Rapid Screening of Carboxylic Acids from Waste and Surface Waters by ESI-MS/MS Using Barium Ion Chemistry and On-Line Membrane Sampling

Negative ion tandem mass spectrometric analysis of aliphatic carboxylic acids often yields only non-diagnostic ([M – H]^–) ions with limited selective fragmentation. However, carboxylates cationized with Ba²⁺ have demonstrated efficient dissociation in positive ion mode, providing structurally diagnostic product ions. We report the application of barium adducts followed by collision induced dissociation (CID), to improve selectivity for rapid screening of carboxylic acids in complex aqueous samples. The quantitative MS/MS method presented utilizes common product ions of [M – H + Ba]⁺ precursor ions. The mechanism of product ion formation is investigated using isotopically labeled standards and a series of structurally related carboxylic acids. The results suggest that hydrogen atoms in the β and γ positions yield common product ions ([BaH]⁺ and [BaOH]⁺). Furthermore, the diagnostic product ion at m/z 196 serves as a qualifying ion for carboxylate species. This methodology has been successfully used in conjunction with condensed phase membrane introduction mass spectrometry (CP-MIMS), with barium acetate added directly to the methanol acceptor phase. The combination enables rapid screening of carboxylic acids directly from acidified water samples (wastewater effluent, spiked natural waters) using a capillary hollow fiber PDMS membrane immersion probe. We have applied this technique for the direct analysis of complex naphthenic acid mixtures spiked into natural surface waters using CP-MIMS. Selectivity at the ionization and tandem mass spectrometry level eliminate isobaric interferences from hydroxylated species present within the samples, which have been observed in negative electrospray ionization.

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Surface Acoustic Wave Nebulisation Mass Spectrometry for the Fast and Highly Sensitive Characterisation of Synthetic Dyes in Textile Samples

Surface acoustic wave nebulisation (SAWN) mass spectrometry (MS) is a method to generate gaseous ions compatible with direct MS of minute samples at femtomole sensitivity. To perform SAWN, acoustic waves are propagated through a LiNbO₃ sampling chip, and are conducted to the liquid sample, which ultimately leads to the generation of a fine mist containing droplets of nanometre to micrometre diameter. Through fission and evaporation, the droplets undergo a phase change from liquid to gaseous analyte ions in a non-destructive manner. We have developed SAWN technology for the characterisation of organic colourants in textiles. It generates electrospray-ionisation-like ions in a non-destructive manner during ionisation, as can be observed by the unmodified chemical structure. The sample size is decreased by tenfold to 1000-fold when compared with currently used liquid chromatography–MS methods, with equal or better sensitivity. This work underscores SAWN-MS as an ideal tool for molecular analysis of art objects as it is non-destructive, is rapid, involves minimally invasive sampling and is more sensitive than current MS-based methods.

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环境试样分析

本文是《分析试验室》的定期评述中“环境试样分析”的第５篇评论。它评论了从１９９４年１月至１９９５年１２月期间我国环境试样分析的进展，包括综述、大气分析、水分析、沉积物分析、生物样品分析和有机污染物分析引用参考文献４９４篇。     

环境试样分析

本文是“分析试验室”定期评述中“环境试样分析”专题的第四篇评述。它叙述了１９９２年１月至１９９３年１２月期间我国有关环境试样分析的研究工作进展。内容包括概述、大气分析、水分析、沉积物分析、生物样品分析及有机物测定。共引用文献６７４篇。     

自然水体中生物膜的主要化学组分与水体中相关化学物质的关系

自然水体中大多数微生物是以附着状态而不是以游离状态存在的 [1] .微生物附着在固体表面形成生物膜 ,存在于河流、湖泊及湿地环境中的岩石、表层沉积物和悬浮颗粒物表面 ,由不同种类的微生物组成 [2 ] .从环境微生物学角度来看 ,生物膜被定义为一种活跃地生长发育着的单一或混合的微生物群体 ,其不可逆地附着到一种活跃的或非活跃的表面 [3] ,并由微生物群体组成 [4 ] .从环境化学角度来看 ,生物膜是由金属氧化物、有机质及少量矿物质组成的 .金属氧化物和有机质在影响重金属于固相吸附的相对作用已有报道 [5～ 10 ] .生物膜在自然水体中是…     

环境样品中苯系物的溶剂蒸气吹扫-吸收GC-MS分析法

建立了一种简易而有效的溶剂蒸气吹扫 -吸收样品处理技术 ,适用于分离富集复杂水样和固体/半固体样品中苯系物等挥发性有机物。样品在汽提装置中被含有有机溶剂蒸气(CH2Cl2 或CS2)的氮气流处理 ,进入洗脱气流的挥发性有机物用有机溶剂(CH2Cl2 或CS2)吸收。样品处理过程不存在乳化问题 ,样品有机溶液可直接用于GC -MS分析。苯系物检出限为0.05μg/L或0.1×10-9 。     

