水和土壤中磺胺和激素类药物的同时分析方法

建立了一种水和土壤中磺胺嘧啶、磺胺甲嘧啶、磺胺噻唑、磺胺二甲嘧啶、磺胺二甲氧嘧啶、磺胺甲(噁)唑6种磺胺类药物和17α-雌二醇、17β-雌二醇、雌酮、雌三醇、炔雌醇、乙烷雌酚6种激素类药物同时分析的方法.具体步骤:水样过滤后使用Oasis HLB固相萃取小柱进行净化富集;土壤样品经加速溶剂提取(ASE)之后过Oasis HLB小柱净化富集;采用超高效液相色谱-串联质谱(UPLC-MS/MS)进行检测,分别以乙腈和1mL·L-1甲酸溶液、乙腈和1 mL· L-1氨水溶液作为流动相.磺胺在水和土壤中的回收率分别为87.4％～ 103.6％和58.2％～80.0％,激素在水和土壤中的回收率分别为84.8％～ 101.8％和62.8％～79.3％,相对标准偏差均小于10.3％.水和土壤中磺胺的检测限分别为0.11～0.24ng·L-1和0.01～0.02ng·g-1,激素的检测限分别为0.31 ～2.14 ng·L-1和0.03～0.21ng·g-1.用上述方法检测宿迁某典型养殖场周边的地表水和土壤,结果表明采用该方法检测环境样品中的磺胺和激素类药物是可行的.     

水环境中典型抗生素SPE-UPLC-MS/MS检测方法的建立

应用固相萃取(SPE)及超高效液相色谱-串联质谱(UPLC-MS/MS)技术,建立了快速提取测定水环境中4种四环素类抗生素(四环素、土霉素、强力霉素、金霉素)和6种磺胺类抗生素(磺胺嘧啶、磺胺甲基嘧啶、磺胺二甲基嘧啶、磺胺二甲氧嘧啶、磺胺甲唑和磺胺噻唑)的方法.水样经过HLB小柱浓缩萃取之后以C18柱为分析柱,乙腈和0.1%甲酸水溶液为流动相,采用UPLC-MS/MS多反应监测(MRM)离子模式进行分析.纯水和城市生活污水中抗生素物质检出限分别为0.015—0.12 ng·L-1、0.03—0.09 ng·L-1,平均回收率分别为88.7%—113.5%、73.7%—94.5%,相对标准偏差均在2.6%—10.6%之间(n=8).方法操作简单、定性定量准确,检出限低,能够满足测定各类水环境中四环素类和磺胺类抗生素痕量残留的分析要求.     

在线固相萃取/超高效液相色谱/质谱法测定废水样品中内分泌干扰物

开发了一种利用全自动在线固相萃取/超高效液相色谱/质谱技术(SPE-UPLC-MS/MS)检测污水样品中的27种内分泌干扰物(EDCs)的方法.该方法可在9 min内,完成一个水样的净化、提取、分离、检测,完整的流程.回收率(72%—110%)令人满意,检测限达到每升几个纳克级别(0.3—2.1 ng.L-1),证明了它们对环境样品分析的潜力.为此,我们将该方法应用于从位于Las Palmas de Gran Canaria(加那利群岛,西班牙)的两个废水处理厂(WWTP)采集的样品.     

镍、氮共掺杂碳纳米管的一锅制备法及其对牛奶样品中雌激素的萃取

利用高温煅烧法一步合成制备了磁性镍、氮共掺杂碳纳米管(Ni@N-CNTs)并将其与泡腾片剂结合应用于牛奶中4种雌激素的萃取.研究了萃取剂的质量,pH,洗脱剂种类及体积等对萃取回收率的影响,并通过磁固相萃取结合高效液相色谱法将其成功用于牛奶中雌二醇、雌酮、己烯雌酚和己烷雌酚等4种雌激素的检测.该方法对雌二醇和己烷雌酚的线性范围为1.0—500.0μg·L~(-1),对雌酮和己烯雌酚的线性范围为2.0—500.0μg·L~(-1),4种物质检出限为0.24—0.50μg·L~(-1),日内日间精密度分别为3.18%—4.96%和4.54%—6.32%.牛奶样品中回收率为85.2%—102.9%.因此,建立的方法在微萃取领域有很大的应用前景.     

