高效液相色谱串联质谱法测定某市污水处理厂进出水中的全氟化合物

通过建立直接进样-高效液相色谱串联质谱（HPLC-MS/MS）测定污水处理厂进出水中的10种全氟化合物的方法，了解污水厂进出水中全氟化合物污染情况。10种目标分析物在10~500 ng/L范围内具有良好的线性关系，方法检出限为2.3~8.3 ng/L，精密度为2.1%~7.1%，加标回收率为60.6%~91.7%。应用该方法测定某市典型污水厂进出水中的全氟化合物，进水中全氟化合物质量浓度为90.9~206 ng/L，主要污染物是PFOA、PFHxS和PFBS；出水中全氟化合物的质量浓度为67.4~158 ng/L，环境排放量为6.7~22.9 g/d，主要污染物是PFOA和PFHxS。结果表明，该方法能很好地适用于复杂基质中10种全氟化合物的检测。     

超高效液相色谱-串联质谱法分析土壤及沉积物中氨基甲酸酯农药

利用超高效液相色谱-串联质谱,建立土壤和沉积物中痕量氨基甲酸酯农药的分析方法。该方法用体积比1:1的二氯甲烷/甲醇对土壤和沉积物样品进行加速溶剂萃取,GCB/PSA固相萃取小柱对萃取液进行净化,内标法定量,用超高效液相色谱-串联质谱法分析土壤和沉积物中20种氨基甲酸酯农药。20种氨基甲酸酯农药在0.02~1.0 μg/mL范围内线性良好(r≥0.99),检测限为0.20~0.60 ng/g。沉积物加标样品(20ng/g)和土壤加标样品(20ng/g)的回收率分别为33.2%~101.9%、38.8%~120.5%,相对标准偏差为6.1%~28.0%、2.3%~16.0%。沉积物加标样品(2.0 ng/g)回收率为43.0%~100.0%,相对标准偏差为2.1%~11.3%。     

固相萃取-UPLC-MS/MS法测定水中全氟化合物

水样中全氟辛酸、全氟辛烷磺酸钾、全氟丁酸、全氟丁烷磺酸经弱阴离子交换固相萃取柱富集净化后,用超高效液相色谱-串联质谱法测定。通过优化样品前处理条件和仪器条件,使4种全氟化合物在0.05μg/L~10.0μg/L范围内线性良好,相关系数为0.998 9~0.999 9,方法检出限为0.27 ng/L~0.96 ng/L。空白水样3个质量浓度水平的加标回收率为73.1%~91.3%,6次测定结果的RSD为7.4%~14.3%。     

超高效液相色谱-串联质谱法测定土壤中多种全氟化合物

采用超声提取、固相萃取法处理土壤,用超高效液相色谱-电喷雾串联三重四极杆质谱测定样品中11种全氟化合物,通过优化测定条件,使方法在0.100μg/L~150μg/L范围内线性良好(r~20.995)。当取样量为2.0 g时,方法检出限为0.1 ng/g~0.4 ng/g。实际土壤样品的加标回收率为67.2%~106%,测定6次结果的RSD为6.6%~17.3%。     

大伙房水库多介质中全氟化合物赋存特征、源解析及健康风险评估

大伙房水库属于全国城市供水九大重点水源地之一,作为辽宁省重要的饮用水水源地,库区水质直接影响该区域人民饮水安全及身体健康。对大伙房水库表层水体、沉积物和鱼类样品中全氟化合物（PFAS）的赋存特征及可能的来源进行分析,并运用健康风险商值法评估PFAS的潜在健康风险。结果表明,库区表层水体中ρ（ΣPFAS）为1.18~8.19 ng/L,主要污染物为全氟辛酸及其盐类化合物（PFOA）和全氟戊基羧酸（PFPA）,其浓度水平随时间呈下降趋势;沉积物中只检出3种污染物,分别为PFOA、全氟十一烷基羧酸（PFUnA）和全氟十二烷基羧酸（PFDoDA）,ω（ΣPFAS）为0.16~0.48 ng/g;不同鱼类样品中ω（ΣPFAS）由高到低依次为：武昌鱼（2.49 ng/g）>鲤鱼（2.30 ng/g）>白鲢（2.02 ng/g）>花鲢（2.01 ng/g）,主要污染物均为PFPA。基于主成分分析与相关性分析可知,大伙房水库库区的PFAS主要来自采矿、电镀、涂料等工业污染废水和生活污水;健康风险评估结果表明,表层水体和鱼类样品中的PFAS不存在健康风险。     

