Ultra trace simultaneous determination of 50 polycyclic aromatic hydrocarbons in biota using pMRM GC-MS/MS

Abstract

A saponification extraction method with gas chromatography pseudo-MRM (pMRM) mass spectrometry detection was developed for the determination of 50 total polycyclic aromatic hydrocarbons (TPAH50, a combination of parent and alkylated homologues) in biota. The method was aimed at monitoring and identification of potential TPAH contaminants in bitumen impacted environments. Alkylated PAHs were determined by multi-level, quantitative calibration using parent PAHs. The developed and thoroughly validated method required only one injection for TPAH50 analysis which represents significant saving of time and expensive authentic alkylated standards. The current method was tested with certified reference mussel tissue NIST 1974c and performed well. In a comparison study, the method reached a limit of quantitation (LOQ) for the TPAH50 between 0.1 and 0.2?ng g^?1, while the QuEChERs enhanced matrix removal – lipid (EMR) kit produced by Agilent showed an LOQ of 5–10?ng g^?1. The current method relied on response factors (RF) for the quantitation of alkylated PAHs determined against parent PAHs. These RFs were shown to be stable and consistent over the course of 1 year, during which over 200 routine environmental biota monitoring samples were analyzed. The environmental biota monitoring samples analyzed include muscle, carcass and liver, with an average total PAH50 concentration of 13, 90 and 135?ng g^?1, respectively. Results show significant differences in the distributions of 1 ringed, 2 ringed, 3 ringed, 4 ringed, and 5+ ringed TPAHs between the types of biota samples.     

基质固相分散-快速溶剂萃取-GC/MS法同时测定土壤中有机氯农药和多环芳烃

建立了基质固相分散-ASE提取-GC/MS法同时测定土壤中8种有机氯农药和16种多环芳烃的方法。对方法的线性、检出限、精密度、回收率及土壤质控样品进行了分析,结果表明,8种有机氯农药和16种多环芳烃线性良好,相关系数为0.997 5～0.999 8,方法检出限为0.39～1.57μg/kg,空白加标样品的相对标准偏差小于20%,实际土壤样品加标回收率为60.6%～125%,土壤质控样品结果均在范围内。该方法能够满足土壤中8种有机氯农药和16种多环芳烃的检测要求。     

Natural radionuclide concentrations in two phosphate ores of east Algeria

Ore is considered as an important source of many elements such as the iron, phosphorus, and uranium. Concerning the natural radionuclides, their concentrations vary from an ore to other depending on the chemical composition of each site.In this work, two phosphate ores found in East of Algeria have been chosen to assess the activity concentration of natural radionuclides represented mainly by three natural radioactive series ²³⁸U, ²³⁵U and ²³²Th, and the primordial radionuclide ⁴⁰K where they were determined using ultra-low background, high-resolution gamma-ray spectroscopy.The measured activity concentrations of radioactive series ranged from 6.2 ± 0.4 to 733 ± 33 Bq.kg⁻¹ for the ²³²Th series, from 249 ± 16 to 547 ± 39 Bq.kg⁻¹ for the ²³⁸U series, around 24.2 ± 2.5 Bq.kg⁻¹ for the ²³⁵U series, and from 1.4 ± 0.2 to 6.7 ± 0.7 Bq.kg⁻¹ for ⁴⁰K.To assess exposure to gamma radiation in the two ores, from specific activities of ²³²Th, ⁴⁰K and ²²⁶Ra, three indexes were determined: Radium equivalent (Ra_eq), external and internal hazard indexes (H_ex and H_in), their values ranged from 831 ± 8 to 1298 ± 14 Bq.kg⁻¹ for Ra_eq, from 2.2 ± 0.4 to 3.5 ± 0.7 Bq.kg⁻¹ for H_ex, and from 4.2 ± 0.7 to 4.5 ± 0.7 Bq.kg⁻¹ for H_in.     

Uranium isotopes in Tunisian bottled mineral waters

²³⁴U and ²³⁸U activity concentrations and their relative effective doses have been determined in 10 bottled mineral waters in Tunisia. Alpha spectrometry was used as technique to measure uranium isotopes. The obtained isotopic ratio ²³⁴U/²³⁸U varies between 1.1 and 3 which means that the two isotopes are not in radioactive equilibrium. Measured activity concentration varies between 3.2 and 40 mBq/l for ²³⁴U and between 1.5 and 26.3 mBq/l for ²³⁸U. Effective doses (assuming 2 litres per day of water consumption) coming from this two isotopes are found to vary between 0.16 and 2.02 μSv/a which is lower than the maximum recommended dose level by the WHO.     

