Development of a novel solid-phase extraction element for the detection of nonylphenol in the surface water of Hangzhou

Nonylphenol (NP) is a representative environmental endocrine-disrupting chemical and persistent toxic pollutant. Previous studies have shown that the average concentration of NP in environmental waters was approximately tens to hundreds of ng L(-1) and it could even reach up to tens of μg L(-1). A simple, fast and accurate method employing a novel solid-phase extraction element named "Magic Chemisorber" (MC) followed by high-performance liquid chromatography (HPLC) using a fluorescence detector (FLD) was used for detecting NP. The most important parameters that affect the extraction process, including extraction time, desorption time, desorption solvent and repeatability, were optimized. The MC-HPLC method showed good linearity with concentrations of NP from 10 to 200 μg L(-1), a correlation coefficient of 0.9995 and the limit of detection (LOD) and limit of quantification (LOQ) of this method was 0.44 and 1.47 μg L(-1), respectively. Compared to commercial polydimethylsiloxane (PDMS) glass fiber, MC had both higher capacity and recovery and it could be used repeatedly. Using the MC-HPLC method we found that the concentration of NP in river water from Hangzhou city ranged from 8.54 ± 1.23 μg L(-1) (Qiantang River) to 65.77 ± 3.69 μg L(-1) (Tiesha River), which was similar to that of international regions heavily polluted with NP and higher than that of Bohai Bay, the Yellow River and the Pearl River Delta in China. This level of NP pollution is possibly related to the rapid development of the textile, printing and paper industries of Zhejiang province.     

直接进样-超高效液相色谱——三重四级杆串联质谱法测定地表水中丙烯酰胺

采用直接进样一超高效液相色谱-三重四级杆串联质谱法，建立了对地表水中丙烯酰胺的分析方法。该方法不需要衍生化等前处理步骤。结果表明，丙烯酰胺含量在0．100～10．0μg／L范围内具有很好的线性相关性，实际水样加标回收率为80．0％-105％。该方法的检出限和测定下限分别为0．025μg／L和0．100μg／L，能够满足地表水环境质量标准中关于饮用水中丙烯酰胺最高安全浓度指南的要求，提高了引用水源丙烯酰胺的检测要求。     

加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱测定土壤和沉积物中8种多溴联苯醚

建立了土壤和沉积物中8种多溴联苯醚(PBDEs,BDE-28、BDE-47、BDE-99、BDE-100、BDE-153、BDE-154、BDE-183和BDE-209)加速溶剂同时萃取和净化-气相色谱-三重四极杆串联质谱(ASE-GC-MS-MS)的分析方法。通过优化加速溶剂萃取与弗罗里硅土在线净化和串联质谱多反应监测模式的条件,较好地去除基质干扰,并提高了三重四极杆串联质谱定性的准确性及定量的灵敏性。该方法采用改进的色谱柱能同时分析包括高溴代联苯醚BDE-209在内的8种PBDEs,其浓度范围为1～100 ng/mL(BDE-209为10～1 000 ng/mL),线性良好,线性回归系数均大于0.997。方法检出限为0.004～0.1 ng/g,方法回收率为75%～110%,方法精密度为2.4%～15.6%。适于批量处理土壤和沉积物中含有多组分痕量PBDEs的样品。     

Levels and congener profiles of polybrominated diphenyl ethers (PBDEs) in primipara breast milk from Shenzhen and exposure risk for breast-fed infants

