混酸分解-电感耦合等离子体质谱（ICP-MS）法测定地质样品中铌钽锂铍铷钨

地质样品中的铌、钽、锂、铍、铷、钨元素含量相差大,且同一样品中各元素含量差异也较大。如在原矿中的含量只有几十至几百μg/g,而在精矿中的含量则达到了百分之几至百分之几十,高含量样品中的铌钽元素在强酸性溶液中不稳定,极易水解,准确测定这些元素需要多种方法,分析过程繁琐。传统的分析方法过程复杂、难以实现同时测定多种元素。通过考察分解体系酸的用量选择、提取剂的选择、提取剂用量的选择、测定内标元素的选择,建立了混酸分解-电感耦合等离子体质谱法同时测定地质样品中铌、钽、锂、铍、铷、钨元素的测定方法。本文采用氢氟酸-硝酸-盐酸-高氯酸-硫酸分解样品,用3～4滴氢氟酸+ 5 %硫酸+ 5 %过氧化氢萃取体系代替常规有机酸(酒石酸等。)萃取体系。采用ICP -MS同时测定各含量段地质中铌、钽、锂、铍、铷、钨的不同含量。采用该方法测定国家一级标准物质 GBW07155、GBW07153 、GBW07185,结果表明,各元素的检测结果与认定值无显著性误差,精密度RSD（n=6）0.45%～4.05%,准确度?lgC （n=6）在-0.008%～0.009%之间,适用于地质样品中的铌、钽、锂、铍、铷、钨元素的测定。     

新型螯合树脂在线预富集测定海水中痕量Cd

将新型螯合树脂(XAD-H2Dz)应用于微柱现场在线采样(MFS)新技术中,实现了海水样中痕量Cd的在线原位预富集和实验室中流动注射-火焰原子吸收(FI-FAAS)系统的联机测定。采样体积为5 mL和50 mL时,检出限(3σ)分别为68和6.7 ng/L;相对标准偏差(n=7)分别为2.0%和2.6%。对国家海水微量元素标准物质GBW(E)080040和实际样品(大连老虎滩区域海水以及连云港黄海水域)中镉进行分析,均获得了满意的结果。     

微珠析相微萃取-石墨炉原子吸收法测定岩石样品中痕量铬

采用二苯碳酰二肼为络合剂,正戊醇为萃取剂,乙醇为助溶剂,建立了微珠析相微萃取-石墨炉原子吸收法测定地质样品中痕量Cr的分析方法。实验详细探讨了微珠析相微萃取的析相条件、石墨炉原子吸收工作参数及共存离子的干扰,优化了体系萃取条件。实验结果表明：微珠析相微萃取既起到了分离富集的作用,在石墨炉升温程序中又起到了基体改进剂的作用;当萃取剂用量为0.2～1.5 mL时,使之与水完全互溶所需助溶剂体积约为水相体积的0.2～0.5倍;方法线性范围为0～10 μg·L-1,检出限为0.057 μg·L-1,相对标准偏差（RSD）为3.3%（c= 2.5 μg·L-1,n=11）;当萃取剂用量为1.5 mL、水相体积15 mL时,与直接溶液进样相比其灵敏度可提高10倍。所建立的方法用于地质标准参考物质AGV-2和G-2中Cr的测定,测定值与参考值具有较好的一致性。     

Green Extraction Techniques as Advanced Sample Preparation Approaches in Biological,Food, and Environmental Matrices: A Review

