A new method of simultaneous determination of atmospheric amines in gaseous and particulate phases by gas chromatography-mass spectrometry

As more attention is being paid to the characteristics of atmospheric amines, there is also an increasing demand for reliable detection technologies. Herein, a method was developed for simultaneous detection of atmospheric amines in both gaseous and particulate phases using gas chromatography-mass spectrometry (GC-MS). The amine samples were collected with and without phosphoric acid filters, followed by derivatization with benzenesulfonyl chloride under alkaline condition prior to GC-MS analysis. Furthermore, the method was optimized and validated for determining 14 standard amines. The detection limits ranged from 0.0408-0.421 µg/mL (for gaseous samples) and 0.163-1.69 µg/mL (for particulate samples), respectively. The obtained recoveries ranged from 68.8%-180% and the relative standard deviation was less than 30%, indicating high precision and good reliability of the method. Seven amines were simultaneously detected in gaseous and particulate samples in an industrial park using the developed method successfully. Methylamine, dimethylamine and diethylamine together accounted for 76.7% and 75.6% of particulate and gaseous samples, respectively. By comparing the measured and predicted values of gas-particle partition fractions, it was found that absorption process of aqueous phase played a more important role in the gas-partition of amines than physical adsorption. Moreover, the reaction between unprotonated amines and acid (aq.) in water phase likely promoted water absorption. Higher measured partition fraction of dibutylamine was likely due to the reaction with gaseous HCl. The developed method would help provide a deeper understanding of gas-particle partitioning as well as atmospheric evolution of amines.     

金矿污染物-丁基黄原酸的监测方法研究

替代传统手工法,建立了紫外分光光度法和超高效液相色谱-质谱法测定水中的丁基黄原酸的方法,与传统的分光光度法相比,这两种方法具有较高的准确度和精密度,操作简便、不污染环境。紫外分光光度法检出限为0.005 mg/L、测定上限为12.00 mg/L。超高效液相色谱-质谱法,水样过滤后就可直接测定,检出限为0.2μg/L,在0.5 g/L～50 g/L范围内线性良好,准确度高,加标回收率为90.1%～97.0%,精密度好,相对标准偏差为2.3%～3.4%,适用于水中丁基黄原酸的快速监测。     

基于溶解性有机物分子指纹特征解析城市河道污染来源与机制

溶解性有机物(DOM)是河道污染物的重要组成部分,是构成黑臭的主要原因.在我国城市黑臭水体治理攻坚新形势下,针对广泛存在的复合污染源信息不明确的难题,进一步从分子层面解析河道DOM成分是深入探究河道污染来源、成因和形成机制,从而实现高效治理的关键环节.以某大型城市的中心城区河道作为研究对象,分别选取了受4个分流制和合流制排水系统的放江污水严重影响的共5个河道断面,应用傅里叶变换离子回旋共振质谱(FT-ICR-MS)分别对各点位旱天和雨天时的表层水和沉积物样品中DOM分子式、元素组成和群组成分进行全谱解析与数据分析.结果表明：(1)城市河道DOM虽然以CHO和木质素类化合物为主,但人为源有机物(脂肪类和蛋白质类化合物)以及CHOS等杂原子化合物的较高占比揭示了河道受人为污染的现状,同时带来DOC、 TN和NH⁺₄-N的升高;(2) C₁₇H₂₈O₃S和C₁₈H₃₀O₃S等表面活性剂类化合物普遍存在于所有城市河道中,...     

Characteristics of atmospheric single particles during haze periods in a typical urban area of Beijing: A case study in October, 2014

To investigate the composition and possible sources of particles, especially during heavy haze pollution, a single particle aerosol mass spectrometer (SPAMS) was deployed to measure the changes of single particle species and sizes during October of 2014, in Beijing. A total of 2,871,431 particles with both positive and negative spectra were collected and characterized in combination with the adaptive resonance theory neural network algorithm (ART-2a). Eight types of particles were classified: dust particles (dust, 8.1%), elemental carbon (EC, 29.0%), organic carbon (OC, 18.0%), EC and OC combined particles (ECOC, 9.5%), Na-K containing particles (NaK, 7.9%), K-containing particles (K, 21.8%), organic nitrogen and potassium containing particles (KCN, 2.3%), and metal-containing particles (metal, 3.6%). Three haze pollution events (P1, P2, P3) and one clean period (clean) were analyzed, based on the mass and number concentration of PM_2.5 and the back trajectory results from the hybrid single particle Lagrangian integrated trajectory model (Hysplit-4 model). Results showed that EC, OC and K were the major components of single particles during the three haze pollution periods, which showed clearly increased ratios compared with those in the clean period. Results from the mixing state of secondary species of different types of particles showed that sulfate and nitrate were more readily mixed with carbon-containing particles during haze pollution episodes than in clean periods.     