超声波萃取-高效液相色谱-串联质谱同时测沉积物中10种PPCPs化合物

基于EPA1694方法,应用超声波萃取-高效液相色谱-串联质谱技术,建立了沉积物中对乙酰氨基酚、林可霉素、甲氧苄啶、咖啡因、阿奇霉素、磺胺甲唑、泰乐菌素、地尔硫卓、卡马西平及氟西汀等10种药物和个人护理品(PPCPs)的分析检测方法。样品经超声萃取、离心和SAX阴离子交换柱净化,以高效液相色谱-串联质谱仪多反应监测(MRM)模式进行离子定性、定量分析。10种药物加标回收率实验结果表明:添加低浓度样品20 ng/g,回收率为61.1%~128.5%,相对标准偏差(RSD)为1.7%~17.5%(n=5);添加高浓度样品400 ng/g,回收率为66.4%~126.7%,RSD为2.3%~18.0%(n=5),最低检测限为0.12~4.46 ng/g。该方法具有检测限低和回收率高的特点,并经实际样品验证发现,该方法适用于检测沉积物中10种PPCPs化合物。     

水溶剂加速萃取-超高效液相色谱串联质谱测定土壤中全氟羧酸

采用水溶剂加速萃取-超高效液相色谱串联质谱法（UPLC-MS/MS）建立了土壤中6种全氟羧酸（PFCs）的分析方法,并对色谱分析条件、水溶剂萃取条件、固相萃取柱净化条件及实验材料选择等进行了优化。结果表明,以ACQUITY UPLC BEH C18色谱柱为分离柱,2.0 mmol/L乙酸铵水溶液为流动相A,甲醇为流动相B,梯度洗脱下可在9 min内完成6种PFCs的测试,检出限为0.03~0.4 μg/kg。对实际土壤样品进行测定,加标回收率为90.7%~118%,相对标准偏差为5.6%~18.0%,精密度和准确度均较好。该方法前处理过程简单、易操作,仪器检测效率高、结果准确,能够满足土壤中PFCs的检测要求。     

SPE-GC-MS/MS法测定水源水中多种有机氯EDCs

采用C 18柱固相萃取(SPE)-三重四级杆气相色谱-质谱法同时测定水中18种含有机氯的环境内分泌干扰物,方法在0.500μg/L^100μg/L范围内线性良好,方法检出限为0.04 ng/L^0.8 ng/L,空白水样的加标回收率为61.3%~108%,6次测定结果的RSD为3.8%~18.0%。将该方法用于饮用水源水监测,18种目标化合物的测定值为未检出~1.5 ng/L,平均加标回收率为71.9%~109%,平行测定结果的RSD<15%。     

QuEChERS-GC/ECD法分析土壤和沉积物中残留有机氯农药和多氯联苯

建立了用快速、简单、廉价、有效、可靠及安全(Qu ECh ERS)的方法净化、GC/ECD法测定沉积物中有机氯农药和多氯联苯的分析方法。目标化合物质量浓度在1.0~100μg/L范围内线性良好,相关系数均0.999,检出限为0.08~0.17μg/L。以沉积物标准样品SRM1944为研究对象,用Qu ECh ERS方法和传统方法进行提取比较,并用沉积物样品进行验证,回收率为87.8%~100.3%。方法快速、简单、可靠、安全。     

加速溶剂萃取-固相萃取/超高效液相色谱-串联质谱法测定沉积物中5种微囊藻毒素

建立了加速溶剂萃取-固相萃取/超高效液相色谱-串联质谱法同时测定沉积物中5种微囊藻毒素(MC-LR、MC-RR、MC-LW、MC-LF、MC-YR)的方法。选择甲醇-水(1∶4,V/V)为ASE萃取溶剂,萃取温度和萃取压力分别为80℃和13.1 MPa,固相萃取过程以HLB小柱为萃取柱,采用液相色谱-串联质谱分析。方法在5种微囊藻毒素质量浓度5~100μg/L内线性良好(r0.995),回收率为76.0%~118%,相对标准偏差为1.9%~12.0%,检出限为2~3μg/kg,定量下限为8~12μg/kg。该方法已用于西太湖沉积物的检测,具有较好的方法适用性。     