Green extraction techniques (GreETs) emerged in the last decade as greener and sustainable alternatives to classical sample preparation procedures aiming to improve the selectivity and sensitivity of analytical methods, simultaneously reducing the deleterious side effects of classical extraction techniques (CETs) for both the operator and the environment. The implementation of improved processes that overcome the main constraints of classical methods in terms of efficiency and ability to minimize or eliminate the use and generation of harmful substances will promote more efficient use of energy and resources in close association with the principles supporting the concept of green chemistry. The current review aims to update the state of the art of some cutting-edge GreETs developed and implemented in recent years focusing on the improvement of the main analytical features, practical aspects, and relevant applications in the biological, food, and environmental fields. Approaches to improve and accelerate the extraction efficiency and to lower solvent consumption, including sorbent-based techniques, such as solid-phase microextraction (SPME) and fabric-phase sorbent extraction (FPSE), and solvent-based techniques (μQuEChERS; micro quick, easy, cheap, effective, rugged, and safe), ultrasound-assisted extraction (UAE), and microwave-assisted extraction (MAE), in addition to supercritical fluid extraction (SFE) and pressurized solvent extraction (PSE), are highlighted.     

Assessment of dispersive liquid–liquid microextraction for the simultaneous extraction,preconcentration, and derivatization of Hg2+ and CH3Hg+ for further determination by GC–MS

This work reports the development of a dispersive liquid – liquid microextraction method for the simultaneous extraction, preconcentration, and derivatization of Hg²⁺ and CH₃Hg⁺ species from water samples for further determination by GC – MS. Some parameters of the proposed method, such as volume and type of disperser and extraction solvent, and Na[B(C₆H₅)₄] concentration were investigated using response surface methodology. Suitable recoveries were obtained using 80 μL C₂Cl₄ (as extraction solvent), 1000 μL ethanol (as disperser solvent), and 300 μL 2.1 mmol/L Na[B(C₆H₅)₄] (as derivatizing agent). Accuracy was evaluated in terms of recovery and ranged from 87 to 99% with RSD values <7%. In addition, a certified reference material of water (NIST 1641d) was analyzed and agreed with the certified value about 107% (for Hg²⁺), with RSD values <8.5%. LODs were 0.3 and 0.2 μg/L, with enrichment factors of 112 and 115 for Hg²⁺ and CH₃Hg⁺, respectively. The optimized method was applied for the determination of Hg²⁺ and CH₃Hg⁺ in tap, well, and lake water samples.     

Electropolymerization of single‐walled carbon nanotubes composited with polypyrrole as a solid‐phase microextraction fiber for the detection of acrylamide in food samples using GC with electron‐capture detection

We developed a solid‐phase microextraction coupled to GC with electron‐capture detection method for the detection of acrylamide in food samples. Single‐walled carbon nanotubes and polypyrrole were electropolymerized onto a stainless‐steel wire as a coating, which possessed a homogeneous, porous, and wrinkled surface, chemical and mechanical stability, long lifespan (over 300 extractions), and good extraction efficiency for acrylamide. The linearity range between the signal intensity and the acrylamide concentration was found to be in the range 0.001–1 μg/mL, and the coefficient of determination was 0.9985. The LOD, defined as three times the baseline noise, was 0.26 ng/mL. The reproducibility for each single fiber (n = 6) and the fiber‐to‐fiber (n = 5) repeatability prepared in the same batch were less than 4.1 and 11.2%, respectively.     

Sensitive monitoring of penicillin antibiotics in milk and honey treated by stir bar sorptive extraction based on monolith and LC‐electrospray MS detection

In the present study, a convenient and sensitive method for determination of six penicillin antibiotics (amoxicillin, ampicillin, penicillin G, oxacillin, cloxacillin, and dicloxacillin) in milk and honey samples was developed. Milk and honey samples were diluted with water, then directly treated by stir bar sorptive extraction based on poly (vinylimidazole‐divinylbenzene) monolithic material as coating. The analytes were analyzed by LC/ESI‐ MS/MS. Several extraction parameters including extraction and desorption time, pH value, and ionic strength in sample matrix were investigated in detail. Under the optimized extraction conditions, the calculated detection limits for the target compounds were as low as 0.23–2.66 ng/kg in milk and 0.18–1.42 ng/kg in honey, respectively. Good linearity was obtained for analytes with the correlation coefficients (R²) above 0.997. Excellent method reproducibility was achieved in terms of intraday and interday precisions, indicated by the RSDs of <5.0 and <10.0%, respectively. Finally, the proposed method was successfully applied to the determination of penicillin antibiotics residues in different milk and honey samples.     

