanic/offshore water transport and trophic transfer, have resulted in different CP accumulation levels and homologue patterns in the two cetacean species. This is the first report of systematic temporal trends of SCCPs and MCCPs in marine mammals.
[Show abstract][Hide abstract] ABSTRACT: The enhancement for sludge anaerobic digestion and dewaterability were investigated in sludge pretreated by microwave (MW) and its combined processes. The results showed that microwave and its combined processes can efficiently release soluble organic matter and thus enhance anaerobic digestion of sludge. The cumulative methane production in the test of the MW-H2O2 -OH (0.2) process was increased by 13.34% compared with that of the control. The MW-H process was effective in improving sludge dewaterability, e.g., the capillary suction time (CST) at only 9.85S.
No preview · Article · Sep 2015 · Journal of Water Reuse and Desalination
[Show abstract][Hide abstract] ABSTRACT: The nitrogen removal performance in the combined partial nitritation-anammox (CPNA) process was seriously deteriorated by the nitrate build-up. The purpose of this study was to develop and optimize an in-situ restoring strategy based on hydroxylamine (NH2OH) dosing and solids retention time (SRT) control for the deteriorated CPNA process. Results showed that the 0.55 kgN m−3 d−1 of nitrogen removal rate could be recovered by 20 mgNH2OH L−1 of hydroxylamine dosing and 40 days of SRT control, the nitrate concentration in effluent was decreased from the highest 548.4 mgN L−1 during deterioration to 65.1 mgN L−1 after restoration, and the ratio of NO3−-Nproduced/NH4+-Nconsumed in one SBR cycle was reduced from the highest 87.0% to 9.13% finally. The inhibition of nitrite-oxidizing bacteria (NOB) by NH2OH dosing alone was reversible because the nitrate build-up occurred again from 106.9 to 287.6 mgN L−1 within just 11 days after NH2OH dosing was stopped. The evolution of the anammox bacteria, ammonium-oxidizing bacteria (AOB) and NOB from quantitative PCR (qPCR) assays verified the changes of the nitrogen removal performance of the CPNA process and proved that this in-situ restoration strategy could successfully solve the problem of nitrate build-up in the CPNA process.
No preview · Article · Jun 2015 · Biochemical Engineering Journal
[Show abstract][Hide abstract] ABSTRACT: Rapid screening and identification of hazardous chemicals in complex samples is of extreme importance for public safety and environmental health studies. In this paper, we report a new method for high-throughput, sensitive, and rapid screening of low-mass hazardous compounds in complex media without complicated sample preparation procedures. This method is achieved based on size-selective enrichment on ordered mesoporous carbon followed by matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS) analysis with graphene as a matrix. The ordered mesoporous carbon CMK-8 can exclude interferences from large molecules in complex samples (e.g., human serum, urine, and environmental water samples) and efficiently enrich a wide variety of low-mass hazardous compounds. The method can work at very low concentrations down to part per trillion (ppt) levels, and it is much faster and more facile than conventional methods. It was successfully applied to rapidly screen and identify unknown toxic substances such as perfluorochemicals in human serum samples from athletes and workers. Therefore, this method not only can sensitively detect target compounds, but also can identify unknown hazardous compounds in complex media.
Full-text · Article · Jun 2015 · Analytical Chemistry
[Show abstract][Hide abstract] ABSTRACT: In this study, serum and urine samples were collected from 36 occupational workers in a fluorochemical manufacturing plant in China from 2008 to 2012 to evaluate the body burden and possible elimination of linear and branched perfluoroalkyl acids (PFAAs). Indoor dust, total suspended particles (TSP), diet and drinking water samples were also collected to trace occupational exposure pathway to PFAA isomers. The geometric mean concentrations of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and perfluorohexanesulfonate (PFHxS) isomers in the serum were 1386, 371 and 863 ng mL-1, respectively. The linear isomer of PFOS, PFOA, and PFHxS was the most predominant PFAA in the serum, with mean proportions of 63.3%, 91.1%, and 92.7% respectively, which were higher than the proportions in urine. The most important exposure routes to PFAA isomers in the occupational workers were considered to be the intake of indoor dust and TSP. A renal clearance estimation indicated that branched PFAA isomers had a higher renal clearance rate than the corresponding linear isomers. Molecular docking modeling implied that linear PFOS (n-PFOS) had a stronger interaction with human serum albumin (HSA) than branched isomers did, which could decrease the proportion of n-PFOS in the blood of humans via the transport of HSA.
[Show abstract][Hide abstract] ABSTRACT: The exposure pathways of perfluoroalkyl acids (PFAAs) to humans are still not clear because of the complex living environment, and few studies have simultaneously investigated the bioaccumulative behaviour of different PFAAs in humans. In this study, serum, dust, duplicate diet, and other matrices were collected around a manufacturing plant in China, and homologous series of PFAAs were analysed. PFAA levels in dust and serum of local residents in this area were considerably higher than those in non-polluted area. Although dietary intake was the major exposure pathway in the present study, dust ingestion played an important role in this case. Serum PFAAs in local residents was significantly correlated with dust PFAAs levels in their living or working microenvironment. Serum PFAAs and dust PFAAs were significantly higher in family members of occupational workers (FM) than in ordinary residents (OR) (p < 0.01). After a careful analysis of the PFAAs exposure pathway, a potential pathway in addition to direct dust ingestion was suggested: PFAAs might transferred from occupational worker's clothes to dinners via cooking processes. The bioaccumulative potential of PFHxS and PFOS were higher than other PFAAs, which suggested a substantial difference between the bioaccumulative ability of perfluorinated sulfonic acids and perfluorinated carboxylic acids.
No preview · Article · Mar 2015 · Scientific Reports
[Show abstract][Hide abstract] ABSTRACT: Sulfidation is considered as a natural antidote to toxicity of metallic nanoparticles (NPs). The detoxification contribution from sulfidation, however, may vary depending on sulfidation mechanisms. Here we present the dissolution-precipitation instead of direct solid-state-shell mechanism to illustrate the process of CuO-NPs conversion to CuS-NPs in aqueous solutions. Accordingly, the CuS-NPs at environmentally relevant concentrations showed much stronger interference on Japanese medaka (Oryzias latipes) embryo hatching than CuO-NPs, which was probably due to elevated free copper ions released from CuS-NPs, leading to significant increase in oxidative stress and causing toxicity in embryos. The larval length was significantly reduced by CuS-NPs, however, no other obviously abnormal morphological features were identified in the hatched larvae. Co-introduction of a metal ion chelator [ethylene diamine tetraacetic acid (EDTA)] could abolish the hatching inhibition induced by CuS-NPs, indicating free copper ions released from CuS-NPs play an important role in hatching interference. This work documents for the first time that sulfidation as a natural antidote to metallic NPs is being overestimated, which has far reaching implications for risk assessment of metallic NPs in aquatic environment.
No preview · Article · Jan 2015 · Environmental Science and Technology