Application of neural-based modeling in an assessment of pollution with mercury in the middle part of the Warta River

The level of pollution with various mercury species (organomercury, water- and acid-soluble mercury, mercury bound to humic matter and to sulphides) of the floodplain soils and sediments from middle part of the Warta River has been assessed using self-organizing maps (SOM). Chemometric evaluation allowed identification of moderately (median 173-187 ng g(-1), range 54-375 ng g(-1) in soil and 130 ng g(-1), range 47-310 ng g(-1) in sediment) and heavily polluted samples (662 ng g(-1), range 426-884 ng g(-1)). Heavily polluted were located mainly below and in the area of the Poznań city. Statistical comparison of mercury species distribution in floodplain soils of the Warta River shows different patterns for moderately and heavily polluted samples. In heavily polluted soils the contribution of mobile mercury (sum of organomercury species, water- and acid soluble species) is lower (4.2%) than in moderately polluted soils (6.1%). Higher contribution of mobile mercury was observed in sediments of the Warta River (12%). In case of moderately polluted samples, statistical differences in the contribution of mercury species are relatively low and thus the environmental risk from mercury deposited in aquatic system of the Warta River is relatively low. However, higher water levels and heavy floods may incite remobilisation of some organomercuries (2.2-2.9 ng g(-1) in soil and 10 ng g(-1) in sediment) and acid-soluble species of mercury (2.6-2.9 ng g(-1) in soil and 0.5 ng g(-1) in sediment).     

Trends in background levels of persistent organic pollutants at Kosetice observatory, Czech Republic.2) Part II. Aquatic and terrestrial environments 1996-2005

A multimedia sampling of ambient air, wet deposition, surface water, sediment, soil and biota has been performed at Kosetice background observatory in the southern Czech Republic since 1988. An integrated monitoring approach was applied to assess the current state, anthropogenic impacts, and possible future changes of terrestrial and freshwater environments. Average PCB concentrations in the individual matrices calculated from ten years of sampling on multiple sites varied between 2 ng g(-1) in sediment and 7 ng g(-1) in soil or moss. DDT concentrations were lower in moss and needles (2 ng g(-1) and 4 ng g(-1), respectively) than in sediment (11 ng g(-1)) and soil (20 ng g(-1)), while the HCH level was higher in moss and needles (5 ng g(-1) and 6 ng g(-1), respectively) than in soil or sediment (1 ng g(-1) and 2 ng g(-1), respectively). The highest average level of PAHs was found in soil (600 ng g(-1)), while it was lower in needles (230 ng g(-1)), moss (210 ng g(-1)) or sediment (210 ng g(-1)). Time related trends of concentration levels of persistent organic pollutants in all matrices were investigated. Moss and needle trend patterns resembled those of the ambient air, showing a slight concentration decrease of all compounds, except for hexachlorobenzene. The soil, water and sediment concentrations showed a similar decrease of PAHs, PCBs, and HCHs, but there was no clear trend for DDTs and HCB.     

Perfluorooctane sulfonate (PFOS) distribution and effect factors in the water and sediment of the Yellow River Estuary, China

The distribution of perfluorooctane sulfonate (PFOS) was investigated in a total of 15 water and sediment samples from the Yellow River Estuary, China in April 2011. The results indicated that the concentrations of PFOS in the water and sediment samples averaged 157.5 ng/L and 198.8 ng/g and ranged from 82.30 to 261.8 ng/L and 75.48 to 457.0 ng/g, respectively. The concentrations of PFOS in the sediment column increased from 45.32 to 379.98 ng/g with the decrease of the sampling depth, which showed that the increased PFOS pollution in the sediment appeared in this region in over recent years. The distribution coefficient (K _d) of PFOS between water and sediment linearly increased from 0.37 to 4.80 L/g as the salinity (S‰) increased from 0.18 to 4.47. Correlation analysis revealed that K _d was significantly and positively correlated to the contents of total organic carbon and clay of the sediment, and salinity. Therefore, salinity was an important parameter in controlling the sediment–water interactions and the fate or transport of PFOS in the aquatic environment. The results of this study showed that the estuary was an important sink for PFOS and suggested that PFOS might be carried with the river water and transported for long distances before it reached to the sea and largely scavenged to the sediment in the estuaries due to the change in salinity.     

