Occurrence, homologue patterns and source apportionment of short- and medium-chain chlorinated paraffins in suburban soils of Shanghai, China.

In order to systematically investigate the spatial distribution, homologue profiles, and sources of short- and medium-chain chlorinated paraffins (SCCPs and MCCPs) in suburban soils in Shanghai, SCCPs and MCCPs in soils were analyzed using gas chromatography coupled with low resolution mass spectrometry in electron capture negative ion (ECNI) mode (GC-ECNI-MS). The CP concentrations in soils were between not detected (ND) - 697 ng g-1 with a median value of 3.52 ng g-1 for SCCPs, and ND - 666 ng g-1 with a median value of 15.3 ng g-1 for MCCPs, respectively. The concentrations of MCCPs in most soils were higher than that of SCCPs. The total CP concentrations (sum of SCCPs and MCCPs) in soils varied from ND to 964 ng g-1 with a median value of 20.5 ng g-1. The concentration of MCCPs was higher than that of SCCPs in most soils. The levels of SCCPs and MCCPs in suburban soils in Shanghai were at the medium level when compared to other areas around the world. No significant correlation was observed between soil CP concentrations and total organic carbon contents (p > 0.05). For different use type of soils, the median concentrations of CPs in soils were found higher in greenland than that in other areas probably due to busy traffic, sewage sludge application and/or wastewater irrigation. All soils were divided into two groups by hierarchical cluster analysis (HCA) both for SCCPs and MCCPs. Three discharge sources of CPs in suburban soil of Shanghai were identified by PMF model.

Occurrence, profiles, and ecological risks of polybrominated diphenyl ethers (PBDEs) in river sediments of Shanghai, China.

Fifty-two PBDE congeners in river sediments from Shanghai were analyzed in the present study. The concentrations of Σ51PBDEs (defined as the sum of 51 BDE congeners except BDE209) and BDE209 ranged from 0.231 to 119 ng g(-1) and from nd to 189 ng g(-1), respectively. The most abundant BDE congeners in surface sediments were BDE118, 207, 208, 99, 49, 75, 47, 71 and 209, with median values of 1.67, 1.81, 1.83, 1.87, 1.98, 2.52, 2.73, 4.62 and 45.7 ng g(-1) dw, respectively. The concentrations of Σ52PBDEs were significantly correlated with total organic carbon (TOC) content in sediments (p < 0.05). Weak correlations between all PBDE homologues and TOC (r < 0.32) suggest that TOC had a little influence on sediment PBDE transport and distribution patterns in river sediments of Shanghai. Correspondence analysis (CA) showed that PBDEs in sediments in the studied area originated from commercial BDE formulations, combustion emission sources, and debromination of highly brominated PBDEs by aerobic/anaerobic microbes or sunlight. Risk assessment based on risk quotients (RQ) showed that PBDEs in all river sediments collected from Shanghai posed a high potential ecological risk (RQ > 1) to the sediment dwelling organisms, and pentaBDE, decaBDE and tetraBDE were the major ecological risk drivers.

Occurrence, sources and health risk assessment of polycyclic aromatic hydrocarbons in urban (Pudong) and suburban soils from Shanghai in China.

A comprehensive investigation was conducted to the urban (Pudong) and suburban soils in Shanghai. A total of 154 soil samples were analyzed for 26 PAHs including highly carcinogenic dibenzopyrenes (DBPs). The total concentrations ranged from 25.8 to 7380 µg kg(-1) for Σ26PAHs and 18.8 to 6320 µg kg(-1) for 16 USEPA priority PAHs (Σ16PAHs), respectively. The BaP toxic equivalent (BaPeq) concentrations were between 6.41 and 2880 µg kg(-1) for Σ24PAHs, 1.11 and 620 µg kg(-1) for Σ16PAHs and 2.72 and 2250 µg kg(-1) for Σ4DBPs. The high PAH contamination in green land soils might originate mainly from local road traffic and industrial activities, and sewage sludge application or waste water irrigation for soil. Seven sources of soil PAHs in Shanghai were identified by positive matrix factorization (PMF) model. The mean risk quotient (m-RQ) values indicated that there were medium to high ecological risks in 9.10% of soil samples, pyrene (Pyr), benzo[b]fluoranthene (BbF) and benz[a]anthracene (BaA) were the major ecological risk drivers under agricultural use. The cancer risk (CR) values were within the acceptable range at 35.7%, 35.1% and 31.2% of sampling sites for children, youths and adults, respectively. The total lifetime carcinogenic risk (TLCR) values at 57.8% of sampling sites were within the acceptable range. Overall, cancer risks of soil PAHs in all sampling sites in the studied area were below the highest acceptable risk, suggesting that soil PAHs are unlikely to pose a significant cancer risk for population based on ingestion, dermal contact and inhalation exposure pathways.