This study aimed at revealing the levels of polybrominated diphenyl ethers (PBDEs) in breast milk from primipara in Shenzhen (China), and estimating daily intake of PBDEs for breast-fed infants. Concentrations of 7 PBDEs were measured in 60 breast milk samples by isotope dilution HRGC/HRMS (high-resolution gas chromatography/high-resolution mass spectrometry). The intake of PBDEs for breast-fed infants was estimated based on the infant's daily milk consumption. The range of total concentration of 7 PBDEs congeners in samples was 2.6-188.6 ng g(-1) lipid (mean: 14.8 ng g(-1) lipid; median: 7.2 ng g(-1) lipid). The mean estimated daily intake of PBDEs by breast-fed infants ranged from 9.9 to 335.9 ng kg(-1) body weight (bw) per day (mean: 52.5 ng kg(-1) bw per day; median: 28.6 ng kg(-1) bw per day). The levels of PBDEs body burden in the recruited mothers of Shenzhen were higher than those reported previously for the general population from other areas in China. No significant correlations were found between the body burden of PBDEs and the mothers' age, pre-pregnancy BMI, dietary habits, duration of residence in Shenzhen, weight and length of the newborns. BDE-47 and BDE-153 were major PBDE congeners in milk samples, while the congeners of BDE-183 and BDE-28 were also high in Shenzhen. The situation may be attributed to the special economic pattern including electronic production in Shenzhen in the past three decades. Continuous surveillance on PBDEs levels in human milk is needed in order to accurately evaluate the environmental impact of PBDEs to human health in Shenzhen.     

Toxic and essential elements in blood from delivering women in selected areas of São Paulo State, Brazil

This study was designed to evaluate the degree of environmental contamination and possible exposure of pregnant women to toxic elements in seven selected areas of S?o Paulo State, Brazil. The overall median concentration of Mo in maternal blood was 0.53 μg L?1, highly significant differences found between sites (p < 0.0001). Cd was found to be low overall - 0.09 μg L?1 (0.01-0.58 μg L?1) - with mothers from the Coastal and Rural 1 sites having the highest levels (p < 0.016).Median Hg concentration was 0.60 μg L?1 (0.06 μg L?1-4.35 μg L?1); median Pb level was 16.2 μg L?1 (3.5-57.7 μg L?1) and no differences between sites were observed for both metals. Median Mn level was 16.7 μg L?1 (7.0-39.7 μg L?1), being highest in Urban 2 site (p < 0.016). Concentrations of maternal Co were found to range between 0.06 μg L?1 and 1.1 μg L?1 (median 0.25 μg L?1) and As level was 0.60 μg L?1 (0.10-3.8 μg L?1) overall, with no statistical significance between sites for Co and As. Median Se concentrations were found to be 64 μg L?1 (36-233 μg L?1), with the highest median levels found in Urban 3 site; site differences were statistically significant (p < 0.0001). Correlation for each element (between paired maternal and cord blood) was measured only in Rural site 1; significant correlation was shown for Hg, Pb, Mn and Co (p < 0.05). These findings may be interpreted as indicating low environmental contamination in S?o Paulo State, Brazil. These findings could also indicate that pregnant women have little or no contact with pollutants, possibly due to awareness campaigns carried out by public health practitioners.     

Environmental exposure to POPs and heavy metals in urban children from Dhaka, Bangladesh

Persistent organic pollutants (POPs) and heavy metals are well known environmental pollutants. Even though numerous studies have been carried out to assess human exposures to these compounds, there is still a lack of data on humans from developing countries, especially in underprivileged children. The objective of this study was to assess the exposure to POPs and heavy metals in children from Dhaka, Bangladesh. One specific aim was to investigate whether children working at, or living close to, open waste disposal sites (WDSs) were more heavily exposed than other urban children. In 2008, blood and serum were collected from 73 children aged 7-16 from five neighbourhoods. Some of the children lived and worked at WDSs (N = 31), others lived next to a WDS (N = 17), whereas some children lived far from such sites (N = 25). Blood levels of lead (B-Pb), cadmium (B-Cd), and selenium (B-Se) were determined by ICP-MS for all subjects. The metal levels were high, with B-Pb overall mean 120 μg L(-1) (range 40-220), B-Cd 0.74 μg L(-1) (0.22-4.1), and B-Se 120 μg L(-1) (81-170). There were no marked differences between children from the different neighbourhoods, or between WDS workers and other children. PCB levels were low and with no contrast between neighbourhoods, for CB-153 the overall mean was 7.0 ng g(-1) fat (2.8-51). In contrast, high levels of DDTs were observed in all children, for 4,4'-DDE 1300 ng g(-1) fat (420-4600), and for 4,4'-DDT 326 ng g(-1) fat (44-1400), indicating ongoing exposure. PBDE levels were low, and BDE-209 was quantitated mainly in children working at or living close to WDSs. In conclusion, the high levels of DDTs, lead and cadmium observed in children from Dhaka are of concern. Many children were exposed at levels where health effects have been observed, or at levels without safety margins.     

