分散液液微萃取-能量色散X射线荧光光谱法测定环境水样中的痕量铜

本文采用分散液液微萃取(DLLME)技术来分离富集环境水样中痕量铜,结合薄样技术,利用能量色散-X射线荧光光谱仪(ED-XRF)对其进行检测.实验以二乙基二硫代氨基甲酸钠(DDTC)为螯合剂,对萃取剂、分散剂的种类及体积、螯合剂的用量、pH值、萃取时间等影响实验萃取效率的因素进行了优化,得出在50μL四氯化碳,0.4 m L甲醇,pH=8,DDTC质量分数为0.03%,萃取时间3 min的条件下进行实验,萃取效率最佳.实验采用内标法进行定量,检出限为0.08μg·L~(-1),对两种实际样品进行6次平行检测,相对标准偏差(RSD)分别为3.1%和3.3%,加标回收率为97%—105%.因此本方法适用于环境水样中铜含量的检测.     

离子液体分散液-液微萃取技术测定环境水中的杀菌剂

分散液-液微萃取(DLLME)是一种微型化液相萃取技术,是在一定体积的样品溶液中,快速注入含有萃取剂的分散剂,轻轻振荡,形成乳浊液体系而实现萃取,经离心后吸取聚积在试管底部的萃取剂,直接进样分析.使得目标分析物的富集倍数更高,非常适合进行痕量分析.传统的DLLME使用的提取溶剂大部分是一些含氯溶剂,毒性较高,容易挥发.离子液体以其独特的理化性质作为一种绿色溶剂替代传统DLLME中的提取溶剂.杀菌剂是使用量较多的农药,其残留通过喷雾、废水排放、土壤渗透等途径造成地下和地表水污染,给人们的身体健康造成危害.欧盟的饮用水法则(EC/98/     

中空纤维膜辅助离子液体液相微萃取-高效液相色谱法测定环境水体中的水杨酸

分别以l-辛基-3-甲基咪唑六氟磷酸离子液体([C8MIM][PF6])和三辛基氧化膦(TOPO)作为萃取剂与辅助萃取剂,建立了中空纤维膜辅助的两相液液微萃取-高效液相色谱测定环境水体中水杨酸(Salicylicacid,SA)的新方法.通过对中空纤维膜种类、萃取剂、供体相体积、供体相pH、离子强度和萃取时间相关参数进行优化,获得了较高的富集倍数(1653倍).方法的检出限为0.1μg.L-1,线性范围为0.5—1000μg.L-1.方法对实际样品的加标回收率为89.6%—102.4%,可应用于环境水体中痕量SA的测定.     

磁性介孔硅胶萃取剂的制备及萃取性能研究

合成了C18基团修饰的磁性介孔硅胶材料,并利用该材料建立了磁性固相萃取-色谱分析方法,测定了几种环境水样中酞酸酯类(PAEs)污染物的含量.结果表明,该材料具有较大的比表面积(273 m.2g-1)和饱和磁通量(29 emu.g-1),对水样中痕量的PAEs有较强的萃取能力,而且萃取剂的磁分离特性使得萃取操作更为方便、快捷.在优化条件下,30 mg萃取剂在40 min内即可从500 mL水样中萃取痕量PAEs,回收率可达80%以上.此外,该萃取剂在处理复杂环境样品时仍能保持较强的萃取能力,环境水样中4种PAEs的检测限可达15.6—32.5 ng.L-1,加标回收率为62%—109%,相对标准偏差为2%—8%.     

离子液体1-甲基-3-己基咪唑六氟磷酸用于水中多环芳烃萃取的研究

用疏水性离子液体1-甲基-3-己基咪唑六氟磷酸作为溶剂,液液萃取水中典型污染物多环芳烃,用1ml离子液体萃取50ml含萘、1-甲基萘、2-氯萘、菲、芘、(?)各40μg·1-1的水样,其回收率为:82.2%-101.2%,相对标准偏差(n=4)为2.4%-3.5%,方法的检出限在0.05-0.43μg·1-1范围之间,水样中有机溶剂、盐的含量及pH值对萃取回收率有一定的影响.用该方法测定了卫津河水样上述污染物的含量,并与传统的二氯甲烷萃取相对比,表明离子液体在水样中多环芳烃的富集方面可以取代传统的有机溶剂.     