Influence of pH, inorganic anions, and dissolved organic matter on the photolysis of antimicrobial triclocarban in aqueous systems under simulated sunlight irradiation.

The photolysis of the antimicrobial triclocarban (TCC) in aqueous systems under simulated sunlight irradiation was studied. The effects of several abiotic parameters, including solution pH, initial TCC concentration, presence of natural organic matter, and most common inorganic anions in surface waters, were investigated. The results show that the photolysis of TCC followed pseudo-first-order kinetics. The TCC photolysis rate constant increased with increasing solution pH and decreasing the initial TCC concentration. Compared with the TCC photolysis in pure water, the presence of aqueous bicarbonate, nitrate, humic acids, and its sodium salt decreased the TCC photolysis rate, but fulvic acid increased the TCC photolysis rate. The electron spin resonance and reactive oxygen species scavenging experiments indicated that TCC may undergo two different types of phototransformation reactions: direct photolysis and energy transfer to generate (1)O2. The main degradation products were tentatively identified by gas chromatography interfaced with mass spectrometry (GC-MS), and a possible degradation pathway was also proposed.

Short- and medium-chain chlorinated paraffins in urban soils of Shanghai: spatial distribution, homologue group patterns and ecological risk assessment.

Chlorinated paraffins (CPs) are toxic, bioaccumulative, persistent, and ubiquitously present in the environment. Data on the presence of short- and medium-chain chlorinated paraffins (SCCPs and MCCPs) in urban areas with dense population are still scarce to date. SCCPs and MCCPs were measured in urban soils from Shanghai to comprehensively investigate their levels, spatial distribution, homologue group patterns and ecological risk. The concentrations of CPs in soils varied from ND to 615 ng g(-1) with a median value of 15.7 ng g(-1) for SCCPs and from 1.95 to 188 ng g(-1) with a median value of 7.98 ng g(-1) for MCCPs, respectively. The concentrations of SCCPs in most soils were higher than those of MCCPs. The total CP concentrations in soil samples were between 4.10 and 625 ng g(-1) with a median value of 26.4 ng g(-1). For different functional zones, the median concentrations of soil CPs were found higher in green land including park, greenbelt and campus than those in roadside. The highest concentrations of CPs in soils could be derived from sewage sludge application and wastewater irrigation for green land. Three types of soils were classified by hierarchical cluster analysis (HCA) for SCCPs and MCCPs, the most abundant homologue groups in the bulk of the soil samples were C11Cl5-7 and C13Cl5-7 for SCCPs, and C14Cl7-8 and C15Cl7-8 for MCCPs. Correlation analysis and PCA suggested that SCCPs and MCCPs in soils in the studied area derived from different sources. The preliminary ecological risk assessment indicates that soil CPs at present levels poses no significant ecological risk for soil-dwelling organisms.

Occurrence, distribution, and multi-phase partitioning of triclocarban and triclosan in an urban river receiving wastewater treatment plants effluent in China.