Simultaneous determination of malachite green, enrofloxacin and ciprofloxacin in fish farming water and fish feed by liquid chromatography with solid-phase extraction

An effective and sensitive method for simultaneous analysis of malachite green (MG), enrofloxacin (ENFLX) and ciprofloxacin (CPFLX) by liquid chromatography-diode array detection with solid-phase extraction (SPE) is developed. The conditions of SPE and LC were investigated and optimised. The effective separation of these compounds was achieved using a ZY1104 C18 column (250 × 4.6 mm, 5 μm) with 20 mM tetrabutyl ammonium bromide (pH 3.0)-acetonitrile as mobile phase and gradient elution. The diode array detection was used at 278 nm for ENFLX and CPFLX and at 613 nm for MG. Under the optimal conditions, the method LOD values of MG, ENFLX and CPFLX were 0.01, 0.07 and 0.10 μg L(?-1) for fish farming water samples and 1.5, 10.5 and 15 μg kg(?-1) for fish feed samples, respectively. The relative recoveries of the three analytes were achieved to be 76.7-82.3% with the RSDs (n = 5) of 3.2-4.6% for spiked fish farming water samples and 78.8-93.7% with the RSDs (n = 5) of 3.1-4.8% for spiked fish feed samples.     

Behaviors of dissolved antimony in the Yangtze River Estuary and its adjacent waters

Antimony is a naturally occurring and cumulatively toxic element. With increasing concern as an inorganic contaminant, research on its environmental behavior is becoming a necessity. However, very little is known about this element. To further understand its biogeochemical behaviors and roles in the ecosystem, the main species of dissolved inorganic antimony (Sb(iii) and Sb(v)) in Yangtze River Estuary and its adjacent waters were determined by hydride generation and atomic fluorescence (HG-AFS) in our study. Results show that in surface water, the concentration for Sb(iii) and Sb(v) were in the range 0.029 μg L(-1)～ 0.736 μg L(-1) and 0.121 μg L(-1)～ 2.567 μg L(-1), with averages of 0.152 μg L(-1) and 0.592 μg L(-1), respectively. While concentrations of Sb(iii) and Sb(v) in the bottom layer were much lower, ranging from 0.023 μg L(-1) to 0.116 μg L(-1) (average of 0.050 μg L(-1)) and from 0.047 μg L(-1) to 0.441 μg L(-1) (average of 0.194 μg L(-1)), respectively. Data analysis further demonstrates that the major processes controlling antimony geochemistry in the area are riverine input, atmospheric deposition, incursion of Taiwan Warm Current, and release from particulate phase. The surface-enrichment and bottom-depletion depth profile reveals it does appear as a mildly scavenged element but is less like arsenic than previously believed. Sb(v) was the predominant speciation in aquatic environment of our research, and Sb(iii) was a minor constituent of the total antimony. Regarding the adsorption-desorption process onto SPM, Sb(iii) has a higher affinity to particulate phase than Sb(v). Furthermore, the significant correlation between antimony and nutrients indicates it is an element with great biological potential, which is also an important behavior for antimony.     

煤化工厂烟气中苯并(a)芘现状监测分析

通过试验建立了煤化工厂烟气中苯并(a)芘的液相色谱监测分析方法.通过条件优化,用配有荧光检测器的高效液相色谱仪分析烟气样品中苯并(a)芘的含量,该方法以乙腈、水梯度比例混合作为流动相;流速为1.0 ml/min;激发波长为255nm、发射波长为420nm;保留时间为27.38 min,测定检出限为2×10-3μg/m3...     