超高效液相色谱-电喷雾串联四极杆质谱结合内标物测定水体中微囊藻毒素

本文建立了超高效液相色谱-电喷雾串联四极杆质谱(UPLC-MS/MS)测定水体中MC-RR和MC-LR的方法,比较了内标的加入对不同水样富集体积下MCs测定准确度的影响.结果表明,以乙腈和水(均含0.1%甲酸)为流动相时,MC-RR和MC-LR在Acquity UPLC BEH C18色谱分离柱(2.1 mm×100 mm i.d.粒径1.7μm,孔径130)于4 min内完全分离.经优化质谱参数,选择m/z 519.8>134.3和995.5>134.6分别为MCRR、MC-LR质谱检测的定量离子对.方法学验证表明,在所设定的色谱、质谱参数条件下,UPLC-MS/MS对MC-RR和MC-LR的检出限分别为2.0 ng·L-1和1.0 ng·L-1,定量限分别为为6.0 ng·L-1和3.0 ng·L-1,回收率分别达98.9%—106.5%和98.4%—101.5%.测定太湖梅梁湾水样时,当水体中MCs浓度达到UPLC-MS/MS方法定量限20倍时,可通过加入内标物亮氨酸脑啡肽,实现快速(不经过水样富集)且准确(相对标准偏差<5.0%)的MC-RR与MC-LR测定.     

超高效液相色谱-串联质谱法测定污水中14种有机磷酸酯阻燃剂

建立了超高效液相色谱-串联质谱(UPLC-MS/MS)联用法同时测定污水中14种有机磷酸酯阻燃剂(OPEs)的分析方法.样品采集后,经GF/C膜过滤,HLB固相萃取小柱净化后进样分析.以BEH C18色谱柱为分离柱,乙腈和水混合液为流动相(0.2 mL min-1)梯度洗脱,15 min内可完成14种OPEs的分离.在电喷雾正离子模式下,采用多反应监测模式(MRM)进行质谱测定.在加标浓度为1.0μg·L-1时,14种OPEs在污水处理厂进水和出水中的回收率分别为52.1%—119%、43.6%—114%,相对标准偏差(RSD)分别为1.2%—16.2%、0.4%—9.2%,方法的检出限(LOD)在0.3—6.0 ng·L-1间.方法精密度好,准确度高,可满足同时对污水样品中的14种OPEs进行定性及定量分析的要求.     

天津市污水以及再生水处理过程中的雌/孕激素干扰效应（Estrogen and Progesterone Interference Effect of Sewage and Reclaimed Water Treatment Process in Tianjin）

应用重组基因酵母检测了天津市4个污水处理厂以及2个再生水厂13个水样的雌/孕激素干扰效应.其中3个污水处理厂的进水检出了雌激素诱导活性,最高检测值为10.7ngEEQ·L-1;所有水样均未检测出孕激素诱导活性,但都检测出不同程度的孕激素抑制活性,其中检出了雌激素诱导活性的污水处理厂的进水具有相对较强的孕激素抑制活性.4个污水处理厂均不能完全去除孕激素抑制活性物质,去除率在44%～78%之间.微滤和臭氧氧化两种工艺结合对孕激素抑制活性物质的去除效率略优于MBR反应器.2个再生水厂出水加氯后孕激素抑制活性均有所增强.     

重庆长江流域水体中8种典型环境雌激素污染特征

选择重庆市长江流域为研究区域,调查平水期和蓄水期水体中8种典型环境雌激素雌酮(E1)、雌二醇(E2)、雌三醇(E3)、已烯雌酚(DES)、炔雌醇(EE2)、4-壬基酚(4-NP)、4-辛基酚(4-t-OP)和双酚A(BPA)的浓度、组成和分布特征,并对其雌激素活性进行风险评价。结果表明,重庆市长江流域水体中除E2外,其余7种环境雌激素均有检出,总浓度范围为46.16～10 985.79 ng·L-1,主要污染物为4-NP和BPA。平水期4-t-OP、BPA浓度显著高于蓄水期,而4-NP则相反。空间分布上,各采样位点的环境雌激素污染状况相差较大,并未表现出明显的流向变化趋势或干支流差异。风险评估结果表明,平水期52%的位点及蓄水期22%的位点雌激素总活性高于1 ng·L-1,提示具有高雌激素活性风险,其中,E1为平水期主要雌激素活性贡献物质,而4-NP为蓄水期主要雌激素活性贡献物质。     