Occurrence, distribution, spatial and seasonal variations, and partitioning between aqueous phase and suspended particulate matters (SPM) of triclocarban (TCC) and triclosan (TCS) in Xiaoqing River, which receives wastewater treatment plant (WWTP) effluents, were studied. The distribution of the total TCC and TCS levels in surface water and sediments along the river were discussed. The highest TCC and TCS concentrations were both found near the discharge port of WWTPs, and the TCC and TCS levels decreased downstream of the WWTPs as a result of their distances from the source of WWTP discharges. The mean values of TCC and TCS in low-flow season were 1.62 and 1.80 times, respectively, as much as in high-flow season in surface water. The study on partitioning of TCC and TCS between aqueous phase and SPM shown the mean level of dissolved TCC accounted for about 10 % of the total level in surface water, whereas the TCS level was about 30 %. The TCC concentrations detected in the surface sediment samples (0 to 5 cm) ranged from 226 to 1,956 ng/g, with a mean value of 733 ng/g. The TCS levels were between 85 and 705 ng/g, with a mean value of 255 ng/g. The distribution and variations of TCC and TCS in sediments along the river were highly consistent with those in the water phase. The TCC and TCS levels in deep sediments (5 to 10 cm) were significantly lower than those in surface sediments. The mean TCC level in surface sediments was about 2.4 times as much as in deep sediments, and the TCS level in surface sediments was 3.1 times as much as in deep sediments.

Photodegradation of the antimicrobial triclocarban in aqueous systems under ultraviolet radiation.

This work aimed to investigate the effectiveness of ultraviolet (UV) radiation on the degradation of the antimicrobial triclocarban (TCC). We investigated the effects of several operational parameters, including solution pH, initial TCC concentration, photocatalyst TiO2 loading, presence of natural organic matter, and most common anions in surface waters (e.g., bicarbonate, nitrate, and sulfate). The results showed that UV radiation was very effective for TCC photodegradation and that the photolysis followed pseudo-first-order kinetics. The TCC photolysis rate was pH dependent and favored at high pH. A higher TCC photolysis rate was observed by direct photolysis than TiO2 photocatalysis. The presence of the inorganic ions bicarbonate, nitrate, and sulfate hindered TCC photolysis. Negative effects on TCC photolysis were also observed by the addition of humic acid due to competitive UV absorbance. The main degradation products of TCC were tentatively identified by gas chromatograph with mass spectrometer, and a possible degradation pathway of TCC was also proposed.

Determination of trace triclosan in environmental water by microporous bamboo-activated charcoal solid-phase extraction combined with HPLC-ESI-MS.

A sensitive and efficient analytical method for triclosan (TCS) determination in water, which involves enrichment with bamboo-activated charcoal and detection with HPLC-ESI-MS, was developed. The influence of several operational parameters, including the eluant and its volume, the flow rate, the volume andacidity of the sample, and the amount of bamboo-activated charcoal, were investigated and optimized. Under the optimum conditions, linearity of the method was observed in the range of 0.02-20 µg/L, with correlation coefficients (r(2) ) >0.9990. The limit of detection was 0.002 µg/L based on the ratio of chromatographic signal to baseline noise (S/N = 3). The spiked recoveries of TCS in real water samples were achieved in the range of 97.6-112.5%. The proposed method was applied to analyze TCS in real aqueous samples. All the surface water samples collected in Xiaoqing River had detectable levels of TCS with concentrations of 42-197 ng/L.

Temperature-controlled ionic liquid dispersive liquid-phase microextraction for the sensitive determination of triclosan and triclocarban in environmental water samples prior to HPLC-ESI-MS/MS.

A novel dispersive liquid-phase microextraction method without dispersive solvents has been developed for the enrichment and sensitive determination of triclosan and triclocarban in environmental water samples prior to HPLC-ESI-MS/MS. This method used only green solvent 1-hexyl-3-methylimidazolium hexafluorophosphate as extraction solvent and overcame the demerits of the use of toxic solvents and the instability of the suspending drop in single drop liquid-phase microextraction. Important factors that may influence the enrichment efficiencies, such as volume of ionic liquid, pH of solutions, extraction time, centrifuging time and temperature, were systematically investigated and optimized. Under optimum conditions, linearity of the method was observed in the range of 0.1-20 microg/L for triclocarban and 0.5-100 microg/L for triclosan, respectively, with adequate correlation coefficients (R>0.9990). The proposed method has been found to have excellent detection sensitivity with LODs of 0.04 and 0.3 microg/L, and precisions of 4.7 and 6.0% (RSDs, n=5) for triclocarban and triclosan, respectively. This method has been successfully applied to analyze real water samples and satisfactory results were achieved.

Trace determination of triclosan and triclocarban in environmental water samples with ionic liquid dispersive liquid-phase microextraction prior to HPLC-ESI-MS-MS.

