Use of Passive and Grab Sampling and High-Resolution Mass Spectrometry for Non-Targeted Analysis of Emerging Contaminants and Their Semi-Quantification in Water

Different groups of organic micropollutants including pharmaceuticals and pesticides have emerged in the environment in the last years, resulting in a rise in environmental and human health risks. In order to face up and evaluate these risks, there is an increasing need to assess their occurrence in the environment. Therefore, many studies in the past couple of decades were focused on the improvements in organic micropollutants’ extraction efficiency from the different environmental matrices, as well as their mass spectrometry detection parameters and acquisition modes. This paper presents different sampling methodologies and high-resolution mass spectrometry-based non-target screening workflows for the identification of pharmaceuticals, pesticides, and their transformation products in different kinds of water (domestic wastewater and river water). Identification confidence was increased including retention time prediction in the workflow. The applied methodology, using a passive sampling technique, allowed for the identification of 85 and 47 contaminants in the wastewater effluent and river water, respectively. Finally, contaminants’ prioritization was performed through semi-quantification in grab samples as a fundamental step for monitoring schemes.     

四极杆-轨道阱高分辨质谱联用技术用于食品中罂粟壳特征成份的确证

采用液相色谱-四极杆/轨道阱高分辨质谱(Q-Exactive)技术,建立了火锅底料、食品调味料、烤肉、凉皮中吗啡、可待因、蒂巴因、罂粟碱、那可丁5种生物碱的确证方法。样品在稀盐酸溶液中超声提取,经三氯甲烷除脂,离子交换固相萃取柱净化,氨化甲醇-乙酸乙酯洗脱,Accucore a Q色谱柱分离,电喷雾模式下通过静电场轨道阱全扫描得到5种生物碱的准分子离子峰,同时设定阈值自动触发二级质谱进行定性确证,同位素内标法定量,实现了食品中罂粟壳主要特征成份的筛查,同时对5种生物碱的特征子离子裂解方式进行研究。在最佳实验条件下,5种生物碱的质谱扫描质量精度误差小于5 ppm。吗啡的定量下限(LOQ)为2.0μg/kg,可待因为0.2μg/kg,罂粟碱、蒂巴因和那可丁为0.1μg/kg。分析物浓度与对应峰面积呈良好的线性关系(r20.999),方法回收率为63.4%~112.8%,相对标准偏差(RSD)为5.5%~13.6%。将该方法应用于多种实际样品分析,其定量结果准确,定性可靠。     

超高效液相色谱-四极杆-飞行时间质谱法筛查塑料玩具中邻苯二甲酸酯类增塑剂

建立了塑料玩具中15种邻苯二甲酸酯类增塑剂的超高效液相色谱-四极杆-飞行时间质谱(UPLC-Q-TOF MS)筛查与定量检测方法。不同基质的塑料玩具样品采用溶剂溶解-超声提取-沉淀分离,经石墨化碳固相萃取柱净化、旋转蒸发和氮吹浓缩后,以C_(18)柱(2.1 mm×50 mm,1.7μm)梯度洗脱分离,在电喷雾正离子及一级全扫描和信息相关二级全扫描模式下检测。以一级精确质量数、同位素分布、保留时间及二级质谱与数据库匹配结果 4种手段准确定性,一级提取离子的峰面积定量。实验结果表明,15种邻苯二甲酸酯的质量偏差均小于3 ppm,在各自线性范围内线性关系良好,相关系数(r2)均大于0.996,检出限和定量下限分别为4.66~11.69μg/kg和13.04~30.71μg/kg,日内和日间精密度分别小于3.8%和6.7%,低、中、高3个加标水平的回收率为80.5%~108.3%,相对标准偏差(n=6)为0.4%~12.3%。在实际样品检测中,1例塑料玩具样品中检出邻苯二甲酸苄基丁基酯,含量为136.9μg/kg。该方法准确、高效、灵敏度高,可用于塑料玩具的实际检测。     

High-Resolution Tandem Mass Spectrometry Identifies a Particular Ganglioside Pattern in Early Diabetic Kidney Disease of Type 2 Diabetes Mellitus Patients