Rapid determination of catecholamines in urine samples by nonaqueous microchip electrophoresis with LIF detection

A method was developed for the rapid separation of catecholamines by nonaqueous microchip electrophoresis (NAMCE) with LIF detection, A homemade pump‐free negative pressure sampling device was used for rapid bias‐free sampling in NAMCE, the injection time was 0.5 s and the electrophoresis separation conditions were optimized. Under the optimized conditions, the samples were separated completely in <1 min. The average migration times of the epinephrine (E), dopamine (DA), and norepinephrine (NE) were 34.26, 43.81, and 50.07 s, with an RSD of 1.05, 1.26, and 0.89% (n = 7), respectively. The linearity of the method ranged from 0.0125 to 2.0 mg/L for E and 0.025～4.0 mg/L for DA and NE, with correlation coefficients ranging between 0.9978 and 0.9986. The detection limits of E, DA, and NE were 2.5, 5.0, and 5.0 μg/L, respectively. The recoveries of E, DA, and NE in spiked urine samples were between 86 and 103%, with RSDs of 4.5～6.8% (n = 5). The proposed NAMCE with LIF detection combined with a pump‐free negative pressure sampling device is a simple, inexpensive, energy efficient, miniaturized system that can be successfully applied for the determination of catecholamines in urine samples.     

Use of Cdse/ZnS quantum dots for sensitive detection and quantification of paraquat in water samples

Based on the highly sensitive fluorescence change of water-soluble CdSe/ZnS core-shell quantum dots (QD) by paraquat herbicide, a simple, rapid and reproducible methodology was developed to selectively determine paraquat (PQ) in water samples. The methodology enabled the use of simple pretreatment procedure based on the simple water solubilization of CdSe/ZnS QDs with hydrophilic heterobifunctional thiol ligands, such as 3-mercaptopropionic acid (3-MPA), using microwave irradiation. The resulting water-soluble QDs exhibit a strong fluorescence emission at 596 nm with a high and reproducible photostability. The proposed analytical method thus satisfies the need for a simple, sensible and rapid methodology to determine residues of paraquat in water samples, as required by the increasingly strict regulations for health protection introduced in recent years. The sensitivity of the method, expressed as detection limits, was as low as 3.0 ng L⁻¹. The lineal range was between 10–5 × 10³ ng L⁻¹. RSD values in the range of 71–102% were obtained. The analytical applicability of proposed method was demonstrated by analyzing water samples from different procedence.     

Dispersive liquid–liquid microextraction followed by high-performance liquid chromatography for the determination of three carbamate pesticides in water samples

A simple, rapid and efficient method, dispersive liquid–liquid microextraction (DLLME) in conjunction with high-performance liquid chromatography (HPLC), has been developed for the determination of three carbamate pesticides (methomyl, carbofuran and carbaryl) in water samples. In this extraction process, a mixture of 35 µL chlorobenzene (extraction solvent) and 1.0 mL acetonitrile (disperser solvent) was rapidly injected into the 5.0 mL aqueous sample containing the analytes. After centrifuging (5 min at 4000 rpm), the fine droplets of chlorobenzene were sedimented in the bottom of the conical test tube. Sedimented phase (20 µL) was injected into the HPLC for analysis. Some important parameters, such as kind and volume of extraction and disperser solvent, extraction time and salt addition were investigated and optimised. Under the optimum extraction condition, the enrichment factors and extraction recoveries ranged from 148% to 189% and 74.2% to 94.4%, respectively. The methods yielded a linear range in the concentration from 1 to 1000 µg L^?1 for carbofuran and carbaryl, 5 to 1000 µg L^?1 for methomyl, and the limits of detection were 0.5, 0.9 and 0.1 µg L^?1, respectively. The relative standard deviations (RSD) for the extraction of 500 µg L^?1 carbamate pesticides were in the range of 1.8–4.6% (n = 6). This method could be successfully applied for the determination of carbamate pesticides in tap water, river water and rain water.