吹扫捕集-气相色谱联用同时测定水中致嗅挥发性有机硫化物

建立了一种利用吹扫捕集(PT)-气相色谱(GC)/火焰光度检测器(FPD)同时测定水中16种致嗅类有机硫化物的分析方法。研究并优化了捕集阱类型、吹扫温度、吹扫时间,解吸温度以及解吸时间对PT的影响。实验表明:大部分硫醚类和硫醇类化合物分别在1~100 ng/L和3~300 ng/L范围内线性良好,线性相关系数大于0.99;相对标准偏差小于9.47%(n=6);加标回收率为81.68%~115.18%。定量下限(10倍信噪比)范围从0.19 ng/L(二乙基二硫醚)到2.67 ng/L(2-甲基-1-丙硫醇)。采用此方法对北京市3条河流水样进行了检测,除1-丙基二硫醚和2-甲基-2-丙硫醇外,其他14种有机硫化物都有检出,质量浓度为1.95~1 282.35 ng/L。     

Sediment load and bioconcentration of heavy metals by shrimp (Peaneus notalis) from Epe Lagoon, Nigeria

In many developing countries, surface waters, especially rivers and lagoons, have become deposition sites for all sorts of wastes. Three sampling sites located trigonally on Epe lagoon, Lagos, Nigeria were identified, and water, sediment, and commonly farmed shrimp, Peaneus notalis, were sampled and assessed for heavy metal concentrations. Zn, Pb, Ni, Cu, Cr, Cd, and Mn were determined in the aqua regia digests of the samples by means of Perkin Elmer AAnalyst 200 atomic absorption spectrophotometer. Heavy metals occurred above detection limits at all sites. The highest load of these trace elements was found in sediment samples followed by the water samples. The levels observed in the shrimp samples, however, were much lower than WHO levels. In the distribution, zinc was the highest metal found in the samples ranging from 17.94 ± 2.60 mg/L in water to 37.85 ± 9.35 μg/g in sediments. The least was Cd 0.03 ± 0.01 mg/L in water and 0.28 ± 0.04 μg/g in sediments. Lead was the most widely varied metal in shrimp with a 84.38% coefficient of variation. Apart from Cr, the metals appeared to be fairly and evenly distributed in the sediment, with coefficient of variation ranging from 14.29% (Cd) to 24.76% (Mn) The variations were between 14.49% (Zn) and 66.67% (Cr) in the water samples. The paired t test carried out between water and sediment, water and shrimp, and shrimp and sediment was significant at p?=?0.05. Three-factor analysis of variance did not reveal any significant difference in metal burdens among the trigonally located sites under investigation. Shrimp samples showed evidence of bioaccumulation but are still below internationally established levels.     

Chemometrics in assessment of seasonal variation of water quality in fresh water systems

The spatial and temporal distribution of polycyclic aromatic hydrocarbons (PAHs) was investigated in Gomti River, a major tributary of the Ganga river (India). A total of 96 samples (water and sediments) were collected from eight different sites over a period of 2 years and analysed for 16 PAHs. The total concentrations of 16 PAHs in water and bed sediments ranged between 0.06 and 84.21 ??g/L (average (n?=?48), 10.33 ± 19.94 ??g/L) and 5.24?C3,722.87 ng/g dw [average (n?=?48): 697.25 ± 1,005.23 ng/g dw], respectively. In water, two- and three-ring PAHs and, in sediments, the three- and four-ring PAHs were the dominant species. The ratios of anthracene (An)/An + phenenthrene and fluoranthene (Fla)/Fla + pyrene were calculated to evaluate the possible sources of PAHs. These ratios reflected a pattern of pyrolytic input as a major source of PAHs in the river. Principal component analysis, further, separated the PAHs sources in the river sediments, suggesting that both the pyrolytic and petrogenic sources are contributing to the PAHs burden. The threat to biota of the river due to PAHs contamination was assessed using effect range low and effect range median values, and the results suggested that sediment at some occasions may pose biological impairment.     