气相色谱法同时测定水中28种多氯联苯单体

采用液液萃取-浓硫酸磺化净化-气相色谱电子捕获检测器同时测定水中28种多氯联苯单体,必要时利用质谱选择离子监测模式定性,考察了萃取溶剂种类和体积及盐析效应对测定的影响,比较了硫酸磺化和弗罗里硅土柱对萃取液的净化效果。方法在1.00μg/L~47.6μg/L范围内线性良好,当取样体积为200 mL时,方法检出限为0.001μg/L~0.002μg/L,基体加标回收率为95.8%~103%,相对标准偏差≤18.7%。     

Optical fiber based methodology for assessment of thiocyanate in seawater

A new methodology for the assessment of thiocyanate (SCN(-)) is proposed based on optical fiber (OF) detection coupled to a liquid chromatography system (LC). The developed methodology showed an adequate performance for the analysis of SCN(-) comparable to a high performance liquid chromatography with UV detector (HPLC-UV) methodology: a detection limit of 3 μg L(-1), a linear range from 4 to 400 μg L(-1), and an analytical time of less than 6 min. The OF based methodology was of compact design and easy operation. This simple system has the potential to be used as a sensing approach for SCN(-) in seawater.     

Temporal trend studies on polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in ringed seals from east Greenland

The concentrations of polybrominated diphenyl ethers (PBDEs) 17, 28, 47, 49, 66, 85, 99, 100, 153, 154, and 183 were determined in ringed seal blubber from central East Greenland collected in 1986, 1994, 1999 and during the period 2001 to 2004. The trend of PBDEs was compared with the trends of polychlorinated biphenyls (PCBs) 28, 31, 52, 101, 105, 118, 138, 153, 156, and 180 during the same period. The levels of sigmaPBDE in East Greenland ringed seals ranged from 21.8 ng g(-1) lipid weight (1w) in 1986 to 39.3 ng g(-1) lw in 2001 and are among the highest observed in ringed seal from the Arctic. The dominating congeners were BDE-47 (75.4%) and BDE-99 (9.7%). The concentrations of PBDEs and PCBs increased with the age of the seals, and therefore only young seals < or =4 years old) were included in the temporal trend analyses. No significant trend (p > 0.14) was observed in sigmaPBDE or the congeners BDE 28, 47 and, 99 during the period while sigmaPCB decreased significantly (p = 0.004) over the period from 1986 to 2004 with an estimated annual rate of 4.3%.     

Brominated flame retardants in plasma samples from three different occupational groups in Norway

Brominated flame retardants (BFRs) are widely used in plastics, textile coatings, electrical appliances and printed circuit boards to prohibit the development of fires. In order to investigate how exposure to BFRs is related to specific occupations, samples were obtained from Norwegian individuals working at an electronics dismantling facility, in the production of printed circuit boards, or as laboratory personnel. Nine BFRs were quantified in the plasma samples: 2,4,4'-tribromodiphenyl ether (BDE-28), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), 2,2',4,4',6-pentabromodiphenyl ether (BDE-100), 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153), 2,2',4,4',5,6'-hexabromodiphenyl ether (BDE-154), 2,2',3,4,4',5',6-heptabromodiphenyl ether (BDE-183), 2,4,6-tribromophenol (TriBP) and tetrabromobisphenol A (TBBP-A). The BFRs were extracted from plasma using solid-phase extraction (SPE). The plasma lipids were decomposed by treatment with concentrated sulfuric acid directly on the SPE column, prior to the elution of the BFRs. Following diazomethane derivatization, the samples were analysed by gas chromatography-electron capture mass spectrometry. The subjects working at the electronics dismantling plant had significantly higher plasma levels of TBBP-A and BDE-153 compared to the other groups, and the heptabrominated congener BDE-183 was only detected in plasma from this group. TriBP was generally the most abundant BFR present, and the plasma concentrations were in the range 0.17-81 ng g-1 lipids. BDE-47 was the dominant BDE congener in all the individual samples and the levels were in the range 0.43-14.6 ng g-1 lipids. The total amounts of the seven BDEs were 8.8, 3.9 and 3.0 ng g-1 lipids for the group of electronics dismantlers, circuit board producers and laboratory personnel, respectively. Generally, large variations in the individual concentration levels were found within the groups, especially in the group of electronics dismantlers, where the relative standard deviations for BDE concentrations were in the range 23-164%. The levels of BFRs were not correlated to age or the level of 2,2',4,4',5,5'-hexachlorobiphenyl (CB-153). The present work indicates that the population in Norway is exposed to several BFRs, probably with food as a major source. The elevated level of higher brominated BDEs and TBBP-A in the plasma from the workers at the dismantling plant suggests an additional occupational exposure for these individuals. Thus, human exposure to BFRs seems to originate from a combination of different sources; however, further studies investigating plasma samples from a larger number of individuals are necessary for a more complete assessment of human exposure pathways to these environmental contaminants.     