Preliminary studies on the stability of arsenolipids: Implications for sample handling and analysis

Human health risk assessments concerning arsenic are now estimating exposure through food in addition to exposure through drinking water. Intrinsic to this assessment is sample handling and preparation that maintains the arsenic species in the form that they occur in foods. We investigated the stability of three arsenolipids(two arsenic fatty acids, As FA-362 and As FA-388, and one arsenic hydrocarbon As HC-332), common constituents of fish and algae, relevant to sample storage and transport, and to their preparation for quantitative measurements. The fate of the arsenolipids was followed by high performance liquid chromatography/electrospray triple quadruple mass spectrometry(HPLC/ESIMS) analyses.Storage of the compounds dry as pure compounds or mixed in fish oil at up to 60?C did not result in significant changes to the compounds, although losses were observed by apparent adsorption onto the plastic walls of the polypropylene tubes. No losses occurred when the experiment was repeated with glass tubes. When the compounds were stored in ethanol for up to 15 days under acidic, neutral, or alkaline conditions(each at room temperature), no significant decomposition was observed, although esterification of the fatty acids occurred at low p H. The compounds were also stable during a sample preparation step involving passage through a small silica column. The results indicate that these typical arsenolipids are stable when stored in glass at temperatures up to 60?C for at least 2 days, and that,consequently, samples of food or extracts thereof can be transported dry at ambient temperatures, i.e. without the need for cool conditions.     

Potential of capillary electrophoresis mass spectrometry for the characterization and monitoring of amine-derivatized naphthenic acids from oil sands process-affected water

Capillary electrophoresis coupled to mass spectrometry(CE–MS) was used for the analysis of naphthenic acid fraction compounds(NAFCs) of oil sands process-affected water(OSPW). A standard mixture of amine-derivatized naphthenic acids is injected directly onto the CE column and analyzed by CE–MS in less than 15 min. Time of flight MS analysis(TOFMS), optimized for high molecular weight ions, showed NAFCs between 250 and 800 m/z. With a quadrupole mass analyzer, only low-molecular weight NAFCs(between 100 and 450 m/z) are visible under our experimental conditions. Derivatization of NAFCs consisted of two-step amidation reactions mediated by 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide(EDC), or mediated by a mixture of EDC and N-hydroxysuccinimide, in dimethyl sulfoxide, dichloromethane or ethyl acetate. The optimum background electrolyte composition was determined to be 30%(V/V) methanol in water and 2%(V/V) formic acid. NAFCs extracted from OSPW in the Athabasca oil sands region were used to demonstrate the feasibility of CE–MS for the analysis of NAFCs in environmental samples, showing that the labeled naphthenic acids are in the mass range of 350 to 1500 m/z.     

顶空气相色谱/质谱法测定水中四乙基铅的关键因素研究

采用顶空气相色谱/质谱法联用技术测定水中的四乙基铅,对涉及的关键操作环节及重点技术问题进行了研究。结果表明,在避光条件下于4℃低温冷藏并密封保存,添加甲醇作为保护剂,保存时间不应超过3 d。实验选择进样口温度为220℃,顶空瓶压力为96.52 kPa,调节载气流量设置实际分流比为51,可以有效改善顶空进样测定样品时存在的不出峰、不稳定或灵敏度降低的问题。对地表水、自来水及生活污水实际样品进行四乙基铅测定和加标回收分析,加标回收率为81.0%~110%,相对标准偏差(RSD)为2.5%~7.4%,能够满足《水质四乙基铅的测定顶空/气相色谱质谱法》(HJ 959—2018)的测定要求。将顶空进样法与吹扫捕集法进行比较,结果表明顶空进样法稳定性更好,适合大批量四乙基铅样品的连续测定。     

Concentrations of chlorine, bromine and iodine in Japanese rivers

Concentrations of halogens (Cl, Br and I) in 30 Japanese rivers were measured by ion chromatography and inductively coupled plasma mass spectrometry to understand their behavior in the terrestrial environment. Concentrations of Cl, Br and I in each river, obtained at 10 sampling points from the upper stream to the river mouth, tended to increase near the river mouth. The ranges of geometric means of Cl, Br and I in each river were 1.0–19.4 mg l⁻¹, 2.5–67.9 μg l⁻¹, and 0.18–8.34 μg l⁻¹, respectively. To compare halogen behavior, the concentration ratios, Br/Cl and I/Cl, were calculated. The Br/Cl range was (2.3–7.8) × 10⁻³ (geometric mean: 3.74 × 10⁻³), and it was nearly constant except for the Yoneshiro river. It was estimated that 60–80% of total Br in the middle to lower parts of this river was the excess Br. The Br chemical form in all the rivers is generally considered to be Br⁻. The I/Cl ratios had different trends in rivers flowing into the Japan Sea and Pacific Ocean, possibly due to the different geological features in the river catchments.     

A methodology for assessing the maximum expected radon flux from soils in northern Latium (central Italy)

Northern Latium (Italy) is an area where the Rn risk rate is potentially high because of the extensive outcropping of Neogene U-rich volcanics and the presence of major active tectonic lineaments. The lack of data on Rn risk rates in that area, which is undergoing major urban and industrial development, has prompted this study. It proposes a methodology to evaluate the maximum potential diffusive Rn flux from soils based on the measurement of ²²⁶Ra, ²³²Th and ⁴⁰K activities by γ-ray spectrometry, and the measurement of main soil parameters influencing the Rn emanation. This methodology provides a simple, reliable and low-cost tool for drawing up radon flux maps useful to both public planners and private individuals, who want to operate safely in the study area. The proposed methodology may also be applied to other geographic areas outside the prescribed study area.     

氢化物发生-原子荧光光谱法测定土壤中的总汞

本文利用氢化物发生-原子荧光光谱法分析技术测定土壤中的总汞,样品用（1＋1）的王水试剂在沸水浴中加热消解,最后经离心分离处理,取上清液待测。该方法检出限为0.002μg/kg,测定上限为0.400 mg/kg。