A~2/O工艺处理污水中雌激素活性和典型雌激素水平变化

针对水环境中内分泌干扰物低浓度、难去除和高危害的特点,为全面了解污水处理过程中雌激素水平和效应的变化情况,采用HPLC-UV-FLD分析了污水中4种固醇类雌激素的浓度水平,采用重组酵母菌雌激素筛检法(YES)评价了城市污水处理流程(A~2/O)中污水的雌激素活性,同时采用酶联免疫吸附法(ELISA)检测污水处理过程中雌二醇(E2)的浓度水平。结果表明,出水中雌酮(E1)质量浓度最高,为87.97 ng·L~(-1),雌二醇(E2)质量浓度最低,为5.50 ng·L~(-1),固醇类雌激素水平去除率为88.83%~95.69%。A~2/O系统对雌激素活性的去除率为73.33%,但出水仍具有一定的雌激素活性,雌激素当量EEQ为1.92 ng·L~(-1)。ELSIA检测得雌二醇(E2)质量浓度为10.01~82.82 ng·L~(-1),去除率为88.23%,与YES法检测结果具有一致性。ELISA检测可以成为体外检测的一个重要补充。     

分散固相萃取-超高效液相色谱-串联质谱法测定城市污水中2种溴代阻燃剂

建立了分散固相萃取-超高效液相色谱-串联质谱法准确测定城市污水中六溴环十二烷(HBCD)和三-(2,3-二溴丙基)异氰脲酸酯(TBC)的方法.对萃取剂用量、萃取时间、淋洗剂、洗脱剂及色谱分离和质谱测定等条件进行了优化.优化后方法为:待测水样加入同位素标记的回收率内标,用0.4 g Silica、C18和HLB(1∶1∶1)混合填料分散固相萃取,回收萃取剂后用5 m L的10%的甲醇水溶液淋洗,8 m L甲醇洗脱,氮吹浓缩,加入同位素标记的进样内标测定.方法在1—200μg·L-1范围线性关系良好,HBCD和TBC的线性相关系数R20.9986,检出限为0.6—1.2 ng·L-1.应用该方法在某大型污水处理厂各工艺段污水中检测出了α-HBCD,浓度水平为1.3—5.4 ng·L-1.该方法操作简单、灵敏度高,尤其适合城市污水复杂基质中HBCD和TBC的分析.     

Biosorbents for solid-phase extraction of toxic elements in waters

Some trace metals are highly toxic for the environment. There is therefore a need for reliable methods for the determination of metals at trace levels. To this end, new sample pretreatment methods such as separation, preconcentration and speciation prior to the determination of metal ions have developed rapidly. Biosorption has become a major tool for solid-phase extraction methods. This review covers selected biosorbents such as algae, bacteria, filamentous fungi and yeasts, as new sorbents used in the solid-phase extraction of metal ions from various water sample matrices. A survey of the literature over 2004-2014 shows possible applications of selected new sorbents available for use in trace metal analysis in waters using solidphase extraction. We highlight the preconcentration of the toxic elements prior to their determination by atomic spectrometry.     

胶州湾某水域蛤蜊(Ruditapes philippinarum)、牡蛎(Crassostrea ariakensis)中的雌激素含量

为了探讨海洋贝类对环境中雌激素的富集情况,采用液-液萃取和固相萃取方法提取了胶州湾李村河入海口蛤蜊、牡蛎和底泥中的雌酮(E1)、雌二醇(E2)、雌三醇(E3)和雌炔醇(EE2),并用GC-MS方法测定了上述4种物质的含量,此外还采用暴露实验方法研究了蛤蜊吸收底泥中雌激素物质的影响因素.测定结果显示,该水域中蛤蜊全组织中E1含量为0.45～5.20ng·g-1,E2含量为nd～4.34ng·g-1,E3和EE2未检出;牡蛎体内的E1、E2和E3含量分别为4.64～29.66、2.16～7.20和0.96～7.96ng·g-1,EE2未检出;底泥中E1、E2和E3含量分别为0.43～2.36、nd～0.59、0.52～1.13ng·g-1,EE2未检出.蛤蜊和牡蛎体内的雌激素物质含量高于其栖息的底泥.暴露实验结果显示,随着底泥中雌激素物质含量的增加或暴露时间增加,蛤蜊体内雌激素物质的含量增加,贝类可吸收并富集底泥中的雌激素物质.     