Considering the valuable information provided by glycosphingolipids as molecular markers and the limited data available for their detection and characterization in patients suffering from Type 2 diabetic kidney disease (DKD), we developed and implemented a superior method based on high-resolution (HR) mass spectrometry (MS) and tandem MS (MS/MS) for the determination of gangliosides in the urine of DKD patients. This study was focused on: (i) testing of the HR MS and MS/MS feasibility and performances in mapping and sequencing of renal gangliosides in Type 2 DM patients; (ii) determination of the changes in the urine gangliosidome of DKD patients in different stages of the disease—normo-, micro-, and macroalbuminuria—in a comparative assay with healthy controls. Due to the high resolution and mass accuracy, the comparative MS screening revealed that the sialylation status of the ganglioside components; their modification by O-acetyl, CH₃COO⁻, O-fucosyl, and O-GalNAc; as well as the composition of the ceramide represent possible markers for early DKD detection, the assessment of disease progression, and follow-up treatment. Moreover, structural investigation by MS/MS demonstrated that GQ1d(d18:1/18:0), GT1α(d18:1/18:0) and GT1b(d18:1/18:0) isomers are associated with macroalbuminuria, meriting further investigation in relation to their role in DKD.     

固相萃取–气相色谱–串联质谱法检测土壤中15种邻苯二甲酸酯

建立了固相萃取结合气相色谱串联质谱联用仪检测土壤中15种邻苯二甲酸酯残留的方法。样品采用丙酮和石油醚超声提取,取上清液浓缩,上弗罗里硅土固相萃取柱净化,收集洗脱液,定容,以气相色谱串联质谱法分析。该方法在20~2 000 ng/g范围内线性关系良好(r~20.999 0),检出限(S/N=3)为0.12~0.61 ng/g。20,50,200 ng/g 3个添加浓度的15种邻苯二甲酸酯的加标回收率在78.9%~101.8%之间,测定结果的相对标准偏差为0.19%~8.34%(n=5)。该方法准确、灵敏,符合痕量分析的要求,适用于土壤中邻苯二甲酸酯类残留的分析。     

Rapid Determination of Dissolved Phosphorus in Environmental Waters Using Inductively Coupled Plasma Tandem Mass Spectrometry

Dissolved phosphorus (P), an important bioavailable nutrient element, is one of the key indicators of eutrophication levels, and has been routinely measured for decades in aquatic environments. The current EPA recommended colorimetric method has been criticized for its time-consuming step of sample preparation and generation of toxic waste through the use of heavy metal catalysts. In this study, a fast, accurate, and interference-free method for the determination of dissolved P in environmental waters based on inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) was developed. This ICP-MS/MS was operated in the MS/MS mode to provide an interference-free measurement. The developed method exhibited excellent linearity (R² = 0.9999) over a concentration range of 0.5–500 μg L^?1, with a limit of detection of 8.1 ng L^?1 in 5% nitric acid solutions. The recoveries (90%–105% in water samples) and the concentrations determined by this method were in good agreement with those determined using the recommended colorimetric method. Comparing with the colorimetric method, the proposed method for determination of dissolved P exhibited great advantages such as shorter experiment time, lower limit of detection and higher sample throughput.     

动物肌肉组织中甾类同化激素多组分残留的液相色谱-质谱检测方法

建立了不同动物肌肉中甾类同化激素(表睾酮、丙酸睾酮、19-去甲基睾酮、甲基睾酮、孕酮、甲羟孕酮、雌二醇、雌三醇、炔雌醇、雌酮)多残留量的LC/MS/MS确证方法。样品加醋酸缓冲溶液均质,加酶溶液酶解后,再加甲醇超声提取,用叔丁基甲醚液-液萃取至少2次,之后经反相固相萃取柱净化,以乙腈-水为流动相,经C18柱分离后进行LC/MS/MS多反应监测模式下的定性及定量分析。其中雄激素,孕激素采用正离子扫描,雌激素则采用负离子扫描。17beta-NT、MTS、ETS、MED、PG、PTS、EST、17beta-ES、EES和ESN的定量检出限为0.5~1.0μg/kg。在1.0μg/kg的定量检出限添加水平,上述10种激素的平均回收率为55%~77%;相对标准偏差为7.1%~35%。可实现样本灵敏、准确的定性定量分析。     