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。     

Distribution and partitioning of aliphatic hydrocarbons and polycyclic aromatic hydrocarbons between water, suspended particulate matter, and sediment in harbours of the West coastal of the Gulf of Tunis (Tunisia)

Harbours of La Goulette, Rades and Sidi Bou Said are considered as the principal largest and most important port in the Gulf of Tunis characterised by a direct influence of different activities (sailing, industry and fishing) to the Mediterranean Sea. Due to their social and economic impact, a comprehensive assessment of the spatial distribution and partitioning of 24 polycyclic aromatic hydrocarbons (PAHs) and 18 aliphatic hydrocarbons (AHs) in summer and in winter among overlying water, suspended particulate matter (SPM) and surface sediments is essential. Distribution of hydrophobic organic contaminants in abiotic compartments is important for describing their transfer and fate in aquatic ecosystems and to identify the potential danger due to mobilization of contaminants produced by managing of the same sediments. Total organic carbon (TOC) contents range between 4.3% and 6.5%, with an average value of 5.9% in summer, and between 2.3% and 9.6%, with an average value of 6.1% in winter. The average concentrations of ΣPAH in winter and in summer were respectively 703.1 ng L?1 and 378.4 ng L?1 in seawater, 4599.1 ng g?1 and 3114 ng g?1 in SPM, and 1507.6 ng g?1 dw (dry weight) and 1294.6 ng g?1 dw in surface sediment. For ΣAH the average concentrations in winter and in summer were respectively 701 ng L?1 and 741.7 ng L?1 in seawater, 6743.5 ng g?1 and 6282.9 ng g?1 in SPM, and 4971.3 ng g?1 and 4588.1 ng g?1 in surface sediment. Higher PAH and AH concentrations were observed in SPM than in surface sediment. SPM and water were dominated by PAH with low molecular weight, while for sediment low and high molecular weight PAHs were present. PAH and AH fingerprint ratios, such as pristane to phytane (Pr/Ph), phenanthrene to anthracene (Phe/An) and fluoranthene to pyrene (Fl/Py), suggest that hydrocarbons in all harbours may originate from both pyrolytic and petrogenic sources derived from discharge of untreated sewage and wastewater or from direct input by ship traffic in the area. The results showed significant difference (ANOVA, p < 0.05) for hydrocarbon mean concentrations between all harbours studied and between different matrixes.     

Gross alpha and beta radioactivity concentration in water, soil and sediment of the Bendimahi River and Van Lake (Turkey)

The concentrations of the natural radioactivity in water, soil and sediment samples collected from Bendimahi River which originates near the Tendürek Mountain (Van, Turkey), its tributaries and Van Lake (Turkey) were measured. The gross-alpha and gross-beta radioactivity concentrations were investigated in May and August in 2005. Determination of the gross-alpha and gross-beta radioactivity of river water, soil and sediment samples was obtained by using gas-flow proportional counter, PIC-MPC 9604-alpha/beta counter. In water samples, the obtained results show that in May; gross-alpha and gross-beta activity concentrations varied between 0.063-0.782 and 0.021-0.816 Bq l(-1) and in August the values were 0.009-0.037 and 0.081-3.116 Bq l(-1), respectively. The gross-alpha and gross-beta activity concentrations in soil samples ranged from 0.800 to 4.277 Bq g(-1) and 0.951 to 11.773 Bq g(-1) in May and 0.686 to 4.713 Bq g(-1) and 0.073 to 9.524 Bq g(-1) in August, respectively. Concentrations ranging from 0.782 to 4.596 Bq g(-1) and from 0.482 to 10.372 Bq g(-1) in May and from 0.580 to 5.824 Bq g(-1) and from 0.303 to 9.702 Bq g(-1) in August for gross-alpha and gross-beta radioactivity were observed in sediments, respectively.