水中痕量亚当氏剂和二苯胺的固相微萃取方法研究

研究了固相微萃取(SPME)-高效液相色谱(HPLC)测定水样中痕量亚当氏剂和二苯胺的分析方法.对SPME的条件如萃取纤维、萃取时间、萃取温度、离子强度、解吸方式、解吸溶剂、解吸时间进行了优化,并用于地下水等实际水样的分析.SPME优化的条件为:选用60μmPDMS/DVB萃取纤维在室温25℃下直接萃取60min,磁力搅拌速度为1100r.min-1,然后萃取纤维在解吸室内静态解吸9min后进行HPLC分析.液相色谱分离条件为ZORBAXSBC18柱(4.6mmi.d.×250mm,5.0μm),流动相为甲醇-水(70:30,V/V),流速为1.0ml.min-1,二极管阵列检测器波长为280nm.方法线性范围为0.005mg.l-1—0.5mg.l-1(R>0.99),两种物质的检出限(S/N=3)分别为0.003mg.l-1和0.002mg.l-1.加标回收率分别在89.6%—100.4%和97.5%—100.1%(n=5)之间,相对平均标准偏差(RSD)分别在4.5%—6.2%和3.8%—6.7%之间.该方法快速、简便,无需使用有机溶剂,适于水样中痕量物质的分析.     

基于分散固相萃取-超高效液相色谱串联质谱法测定沉积物中大环内酯类抗生素

采用分散固相萃取与超高效液相色谱串联质谱技术,建立了快速测定沉积物中9种大环内酯类抗生素(螺旋霉素、阿奇霉素、替米考星、竹桃霉素、红霉素、泰乐菌素、吉他霉素、罗红霉素和交沙霉素)的检测方法。沉积物经磷酸盐缓冲液和乙腈混合液浸提,再经过石墨化炭黑和C18硅胶分散固相萃取材料净化。采用超高效液相色谱串联质谱仪(UPLC-MS/MS)测定,以0.1%甲酸和乙腈为流动相,梯度洗脱,采用多反应监测(MRM)离子模式进行测定。结果表明,沉积物中9种大环内酯类回收率范围为67.6%—96.2%,相对标准偏差3.8%—13.6%(n=6),方法检出限介于0.005—0.01μg·kg^-1(R²>0.995)。以太湖湖区典型沉积物样品作为验证,该方法满足实际样品的检测需求。     

Analysis of a broad range of perfluoroalkyl acids in accipiter feathers: method optimization and their occurrence in Nam Co Basin,Tibetan Plateau

Perfluoroalkyl acids (PFAAs) are ubiquitous in the environment. They are prone to accumulate in organisms and have raised public attention in recent decades. Feather samples have been successfully applied as nondestructive indicators for several contaminants. However, a sophisticated analytical method for determining PFAAs in feathers is still lacking. In the present study, a series of conditions, such as the use of the solid-phase extraction cartridge type and extraction/digestion methods, were optimized for the analysis of 13 PFAAs in feathers. According to the spiked recoveries, a weak-anion exchange cartridge was chosen and the methanol was selected as the extraction solvent. In the present study, an optimized pretreatment procedure combined with high-performance liquid chromatography–electrospray ionization–tandem mass spectrometric (HPLC–ESI–MS/MS) method was established for the determination of PFAAs in feathers. The recoveries and method detection limits of the PFAAs ranged from 71 to 120% and 0.16 to 0.54 ng/g, respectively. Finally, 13 PFAAs in four accipiter feather samples from Nam Co Basin, Tibetan Plateau, were analyzed, indicating that PFOS was the predominant PFAA in accipiter feathers, with an average of 4.67 ng/g, followed by the short-chain PFAAs, PFBS and PFBA, with averages of 1.91 and 1.39 ng/g, respectively. These results partly indicated the current situation of PFAA pollution in the Nam Co Basin, especially the existence of short-chain PFAAs in this region.     

Modelling the concentrations of dissolved contaminants (Cd,Cu, Ni,Pb, Zn) in floodplain soils

Central European floodplain soils are often contaminated with potentially toxic metals. The prediction of their aqueous concentrations is a prerequisite for an assessment of environmental concerns. We tested the aqueous concentrations of cadmium (Cd), copper (Cu), nickel (Ni), lead (Pb) and zinc (Zn) derived from multi-surface adsorption modelling (on hydrous iron, aluminum and manganese oxides, clay and soil organic matter) against those analyzed in situ in the soil solution of four horizons of floodplain soils at the Elbe River, Germany. The input data for the reactive metals were derived from a seven-step sequential extraction scheme or from extraction with 0.43 M nitric acid (HNO₃) and evaluated in four modelling scenarios. In all scenarios, measured and modelled concentrations were positively related, except partially for Pb. Close reproduction of the measured data was obtained using measured data of accompanying cations and anions together with amounts of reactive metals from both the sequential extraction or from 0.43 M HNO₃ extraction, except for Cu, which was often strongly overestimated, and partially Cd. We recommend extraction with 0.43 M HNO₃ to quantify reactive metals in soil because the modelling results were metal-specific with better or equal results using the single extractant, the application of which is also less laborious. Approximations of ion concentrations and water contents yielded similar results. Modelled solid-phase speciation of metals varied with pH and differed from that from sequential extraction. Multi-surface modelling may be an effective tool to predict both aqueous concentrations and solid-phase speciation of metals in soil.     