A novel and environmentally friendly microextraction method, termed ionic liquid dispersive liquid-phase microextraction (IL-DLPME), has been developed for rapid enrichment of triclosan and triclocarban before analysis by high-performance liquid phase chromatography-electrospray tandem mass spectrometry (HPLC-ESI-MS-MS). Instead of using toxic organic solvents, an ionic liquid was used as a green extraction solvent. This also avoided the instability of the suspending drop in single-drop liquid-phase microextraction, and the heating and cooling step in temperature-controlled ionic liquid dispersive liquid phase microextraction. Factors that may affect the enrichment efficiency, for example volume of ionic liquid, type and volume of dispersive solvent, pH, extraction time, and NaCl content were investigated in detail and optimized. Under optimum conditions, linearity of the method was observed over the range 0.2-12 microg L(-1) for triclocarban and 1-60 microg L(-1) for triclosan with correlation coefficients ranging from 0.9980 to 0.9990, respectively. The sensitivity of the proposed method was found to be excellent, with limits of detection in the range 0.040-0.58 microg L(-1) and precision in the range 7.0-8.8% (RSD, n = 5). This method has been successfully used to analyze real environmental water samples and satisfactory results were achieved. Average recoveries of spiked compounds were in the range 70.0-103.5%. All these results indicated that the developed method would be a green method for rapid determination of triclosan and triclocarban at trace levels in environmental water samples.

Sonochemical synthesis of silver nanorods by reduction of silver nitrate in aqueous solution.

The sonochemical synthesis of silver nanorods has been achieved by ultrasonic irradiation of the aqueous solution of silver nitrate, methenamine (HMTA) and poly (vinyl pyrrolidone) (PVP) for 60 min. The silver nanorods obtained have lengths of 4-7 microm and mean diameters of about 100 nm. The structures of the samples were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), selected area electron diffraction (SAED) and X-ray powder diffraction (XRD), and the chemical composition of the sample was examined by energy-dispersive X-ray spectrum (EDS). The effects of the irradiation time, the concentration of PVP and the reaction temperature on the morphology of silver nanorods were discussed, and the mechanism of the silver nanorods formation was tentatively inferred.

Synthesis of dendritic silver nanostructures by means of ultrasonic irradiation.

In this paper, a simple and effective route for the synthesis of silver dendritic nanostructures by means of ultrasonic irradiation has been developed. Well-defined silver dendritic nanostructures were obtained by sonicating the aqueous solution of 0.04mol/L silver nitrate with 4.0mol/L isopropanol as reducing agent and 0.01mol/L PEG400 as disperser for 2h. The effects of the irradiation time, the concentration of Ag(+) and the molar ratio of PEG to AgNO(3) on the morphology of silver nanostructures were discussed. The structures of the obtained samples were characterized by transmission electron microscopy (TEM), selected area electron diffraction (SAED) and X-ray powder diffraction (XRD), and the chemical composition of the dendrites was examined by energy-dispersive X-ray spectrum (EDS).

Heterogeneous photocatalytic degradation kinetic of gaseous ammonia over nano-TiO2 supported on latex paint film.

OBJECTIVE: To investigate the photocatalytic degradation of gaseous ammonia in static state by using nano-TiO2 as photocatalyst supported on latex paint film under UV-irradiation. METHODS: Experiments were conducted to study the relationship between the initial concentration of ammonia and the degradation products competing to be adsorbed on catalyst surface. Degradation of ammonia and its products were detected by spectrophotometry and catalytic kinetic spectrophotometry, respectively. RESULTS: On the one hand, TiO2 catalyst was excellent for degradation of ammonia, and the crystal phase of TiO2, anatase or rutile, had little effect on degradation of ammonia, but the conversion of ammonia grew with the increase of catalyst content. On the other hand, apparent rate constant and conversion of ammonia decreased with the increase of initial concentration of ammonia, and the photocatalytic degradation reaction followed a pseudo-first-order expression due to the evidence of linear correlation between -lnC/C0 vs. irradiation time t, but the relationship between initial concentration and the degradation products was not linear in low initial concentration. CONCLUSION: Whether the photocatalytic degradation of ammonia in static state follows a first-order reaction depends on the initial ammonia concentration due to competition in adsorption between reactant and the degradation products.