New evidences in the complexity of contamination of the lagoon of Venice: polybrominated diphenyl ethers (PBDEs) pollution

This study presents the first evaluation of the current pollution by polybrominated diphenyl ethers (PBDEs) of surface sediments from the Lagoon of Venice. We focused the research on tri-to hepta-BDEs, the main components of penta- and octa-mixtures, which are considered to be the most toxic for the biocoenosis. The results pointed out a quite homogeneous contamination of this keystone European transitional environment, with ∑ ₁₃PBDEs values ra nging from 0.39 to 6.78 ng/g dry weight; these values reflect low to moderate pollution levels, which is in conformity to other coastal European ecosystems. The average PBDE profile of the lagoon sediments follows this decreasing trend of congeners: BDE-47>BDE-99> >BDE-190>BDE-28>BDE-153>BDE-154>BDE-138, BDE-183, and BDE-17, which is similar to the worldwide distribution pattern. BDE-47 and BDE-99 revealed a recent use of a penta-BDE mixture, while the presence of hepta-BDEs (BDE-183 and BDE-190) in all of the sites can indicate the actual use of a deca-BDE formulation, because these congeners are considered to be debrominated byproducts of BDE-209 degradation.     

Dissipation studies of fentrazamide (YRC-2388) in soil under anaerobic condition

Dissipation of fentrazamide in soil and water under flooded (anaerobic) conditions was studied. Fentrazamide was applied to soil at 100 g ha(-1). Soil was extracted with 0.1 N HCl?:?acetone (1?:?1 v/v) followed by partition and cleanup with silica SPE. Separation was achieved in an ODS-II column with a mobile phase of acetonitrile?:?water (70?:?30 v/v) and detection at 214 nm. Recovery of fentrazamide varied from 75.2-90.4% and 89.9-97.8% in soil and water, respectively. Fentrazamide dissipated rapidly and fentrazamide residues were not detected after 100 and 35 days of application in soil and water, respectively. Half life in soil and water was 9.06 and 3.66 days, respectively. Dissipation followed monophasic first order kinetics pattern. No fentrazamide was detected in soil, rice grain and rice straw at harvest of crop. Calibration curves for quantification were linear and relative standard deviation (RSD) was 1.78%. LOD for instrument was 0.002 μg mL(-1) and LOQ for methods were 0.005 μg g(-1) for soil and water.     

Polybrominated diphenyl ethers and organochlorine pesticides in human breast milk from Massachusetts, USA

Concentrations of polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCPs; DDTs, HCHs, CHLs, and HCB) were measured in human breast milk samples collected across Massachusetts, USA, in 2004. Seventeen PBDE congeners were found in the samples, ranging in concentration from 0.06 to 1910 ng g(-1) lipid wt. BDE-47 (2,2',4,4'-tetraBDE), BDE-99 (2,2',4,4',5-pentaBDE), and BDE-100 (2,2',4,4',6-pentaBDE) were the major congeners detected in breast milk samples. Overall mean (+/-SD) concentrations of DDTs, HCHs, CHLs, and HCB were 64.5 +/- 75, 18.9 +/- 19, 32.4 +/- 36, and 2.3 +/- 2.2 ng g(-1) lipid wt, respectively. Concentrations of PBDEs were strongly correlated with concentrations of OCPs in the samples. Based on the concentrations of organohalogens and the intake rates of breast milk by infants in the United States, daily ingestion rates of contaminants were calculated. The median ingestion rates for PBDEs, HCHs, DDTs, CHLs, and HCB were 4.0, 212, 141, 44, and 5.79 ng kg(-1) body wt day(-1), respectively. The estimated daily intake of organohalogens by infants was compared with threshold reference values suggested by the United States Environmental Protection Agency (USEPA) and the Agency for Toxic Substances and Disease Registry (ATSDR), for calculation of hazard quotients (HQs). HQs for individual organohalogens and the sum of HQ for all organohalogens were calculated as HQ indices (HQI). The results suggest that one or more of the contaminants analyzed in this study exceeded the threshold reference values in at least 26% of the breast milk samples.     