Screening and Quantification of Organic Pollutants in Soil Using Comprehensive Two-dimensional Gas Chromatography with Time-of-flight Mass Spectrometry

The identification and quantification of organic compounds in leaching basin soil is important for the evaluation of soil pollution. In this study, a non-target screening strategy and a quantitative analytical method were developed based on the accelerated solvent extraction method followed by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry. First, a screening method for potential risk compounds in soil samples was established, and the major compounds were screened under the conditions such as matching similarity, signal-to-noise ratio, and relative area ratio. Second, a quantitative method was further developed by internal calibration curves for 50 main organic pollutants in the soil samples, including 27 polycyclic aromatic hydrocarbons and their derivatives (PAHs), 10 phthalic acid esters, eight phenolic compounds, and five benzene derivatives. The quantitative procedure exhibited good selectivity, accuracy, precision, low limits of detection (0.03–1.02?ng/g), and quantification (0.1–3.0?ng/g) for all target compounds. Finally, the proposed strategy was applied to the soil samples that were collected from a leaching basin and polluted by electroplating wastewater. Abundant PAHs and phenolic compounds were detected in the topsoil sample, which were mainly released from the electroplating wastewater. The application of this multi-dimensional strategy in leaching basin soil samples can also be used for the assessment of organic pollution in other complex soil samples.     

四极杆/静电场轨道阱高分辨质谱在青椒中农药多残留快速筛查的应用

建立了分散固相萃取法(d-SPE)萃取,高效液相色谱-四极杆/静电场轨道阱高分辨质谱快速筛查青椒中农药多残留的分析方法。样品采用乙腈提取,经N-丙基乙二胺(PSA)和C18分散固相萃取净化,以BEH C18色谱柱为分析柱,0.1%甲酸乙腈及含0.1%甲酸和4 mmol/L甲酸铵水溶液作为流动相进行梯度洗脱分离。采用正、负离子切换,同时对欧盟青椒定性和定量考核样品进行快速筛查,并对定量考核样品筛查到的16种农药进行定量测定。16种农药在一定浓度范围内呈良好的线性关系,相关系数(r2)大于0.995,该方法的定量下限为0.4~2.0μg/kg。在不同加标水平下的平均回收率为81.6%~116.5%,相对标准偏差为0.4%~7.5%。以欧盟青椒定量考核样品为研究对象,对其分别进行四极杆/静电场轨道阱高分辨质谱和三重四极杆质谱测定,结果表明,四极杆/静电场轨道阱高分辨质谱定量结果可与三重四极杆质谱结果相媲美。本方法简单、灵敏、准确,适用于农产品中农药多残留的快速筛查和分析测定,具有很好的实际应用价值。     

Determination of Pesticides in Organic Carrots by High-Performance Liquid Chromatography/High-Resolution Mass Spectrometry

Food contamination by pesticide residues, which may cause serious human health problems, is an ongoing challenge. Safer organically grown food is therefore needed. However, best practices are not always followed for farming organic foods, necessitating analytical testing. To this end, this report describes an analytical method for the evaluation of 82 pesticides by high-performance liquid chromatography–high-resolution mass spectrometry in organically grown carrots. The method was validated in terms of linearity, precision, and limits of detection and quantification that ranged from 0.3 to 5 and 5–40?µg?kg^?1, respectively. From the 82 pesticides evaluated in this multiresidue method, three were detected in real samples, with bendiocarb detected at the highest concentration (199.11?µg?kg^?1), which was above the maximum residue limit. Chlorpyriphos (43.20?µg?kg^?1) and amitraz (11.22?µg?kg^?1) were also detected. Measurement of contaminants in organic foods should be a standard practice, which would contribute to improved food safety. It is observed that even organic foods can be contaminated by pesticides, intentionally or unintentionally, perhaps by cross-contamination. Pesticides in organic foods are a public health problem because consumers expect organic foods to be free of pesticide contamination, but this is not necessarily the case.     