温度驱动的离子液体分散液-液微萃取法同时检测环境水体中磺胺类药物

以l-辛基-3-甲基咪唑六氟磷酸离子液体([C8MIM][PF6])为萃取剂,利用温度驱动离子液体分散液-液微萃取技术,结合高效液相色谱(HPLC)同时测定环境水体中2种磺胺类化合物:磺胺间二甲氧嘧啶(sulfadimethoxine,SDM)和磺胺甲噁唑(sulfamethoxazole,SMZ).对影响萃取效果的一系列因素(萃取剂、分散剂、萃取剂和分散剂的体积、pH、温度、萃取时间、盐度和离心时间等)进行了优化,在最优条件下,该方法具有较宽的线性范围(2—200μg.L-1)、较低的检出限(SDM,1.22μg.L-1;SMZ,0.50μg.L-1)、良好的重现性(RSD:SDM,1.94%;SMZ,1.9%;n=7)和较高的准确性(回收率,SDM,88.7%;SMZ,101.3%;n=7).以该方法对几处环境水样进行测定,获得了良好的回收率(63.0%—124.0%;RSD:2.1%—4.9%;n=6).     

萃取色层-原子吸收法测定废水中痕量铅和镉

本文采用吸附树脂GDX-301为支持体,以双硫腙-MIBK混合为萃取剂的萃取色层柱分离富集废水中痕量铅、镉,以0.5N盐酸洗脱后进行原子吸收测定。测定精密度优於5％,回收率96—104％,测定下限:铅50ppb,镉5ppb。方法可用於铀矿冶外排废水、一般工业废水和生活饮用水中微量铅、镉的测定。 文章对色层柱的基本特性及其制备、再生、萃取色层分离的条件、共存元素的干扰、方法的准确度、精密度进行了研究,结果比较满意。     

环境样品中炸药的痕量富集及HPLC分析

炸药对环境的影响主要来自于军工企业及军事单位的武器生产、贮存及试验过程中的污染.痕量炸药的分析一般采用高效液相色谱法,如美国环保局(EPA)批准的方法(SW846中的方法8330),Waters最近推出的环境样品中炸药的痕量富集及HPLC分析方法,对于现有的方法提出了以下改进.1.固相萃取技术富集样品为了改进现有方法及减少有机溶剂的使用量,EPA正在就使用新的样品处理技术替代传统的液-液萃取进行探讨.固相萃取由于快速、经济、操作简便而倍受青睐.Waters生产的Porapak RDX预处理柱由一种低萃取度树脂制成,专门用于水中芳香硝基化合物及硝氨的富集,这种柱子具有很高的选择性,回收率达到90%以上.Ippb和10ppb样品富集,分析的变异系数分别好于7%和5%.图1为纯水中含lppb各化合物经Porapak RDX柱富集40倍后在waters反相色谱系统上的分离谱图.     

在线固相萃取-超快速液相色谱-质谱联用测定水中超痕量呋喃丹和甲萘威

采用在线固相萃取技术对水体中痕量甲萘威和呋喃丹富集,并利用快速液相色谱串联质谱检测器检测.采用固相萃取小柱富集待测物,以色谱梯度泵完成样品的在线净化后,利用阀切换技术将待测物反冲至分析柱进行分离,以串联质谱定性及定量.水样无需样品浓缩富集,过滤后即可进样.方法在1.0—100μg·L~(-1)范围内线性良好,呋喃丹和甲萘威的线性相关系数R~2 0.999.呋喃丹和甲萘威的检出限(S/N=3)分别为0.3、0.15 ng·L~(-1),加标回收率在90.1%—108%.用所建立的方法测定了自来水中的痕量甲萘威与呋喃丹,结果令人满意.     

聚乙烯醇缩-5-甲酰基-2,4-二羟基苯偶氮安替比林液-固萃取和光度测定镍的研究

本文报道了2,4-二羟基-5-安替比林偶氮苯甲醛(DAP)及DAP与聚乙烯醇(PVA)的缩合产物(PV·DAP)的合成.并利用PV·DAP做萃取剂,析相萃取和光度测定了铝合金和环境水样中的镍.实验结果还表明,高分子显色剂与相应的小分子试剂相比,在液-固萃取方面表现为易获得高萃取率且不受萃合物电性的影响,在光度测定方面则表现出较高的灵敏度和稳定性.从而说明试剂的高分子化可改善其性能.     

Dispersive liquid–liquid microextraction of cadmium(II) for preconcentration prior to flame atomic absorption spectrometric detection in water

A dispersive liquid–liquid microextraction procedure for cadmium(II) as its 2-(5-bromo-2-pyridylazo)-5-diethylamino-phenol chelate is presented. Carbon tetrachloride and methanol were used as extraction and dispersive solvents, respectively. After phase separation, the preconcentrated-separated cadmium(II) is determined by flame atomic absorption spectrometry with a microinjection technique. The factors which affected the extraction efficiency, i.e. the pH of the sample solution and the volumes of reagent and sample were investigated. The effects of some alkali, alkali earth, and transition metal ions, and of some anions on the recovery of cadmium were also studied. A preconcentration factor of 250 was obtained for a sample volume of 50?mL under optimum conditions. The method was validated by analysis of certified reference materials and applied to some water samples from Turkey.     