Determination of naphthalene by competitive fluorescence immunoassay

A reliable and sensitive competitive fluorescence immunoassay for the quantitative determination of naphthalene (NA) was developed. 2-naphthoxy acetic acid (NAA) was selected as the hapten of naphthalene. Active ester method (AEM) was used to couple the NAA to carrier proteins (bovine serum albumin) to form artificial immune antigen. Male New Zealand white rabbits were immunized with this antigen to obtain polyclonal antibodies, with which, a novel fluorescence immunoassay for detection of NA was described. Under best conditions, NA can be determined in the concentration range of 0.1-100 microg/L with a detection limit of 0.05 microg/L. The cross-reactivities of the anti-NA antibody to seven structurally related compounds were below 15%. Some environmental samples were analyzed with satisfactory results. It shows a good accuracy and suitability to analyze NA in environmental water.     

BDE-47在土壤矿物质与有机质上的吸附解吸特征

以多溴联苯醚典型单体2，2′，4，4′?四溴联苯醚（BDE?47）为研究对象，阐明了其在土壤矿物质与有机质上的吸附解吸行为及特征。结果表明：土壤中无机矿物质对BDE?47的吸附贡献不大，而有机质是调控BDE?47在土壤中吸附行为的关键组分；有机质对BDE?47的吸附能力与其有机碳含量和物理化学特性相关；BDE?47在腐殖酸上的解吸存在显著的滞后现象。     

The impact of a rice based diet on urinary arsenic

Rice is elevated in arsenic (As) compared to other staple grains. The Bangladeshi community living in the United Kingdom (UK) has a ca. 30-fold higher consumption of rice than white Caucasians. In order to assess the impact of this difference in rice consumption, urinary arsenicals of 49 volunteers in the UK (Bangladeshi n = 37; white Caucasians n = 12) were monitored along with dietary habits. Total urinary arsenic (As(t)) and speciation analysis for dimethylarsinic acid (DMA), monomethylarsonic acid (MA) and inorganic arsenic (iAs) was conducted. Although no significant difference was found for As(t) (median: Bangladeshis 28.4 μg L(-1)) and white Caucasians (20.6 μg L(-1)), the sum of medians of DMA, MA and iAs for the Bangladeshi group was found to be over 3-fold higher (17.9 μg L(-1)) than for the Caucasians (3.50 μg L(-1)). Urinary DMA was significantly higher (p < 0.001) in the UK Bangladeshis (median: 16.9 μg DMA L(-1)) than in the white Caucasians (3.16 μg DMA L(-1)) as well as iAs (p < 0.001) with a median of 0.630 μg iAs L(-1) for Bangladeshi and 0.250 μg iAs L(-1) for Caucasians. Cationic compounds were significantly lower in the Bangladeshis (2.93 μg L(-1)) than in Caucasians (14.9 μg L(-1)). The higher DMA and iAs levels in the Bangladeshis are mainly the result of higher rice consumption: arsenic is speciated in rice as both iAs and DMA, and iAs can be metabolized, through MA, to DMA by humans. This study shows that a higher dietary intake of DMA alters the DMA/MA ratio in urine. Consequently, DMA/MA ratio as an indication of methylation capacity in populations consuming large quantities of rice should be applied with caution since variation in the quantity and type of rice eaten may alter this ratio.     

地表水样品中10种卤代烃测定方法的优化

对地表水样品中10种卤代烃测定方法进行优化,找出空白偏高的原因。方法优化后的加标回收率为90.1%~104%,相对标准偏差为1.1%~6.9%,检出限为0.000 3μg/L~2.0μg/L,可满足地表水环境质量分析要求。