Synthesis of 2,3-dihydroxynaphthalene-functionalized Amberlite XAD-4 resin: Applications for the separation and preconcentration of trace metal ions prior to their determination by inductively coupled plasma atomic emission spectrometry

A simple, sensitive column solid-phase extraction procedure for separation and preconcentration of Cu(II), Ni(II), Co(II), and Cd(II) in spiked and natural water samples using 2,3-dihydroxynaphthalene-functionalized Amberlite XAD-4 (XAD-4-DHN) chelating resin prior to their determination by inductively coupled plasma atomic emission spectrometry was discussed. The optimum experimental parameters such as pH, volume of sample and eluent, flow-rates of uptake and stripping, and sorption capacity of the chelating resin, were evaluated. The effect of the electrolytes and the cations on the preconcentration of metal ions was also investigated. The chelating resin could be reused for more than 20 cycles of sorption–desorption without any significant change (<1.0%). Recoveries obtained from this method range from 96 to 102% with R.S.D of 2.50 (n = 4). The detection limits for Cu(II), Ni(II), Co(II), and Cd(II) were found to be 1.9, 0.9, 1.2 µg, and 1.4 µg L^?1, respectively. The proposed method was applied for the determination of Cu(II), Ni(II), Co(II), and Cd(II) in spiked, tap water, and river water samples.     

Occurrence of endocrine disruptor compounds in the estuary of the Iberian Douro River and nearby Porto Coast (NW Portugal)

Previous studies in the Douro River estuary, based on occasional sampling, showed the presence of several estrogenic disrupting chemicals (EDCs). In sequence, we hypothesized that such type of pollution was more likely an enduring issue than an occasional phenomenon, and that it may even affect recreational beaches in each side of the estuarine mouth. Thus to conclude about the continuous influx of EDCs, water samples were taken twice a day, once per a week, from March to May of 2009, at four sites within the estuary and at two sites in the coastline. After solid-phase extraction, the extracts were prepared for GC-MS analysis of 11 reference EDCs. These embraced natural and pharmaceutical estrogens (17β-estradiol, estrone and 17α-ethynylestradiol) and xenoestrogenic industrial pollutants (4-octylphenol, 4-nonylphenol, and their mono and diethoxylates and bisphenol A). Data showed the ubiquitous presence of potentially hazardous amounts of natural estrogens (particularly of estradiol, ca 5.5?ng?L^?1) and persistent organic pollutants such as nonylphenol mono (up to 550?ng?L^?1) and diethoxylate (up to 2000?ng?L^?1). It was concluded that the targeted area is continuously polluted by the assayed EDCs, and as a consequence, conditions exist for endocrine disturbance in the biota by chronic exposure to EDCs.     

近岸海水中全氟化合物的液相色谱-离子阱质谱法测定

建立了利用高效液相色谱-电喷雾离子阱质谱(HPLC-ESI-IT-MS/MS)测定近岸海水中多种常见全氟化合物(PFCs)的分析方法.采用固相萃取法(SPE)对海水中的PFCs净化富集,用HPLC-ESI-IT-MS/MS多反应离子监测(MRM)模式对各组分(全氟己烷磺酸、全氟辛烷磺酸、全氟辛烷磺酰胺、全氟己酸、全氟庚酸、全氟辛酸、全氟壬酸、全氟癸酸、全氟十一酸、全氟十二酸)进行测定.在最佳实验条件下,采用基质匹配标准曲线法定量,以消除海水基质的影响,8种目标化合物的检出限介于0.50—1.00 ng·L-1,9种PFCs的回收率在71.0%—130.2%之间,能满足近岸海水中多种PFCs检测的要求.青岛沿岸表层海水样品测定结果显示,全部采样站点的海水样品中均检测到≥4种PFCs,说明青岛沿岸海水中已有一定程度的PFCs污染.     

新型固相萃取器用于污染水样中痕量杀虫剂的浓缩及热解吸气相色谱-质谱分析

1　IntroductionSolid phasemicro extraction (SPME)asasimpleandrapidextractiontechniqueiswidelyusedinvariousareasforextractingdiluteanalytesfromliquid ,gaseousandsolidsamplesbecauseofitshighextractionefficiency[1 ].Recently ,astirbarsorptiveextraction (SBSE…