Measuring the radium quartet (Ra, Ra, Ra, Ra) in seawater samples using gamma spectrometry

Radium isotopes are widely used in marine studies (eg. to trace water masses, to quantify mixing processes or to study submarine groundwater discharge). While ²²⁸Ra and ²²⁶Ra are usually measured using gamma spectrometry, short-lived Ra isotopes (²²⁴Ra and ²²³Ra) are usually measured using a Radium Delayed Coincidence Counter (RaDeCC). Here we show that the four radium isotopes can be analyzed using gamma spectrometry. We report ²²⁶Ra, ²²⁸Ra, ²²⁴Ra, ²²³Ra activities measured using low-background gamma spectrometry in standard samples, in water samples collected in the vicinity of our laboratory (La Palme and Vaccarès lagoons, France) but also in seawater samples collected in the plume of the Amazon river, off French Guyana (AMANDES project). The ²²³Ra and ²²⁴Ra activities determined in these samples using gamma spectrometry were compared to the activities determined using RaDeCC. Activities determined using the two techniques are in good agreement. Uncertainties associated with the ²²⁴Ra activities are similar for the two techniques. RaDeCC is more sensitive for the detection of low ²²³Ra activities. Gamma spectrometry thus constitutes an alternate method for the determination of short-lived Ra isotopes.     

复合分子筛去除水中氟化物的研究

通过使用复合分子筛对模拟含氟水进行静态吸附实验,研究了复合分子筛对水中氟化物的吸附性能,并分析了吸附过程中温度、pH值和停留时间等因素对分子筛除氟效率的影响。结果表明,用80 g粒径0.9 mm的分子筛处理150 mL浓度为5 mg/L的模拟含氟水,分子筛的除氟效率达到90%以上,而同样条件下天然沸石和改性涂铁沸石的去除率分别为23.35%和80.69%。分子筛的除氟效率随着温度呈现先上升后下降的趋势,50℃时去除效率达到最高,为92.7%;在弱酸性条件下的去除率比碱性条件要高,在pH=4时去除率最大,为91.8%;停留时间初始阶段与去除率保持正相关,在45 min后反应达到平衡。分子筛的吸附速率符合二级动力学方程dqe/dt=k(qe-qt)2,吸附等温线符合Langmuir方程。     

Fractionation of natural radionuclides in soils from the vicinity of a former uranium mine ?irovski vrh, Slovenia

As a result of former uranium mining and milling activities at ?irovski vrh, Slovenia, 0.6 million tons of uranium mill tailings (UMT) were deposited onto a nearby waste pile Boršt. Resulting enhanced levels of natural radionuclides in UMT could pose threat for the surrounding environment. Therefore, sequential extraction protocol was performed to assess mobility and bioavailability of ²³⁸U, ²³⁴U, ²³⁰Th and ²²⁶Ra in soils from the waste pile and its surrounding. The radionuclides associated with exchangeable, organic, carbonate, Fe/Mn oxides and residual fraction, respectively, were determined. Results showed that the highest activity concentrations for the studied radionuclides were on the bottom of the waste pile. In non-contaminated locations, about 80% of all radionuclides were in the residual fraction. Considering activity concentrations in the UMT, ²³⁸U and ²³⁴U are the most mobile. Mobility of ²²⁶Ra is suppressed by high sulphate concentrations and is similar to mobility of ²³⁰Th.     

Correlations between radiometric analysis of Quaternary deposits and the chronology of prehistoric settlements from the southeastern Brazilian coast

Natural gamma radiation measurements of sand deposits were carried out in order to study the chronology of prehistoric colonization of the Brazilian coast during the Holocene. The method employs thorium, uranium and potassium as tracers of the geological provenance of Quaternary deposits, where artificial shellmounds are found. The so-called sambaquis are archaeological settlements, characteristic of fisher-gatherers, specialized in the exploitation of shellfish. Our results show a considerable positive correlation between the formation of coastal deposits, based on cross plots of eTh/eU and eTh/K, and the antiquity of its prehistoric human occupation.     

OI~2-WFGD-Ⅱ烟气脱硫技术介绍

简要介绍了江苏苏源环保工程有限公司开发的OI^2-WFGD-Ⅱ湿法烟气脱硫技术的工艺特点、设备布置、技术参数、设备国产化以及技术应用。     

微波消解-原子吸收光度法测定堆肥中微量镉、锌和铜

研究并确定了微波消解堆肥的最佳条件,应用原子吸收与数据导数处理系统相结合方法解决了堆肥体系中微量金属Cd.Zn和Cu的测定问题,对应元素的灵敏度可提高一个数量级.检出限均有不同程度的降低,从而极大提高分析的准确度.同时对堆肥实际样品进行加标回收实验,测定了堆肥样品中金属的回收率,其回收率分别在99.5%-102.0%、98.7%-99.1%和98.8%-104.0%之间.实验结果显示,该方法快速、准确、可信.