Effervescence assisted dispersive liquid–liquid microextraction followed by microvolume UV-Vis spectrophotometric determination of surfactants in water

The novel and simple methods for the sensitive determination of cationic and anionic surfactants in water based on effervescence assisted dispersive liquid–liquid microextraction and microvolume UV-Vis spectrophotometry have been developed. The method involves ion-pair extraction of cationic and anionic surfactants with organic dyes (methyl orange and azure A, respectively) during the dispersion of extraction solvent (CHCl₃) by CO₂ bubbles which are formed by the injection of a mixture of the extraction solvent and proton donor solvent into the sample solution which contains carbonate-ions as effervescency agent. The analytical performance of the proposed procedure was compared with the conventional dispersive liquid–liquid microextraction. Appropriate experimental conditions for both methods were investigated. The absorbances of the colored extracts at wavelengths of 440 and 625 nm obey Beer's law within the range of 0.1–5.0 mg/L for both cationic and anionic surfactants. The limit of detection (LOD) obtained using the effervescence assisted extraction method was 30 µg/L for cationic and anionic surfactants. The proposed methods were successfully applied to determination of surfactants in water samples.     

A simple ligandless microextraction method based on ionic liquid for the determination of trace cadmium in water and biological samples

A simple and efficient ionic liquid-based ligandless microextraction method has been developed for preconcentration of cadmium ions (Cd²⁺) as a step prior to its determination by flame atomic absorption spectrometry (FAAS) with a micro-sample introduction system. In this approach, the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate [C₄mim][PF₆] and ethanol were used as extractant and dispersive solvents to preconcentrate the Cd²⁺ in different waters, acid digested scalp hair, and nail samples. Some analytical parameters influencing the extraction efficiency of Cd²⁺ and its subsequent determination, including pH, IL volume, dispersant solvent volume, sample volume, temperature, incubation time, and matrix effect, were optimized. Under optimal conditions, the limit of detection (LOD), limit of quantification (LOQ), and enhancement factor (EF) were 0.4 μg L^?1, 1.3 μg L^?1, and 50, respectively. The relative standard deviation (RSD) of 100 μgL^?1 Cd²⁺ was 4.3% (n = 6). The validity of the proposed method was checked by determining Cd²⁺ in certified reference material (TM-25.3 fortified water) and standard addition; the results showed sufficient recovery (>98%) of Cd²⁺ within the certified value. The method was applied for preconcentration and determination of cadmium in waters and biological samples.     

皮氏罗尔斯通氏菌株DX-T3-01的耐镉性能及镉富集机理

从江西德兴铜矿土壤中分离筛选到一株具有较强耐镉(Cd)能力的细菌DX-T3-01,经生理生态及16S rRNA分析进行鉴定,研究其对不同浓度Cd2+的耐受特性及对重金属Zn2+、Cu2+、Ni2+的耐受性,进一步利用扫描电镜-能谱仪(SEM-EDX)和红外光谱(FTIR)探讨菌株对Cd2+累积去除的机理.经鉴定,耐镉细菌DX-T3-01为皮氏罗尔斯通氏菌(Ralstonia pickettii);Cd2+最高耐受浓度(MTC)为16 mmol L-1,最低抑制浓度(MIC)为4 mmol L-1,并可耐受一定浓度的Zn2+、Cu2+;菌体积累Cd2+后细胞表面有沉淀物附着并有镉元素检出,对Cd2+的累积主要依靠细胞壁上—PO43-、胺基中的—C—N—、—M—O(O—M—O)、C=O和酰胺基(—CO—NH—)基团.图5参16     

2个镉耐性差异箭舌豌豆品种中镉的化学形态及亚细胞分布

通过溶液培养实验,研究了镉胁迫下2个箭舌豌豆(Vicia sativa)品种(镉耐性品种L3,镉敏感品种ZM)中镉的积累、镉的亚细胞分布和化学形态以及非蛋白巯基化合物(NPTs)的响应。结果表明2个箭舌豌豆品种根较地上部积累更多的镉。镉在箭舌豌豆根、茎和叶中主要分布于可溶性组分,敏感品种ZM根中可溶性组分的镉含量和占总镉的比例显著高于耐性品种L3。细胞壁结合镉占总镉的比例在2个品种中均为叶>茎>根。镉在箭舌豌豆根和茎内主要以去离子水(d-H2O)提取态和1 mol·L-1氯化钠(Na Cl)提取态存在,ZM根中d-H2O提取态镉的含量和比例显著大于L3。箭舌豌豆叶中镉主要以2%醋酸(HAc)提取态存在。ZM叶中80%乙醇提取态镉的比例大于L3,0.6 mol·L-1盐酸(HCl)提取态镉和残渣态镉的比例小于L3。2个品种根和茎中NPTs的含量在镉胁迫下显著升高,ZM根中NPTs的含量显著大于L3。研究结果表明,箭舌豌豆镉解毒的主要机制包括限制镉由根部向地上部转运和液泡隔离。此外,根和茎中镉与有机酸结合和NPTs螯合,叶中镉以移动性低、毒性低的形态存在也是箭舌豌豆镉解毒的重要机制。ZM较L3根中更多镉以移动性高的形态存在,L3较ZM叶中更多镉以难移动的形态存在,是L3较ZM具有更高镉耐性的重要原因。     