中兽药口服液中非法添加化学药物高分辨质谱筛查

建立了适用于中兽药口服液中167种非法添加化学药物的超高效液相色谱-四极杆静电场轨道阱质谱高通量筛查方法。样品采用0.5%甲酸乙腈-水进行振荡超声提取,电喷雾电离源（ESI）、正负离子同时扫描方式进行数据采集。通过与自建的167种化合物的基本信息及色谱-质谱信息数据库进行比对,对色谱-质谱条件、提取溶剂的种类和净化条件进行优化。将经前处理后的口服液样品上机测试后,采用Trace Finder筛查软件对数据结果进行分析。结果显示,50 ng/mL非法添加药物（头孢类和内酰胺类药物为100～200 ng/mL）上机时可定性检出。不同药物配方因基质影响,其非法添加药物的检出率略有差异。该方法可基本实现中兽药口服液中非法添加化学药物的高通量快速筛查,具备操作简便、快速高效的特点,为其他兽药剂型中非法添加药物的筛查奠定了基础。     

金属-有机纳米管分散固相萃取-气相色谱-串联质谱高灵敏分析环境水样中痕量多氯联苯

采用含铅金属-有机纳米管为吸附剂,基于分散固相萃取和气相色谱-串联质谱建立了一种高灵敏分析环境水样中痕量多氯联苯的方法.采用正交设计响应面法对影响萃取效果的重要因素(如离子强度、萃取时间和吸附剂用量等)进行了优化.获得的最优条件为:离子强度4.92 %(w/V)NaCl,萃取时间4.5 min,正己烷为解吸剂,吸附剂用量62.5 mg.在优化条件下,方法的线性范围为2~1000 ng/L,检出限为0.26~0.82 ng/L. 日内和日间相对标准偏差分别为0.8%~5.5% (200 ng/L, n=6)和2.7%~7.4% (200 ng/L, n=6).将本方法应用于实际环境水样中多氯联苯的分析,回收率为78.9%~113.3%,结果满意.     

液相色谱-串联质谱法测定小麦中T-2、ZEN及DON 3种镰刀菌毒素

采用液相色谱-串联质谱建立了小麦中T-2、玉米赤霉烯酮（ZEN）和脱氧镰刀菌烯醇（DON）的测定方法。样品经80% 乙腈-水提取,氨基柱（500 mg,6 mL）杂质吸附模式净化,以5 mmol/L乙酸铵溶液和甲醇为流动相,ZORBAX Extend-C18柱（150 mm×2.1 mm,1.8 μm）进行色谱分离;在电喷雾正离子化模式下,多反应监测方式测定。结果表明：T-2、ZEN和DON分别在0.5~500、5~500、10~2 000 μg/L质量浓度范围内呈良好线性,相关系数分别为0.998 9、0.999 7和0.999 1。通过对空白小麦样品进行3个水平的加标回收实验,T-2、ZEN和DON的回收率分别为86%~94%、80%~101%和81%~105%,相对标准偏差（RSD）分别为2.6%~5.5%、3.6%~8.9%和2.2%~8.1%,方法检出限分别为0.5、8.0、10.0 μg/kg。该方法准确、灵敏、成本低,适用于小麦中T-2、ZEN和DON的同时分析。     

液相色谱-串联质谱法同时测定化妆品中的16种激素

建立了同时测定化妆品中糖皮质激素、雌激素、雄激素、孕激素等各类共16种激素的液相色谱-串联质谱分析方法。不同形态的化妆品样品以甲醇为提取溶剂进行超声提取,样品提取液高速离心处理,上清液以Oasis HLB固相萃取柱净化,经Agilent ZORBAX XDB-C8(250mm×4.6mm,5μm)反相色谱柱分离后进行LC/MS/MS多反应监测模式下的定性及定量分析。其中糖皮质激素、雄激素和孕激素采用正离子扫描方式,雌激素采用负离子扫描方式进行质谱分析。16种激素的方法检出限为1~13μg/kg,在10~100μg/kg的3个添加水平范围内的平均回收率为72.8%~93.4%,相对标准偏差均小于10.2%。     

Comparative Evaluation of Red Wine from Various European Regions Using Mass Spectrometry Tools