Efficient Separation of Ar and Kr from Environmental Samples for Trace Radioactive Noble Gas Detection

Radioactive noble-gas isotopes, ⁸⁵Kr (half-life t_1/2=10.8 y), ³⁹Ar (t_1/2=269 y), and ⁸¹Kr (t_1/2=229,000 y), are ideal tracers and can be detected by atom trap trace analysis (ATTA), a laser-based technique, from environmental samples like air and groundwater. Prior to ATTA measurements, it is necessary to efficiently extract krypton and argon gases from samples. Using a combination of cryogenic distillation, titanium chemical reaction and gas chromatography, we demonstrate that we can recover both krypton and argon gases from 1-10 L "air-like" samples with yields in excess of 90% and 98%, respectively, which meet well the requirements for ATTA measurements. A group of testing samples are analyzed to verify the performance of the system, including two groundwater samples obtained from north China plain.     

Fast Colorimetric Assay for Screening NSR Catalyst

The NSR (NOx storage and reduction) technology is one of the most promising methods for removing NOx from next-generation lean-burn and diesel engines. Three major drawbacks, including the low temperature activity, the catalyst sulfur tolerance and the use of the large amount of the noble metals for the commercial application of NSR catalytic system, may be resolved by the development of a better catalytic system through a fast assay method in line with the combinatorial chemistry technique. The colorimetric method is the most effective way for screening a large number of the catalyst samples at once, although an appropriate dye for revealing the color specific to NOx should be examined in advance. A knowledge-based colorimetric methodology for screening a better NSR catalyst by combinatorial approach has been developed and validated by the experimental results determined by means of traditional, time-consuming techniques such as TPD.     

Trace Analysis of Iron in Environmental Water and Snow Samples from Poland

Abstract

A voltammetric method for the determination of iron at detection limit of 4 μg/l is described, using the catalytic current of the reduction of the Fe(III)-triethanolamine (TEA) complex in the presence of bromate ions. the determination was performed at a mercury hanging drop electrode without preconcentration, using the TEA alkaline solution as a supporting electrolyte and the differential pulse technique. A peak current for the Fe(III)-TEA catalytic reduction was observed at a potential of-1.0 V (Ag/AgCl saturated electrode). the influence of TEA, BrO³ and NaOH concentrations on the peak height was studied. It was found that a 100-fold excess of Mn, a 50-fold excess of Cr(VI) and Zn did not interfere in the determination. This method was applied to the determination of iron in water, snow and waste water samples.     

Radioanalytical Determination of Biogenic Volatile Iodine Emitted from Aqueous Environmental Samples

A reliable method using ¹²⁵I tracer for direct determination of volatile iodine formed in aqueous environmental samples was established. Soil solution, seawater and bacterial cell suspension were selected as model samples, and incubated with ¹²⁵I^–. Volatile inorganic and organic iodine species produced during incubation were collected in silver wool and activated charcoal traps, separately the efficiency of the traps, the storage conditions of ¹²⁵I^– stock solution and the procedures to expel the dissolved volatile iodine from the sample solutions were examined. Formation of biological volatile iodine was observed in all samples, and the dominant iodine species was found to be organic iodine. The advantages of this method are its simplicity, low cost and low detection limit.     

Speciation of Arsenic in Environmental and Biological Samples

A novel arsine generator glass assembly is constructed and reported for the spectrophotometric determination and speciation of arsenic in real samples. In an arsine generator, sodium borohydride is added dropwise to the acidic sample solution and arsine thus formed is reacted with silver diethyldithiocarbamate (Ag‐DDTC) ‐ Tritron‐X (TX‐100) solution in pyridine to form a red coloured complex. The complex showed the absorption maximum at λ_max 540 nm. The molar absorptivity of the method was found to be (1.55) × 10⁴ L mole^?1 cm^?1 at this wavelength. The presence of non‐ionic surfactant, i.e. TX‐100 in the Ag‐DDTC solution, makes the method ≈ 3 times more sensitive than the conventional Ag‐DDTC method. Beer's law is obeyed in the concentration range of 0.05–2.80 mg L^?1 of arsenic. The detection limit of the method was calculated to be 20 μg L^?1 As. Speciation of arsenite from other forms of arsenic in sample solutions was carried out by extraction of arsenite with Pb‐DDTC in chloroform, followed by spectrophotometric determination. After arsenite separation the sample is used for the arsenate determination. Total arsenic was determined by acid decomposition of the same sample. The speciation data were found to be comparable (±2%) with ICP‐MS, with better precision (< 1%). The method has been successfully applied for the speciation of arsenic in drinking water and dust samples of arsenic affecting the Rajnandgaon district of Chhattisgarh, India, and urine and blood samples of patients with arsenical diseases. Concentration of total arsenic in tube‐well water of this area was 3–6 times more than the permissible limit. Dust samples contained less amounts of arsenic than the ground water.     