植物类脂的提取及对菲吸附的影响

讨论了有机溶剂极性对植物类脂提取的影响,分别采用(Ⅰ)非极性正己烷和(Ⅱ)极性三氯甲烷∶甲醇(2∶1)溶液从青椒和油麦菜干样中索氏提取植物类脂,进一步研究了上述植物干样、提取类脂和去类脂组分对菲的吸附.实验结果表明,两种方法提取得到的类脂含量不同,方法(Ⅰ)从青椒和油麦菜中提取得到类脂含量为(1.9±0.1)%和(5.0±0.4)%;而方法 (Ⅱ)提取得到的相应值分别为(2.6±0.2)%和(9.5±0.5)%.两种方法得到提取类脂对菲的吸附贡献无显著性差异(P>0.05),均约占整个青椒干样对菲吸附的20%,而油麦菜的这一比例约为60%.但采用正己烷提取可避免极性物质的析出而更好地分离类脂和去类脂组分.去类脂组分在青椒和油麦菜中对菲的吸附贡献分别约为80%和40%,即去类脂组分对菲仍有较强的吸附能力,因此不能简单视为碳水化合物.     

铜陵矿区土壤中镉存在形态及生物有效性

采取Tessier连续提取法，研究铜陵矿区不同功能区表层土壤中镉的化学形态分布和生物有效性。结果表明，各种土壤中的镉含量全部高于地区背景值，主要来源与矿业活动有关，部分样品还有矿体的风化富集叠加，土壤镉污染指数PCd为1．15～79。镉含量依次为矿体风化土壤→废矿堆下垫土→市郊菜地土→矿区铜草土、路边土和稻田土→其它土壤。其形态分布，酸性土壤中以Fe-Mn氧化态和可交换态为主，其余三态相对较低；碱性土壤中有机态和残渣态比例较高，碳酸盐态和可交换态所占的比例低。土壤中生物可利用态镉的含量较高，占土壤总镉的60．20%-98．3％，生物不可利用态仅占1．7％-39．2％。     

Preconcentration of cadmium and copper ions on magnetic core–shell nanoparticles for determination by flame atomic absorption

Magnetic core–shell nanoparticles modified by (3-aminopropyl) trimethoxy silane were prepared and used as adsorbent for the extraction and preconcentration of cadmium and copper ions. The ions were desorbed with nitric acid followed by determination with flame atomic absorption spectrometry. The extraction conditions were investigated systematically. The method was applied for the determination of Cd(II) and Cu(II) ions in different water samples. The accuracy was also evaluated through analysis of certified reference material.     

Dispersive solid phase extraction of chlorophenols using carbon-coated magnetic nanoparticles

Abstract

Carbon-coated magnetic nanoparticles were modified with cationic surfactant and used for the dispersive solid phase extraction of chlorophenols from aqueous samples. Surfactant adsorbed on the surface of the nanoparticles resulted in mixed hemimicelles for high extraction efficiency of chlorophenols. Under optimized conditions, calibration curves were linear from 0.5–20?mg L^?1 for analytes with limit of detection between 0.2 and 0.4?mg L^?1. The method was applied to extraction of chlorophenols from tap water, well water and industrial effluent. Recoveries were in the range of 94.0–99.4%, suggesting that sample matrix had little effect on the yields of extraction.     

Substitution of toxicologically critical solvents in the residue analysis of acetamiprid: Towards green chemistry

The article presents the reduced use of toxicologically critical solvents for the extraction and clean-up of a neo-nicotinoid pesticide, acetamiprid from vegetables. Acetamiprid was extracted from spiked vegetable samples of cabbage by the use of different techniques like microwave-assisted extraction (MWAE), sonication and by the conventional method of homogenization. The study revealed that though higher percent recoveries of 78–92 were obtained in the blending method, solvent use was high as compared to MWAE. In MWAE, the percent recoveries recorded were in the range of 46–89 depending upon the solvent used and power employed. A mixture of methanol–water and methanol–acetone at 400 W power levels gave percent recoveries of 72 and 82, respectively, as compared to solvent mixtures, namely, acetone–hexane and acetone–hexane–water, which recorded recoveries of 49 and 67%. The study indicates that the choice of solvent and power employed plays a significant role in MWAE for enhanced recoveries.