The goal of this work was to assess differences in the composition of red wine produced in Poland, Hungary, Moldova, and Bulgaria, related to their geographical origin. Inductively coupled plasma–mass spectrometry results obtained for 23 elements were submitted to principal component analysis, indicating the association of Li, Co, Se, Cu, Sr with Moldovan products; Hungarian and Moldovan wines were characterized by V, As, Al, Fe variables, whereas Be was distinctive for Hungarian products. Polish wines were grouped with Cd and Pb and Bulgarian with Tl, Ba, Rb, and Mo; U and Mn were found as characteristic variables for wines from Bulgaria and Moldova. According with current legislation, the investigated wines were not contaminated with heavy metals and might be even considered a good source of essential elements (Cu, Mn, Fe, Zn, Cr, and Co). Gas chromatography–high-resolution time-of-flight mass spectrometry was used as a complementary analytical tool, targeting nonvolatile organic compounds amenable for silylation. Statistical data analysis revealed that geographical factors strongly affected the metabolic profiles. Specifically, 15 compounds presenting higher abundances in Bulgarian as compared to Polish wines were found, including monosaccharides, polyols, organic acids, sugar acids, and the amino acid proline. The highest fold change was obtained for ribose (37.9), followed by proline (12.2) and inositol (5.68), suggesting that these compounds might be especially useful for discrimination purposes. The obtained results encourage for further studies aimed at the discrimination of wine produced over the entire Central-East European region based on metal/metalloid profiling and on the evaluation of specific metabolites.     

Gas Chromatographic–Mass Spectrometric Analysis of Hydrocarbons and Other Neutral Organic Compounds in Volcanic Gases Using SPME for Sample Preparation

Knowledge of the chemical composition of volcanic exhalation is important in providing information on volcanic feeding systems and on the characteristics of the gaseous compounds emitted into the atmosphere. This paper reports a novel analytical method that makes use of capillary gas chromatography coupled to mass spectrometry, preceded by solid-phase micro extraction for sample enrichment. Such an approach enables considerable expansion of the number of neutral organic compounds that can be positively identified in volcanic exhalation. Data obtained from analysis of real samples are also reported.     

液相色谱-电喷雾电离质谱法测定水中的微囊藻毒素

通过固相萃取富集微囊藻毒素，并采用液相色谱-电喷雾电离质谱测定水中的微囊藻毒素-RR，-LR。分别在m／z为520．4、996．3时，采用选择离子扫描方式，提高检测灵敏度。该法检出限为0．01μg／L；线性定量范围为0．02～20μg／L。方法灵敏度高，实用性强，可为水质藻毒素风险评价和监测水处理脱毒效能，提供灵敏、准确的分析方法。     

液相色谱-串联质谱法同时测定蔬菜中7种三唑醇类杀菌剂的残留量

采用高效液相色谱-串联质谱(HPLC-MS/MS)建立了同时测定蔬菜中环唑醇、三唑醇、粉唑醇、戊唑醇、己唑醇、烯唑醇和联苯三唑醇残留量的分析方法.样品经甲醇提取,分散固相萃取净化后,采用C8色谱柱(150 mm×2.1 mm,3 μm)分离,以甲醇-0.05%甲酸梯度洗脱,串联质谱测定,外标法定量.在优化实验条件下,7...     

固相萃取–气相色谱–串联质谱法测定茶叶中9种农药残留量

建立固相萃取净化–气相色谱–串联质谱法同时测定茶叶中9种农药残留量的方法。茶叶样品用乙腈均质提取,提取液经固相萃取净化处理后,采用DB–5MS毛细管色谱柱分离,在多反应监测模式下测定,外标法定量。9种农药组分的质量浓度在0.01~0.50 mg/L范围内与其色谱峰面积呈良好线性,相关系数r~2大于0.998,方法测定下限(10 S/N)为0.002~0.01 mg/kg。以空白绿茶、红茶、普洱茶和乌龙茶为基体,在0.05,0.1,0.2 mg/kg 3个添加水平进行加标回收试验,加标回收率在73.6%~99.7%之间,相对标准偏差为4.2%~8.7%(n=6)。该法操作简便、快速,适用于茶叶中多种农药残留的测定。     

体液的在线样品前处理技术及其小分子化合物的液相色谱-质谱分析

在线样品前处理液相色谱-质谱联用技术为体液中痕量小分子化合物提供了高灵敏度、高选择性和高通量的分析方法。该文以在线固相萃取柱为主线,总结了不同种类富集柱的特点及其近5年来在相关领域的应用,并简要介绍了在线液相色谱-质谱分析的流路系统。