Automated Monitor Systems for the Continuous Surveillance of Environmental Samples

Abstract

Todays progress in chemical and allied industries as well as the product development leading to such progress depend upon the successful mastering of environmental and safety and health problems. There is a challenging need for the identification and quantification of hazardous substances in the air and water at concentrations in the ppm, ppb and often ppt range or below that value. A continuous surveillance is best achieved by automated monitor devices, responding to specific chemicals of choice. In our Department of Analytical Research we have been developing surveillance monitor systems for several years and we accumulated experience in the field of ambient air and waste water control. Our instrumental concept was to construct an easily controlled mobile instrument, distinguished by its high sensitivity and specificity for trace and ultratrace substances, and its versatility and sturdiness in field measurements. The monitor systems represent integrated analysis systems in which standardization and calibration procedures, trace enrichment steps and gas chromatographic separations are linked together on-line thus permitting a continuous, automated operation. Conventional as well as unconventional detectors, such as a mass spectrometer may be coupled with the separation step, The monitor systems are designed to perform survey analyses at a rate of one to ten analyses per hour on the hour and may be equipped with an acoustic or optical warning device, indicating the moment when a specific substance surpasses a certain critical concentration limit. The paper describes three types of instrument designs, distinguished by their degree of sophistication, i.e. the detection limit on one side and the different media in which it operates on the other     

Colorimetric Determination of Seleniumin Various Environmental Samples

A new reagent system using rhodamine‐B dye for the determination of selenium is described. The method is based on the reaction of selenium with acidified potassium iodide to liberate iodine. The liberated iodine bleaches the pink colour rhodamine‐B, which is measured at 555 nm. Beer's law is obeyed over the concentration range of 1–10 μg of selenium final solution volume of 25 mL (0.04–0.4 ppm) and the apparent molar absorptivity and Sandell's sensitivity was found to be 1.96× 10⁵ l mol^?1 cm^?1 and 0.0004 μg cm^?2, respectively. The method is simple, sensitive, and selective and is satisfactorily applied to micro‐level determination of selenium in various environmental and cosmetic samples.     

环境与生物样品中铝测定的吸光光度和荧光光度分析方法进展

本文评述了九十年代以来环境与生物样品分析中测铝的吸光光度和荧光光度分析方法的进展。对不同的方法进行了详尽的比较和讨论     

生物和环境样品中硒元素的形态分析研究

金属组学是继基因组学/蛋白质组学和代谢组学后提出的一种新的组学,其研究重点在于对所研究的金属和类金属元素的各种存在形态进行分析。硒是生物环境中存在的一种重要的类金属元素。形态与浓度不同的硒化合物可能是生物体的必需元素,同时也可能导致中毒。本文对目前存在的硒元素形态分析方法的研究现状进行了总结,并对前景进行了展望。     

Synthesis and Characterization of Gold Nanoparticles with Surface Ligands Derived from a Primary Phosphine

Reduction of HAuCl₄ · 3H₂O with NaBH₄ in THF/H₂O in the presence of the primary phosphine PH₂Mes* (Mes* = 2,4,6-(t-Bu)₃C₆H₂) gave a mixture of ca. 1.3 nm diameter gold nanoparticles (1) and the known oligomers [Au(PHMes*)]_n (2). Nanoclusters 1 might contain phosphido (PHMes*) or phosphinidene (PMes*) surface ligands, or both; they were characterized by elemental analysis, TGA, XPS, TEM, NMR, IR, and UV–Vis spectroscopies, and by their reactions with dodecanethiol, which gave PH₂Mes*. Solid-state ³¹P-NMR cross-polarization studies of 1 and 1D (prepared using NaBD₄ and PD₂Mes* in THF/D₂O) were consistent with the presence of phosphinidene surface groups.     

An Improved Rapid On-Site Immunoassay for Triazophos in Environmental Samples

The suitability of enzyme-linked immunosorbent assay for rapid and on-site determination of triazophos in environmental samples was investigated. The optimized rapid ELISA can be completed in around 10 min at ambient temperature. A rapid sample preparation procedure was developed which can be performed on field site for fresh water and soil samples. The rapid assays can process 40 samples within 1 h including the sample preparation time. It can be concluded that this rapid assay would be a potential, effective method for monitoring triazophos in the environment, especially when quick Judgment regarding low or high contamination is critical.     

环境样品中壬基酚及相关化合物的分离富集与测定

对近 2 0年来环境样品中壬基酚及其相关化合物分析方法的研究进展进行了综合评述 ,重点讨论了样品前处理方法、柱分离和测定技术