High-molecular weight sulfur-containing aromatics refractory to weathering as determined by Fourier transform ion cyclotron resonance mass spectrometry

Biomarkers and low-molecular weight polyaromatic compounds have been extensively studied for their fate in the environment. They are used for oil spill source identification and monitoring of weathering and degradation processes. However, in some cases, the absence or presence of very low concentration of such components restricts the access of information to spill source. Here we followed the resistance of high-molecular weight sulfur-containing aromatics to the simulated weathering condition of North Sea crude oil by ultra high-resolution Fourier transform ion cyclotron resonance mass spectrometry. The sulfur aromatics in North Sea crude having double bond equivalents (DBE) from 6 to 14 with a mass range 188-674 Da were less influenced even after 6 months artificial weathering. Moreover, the ratio of dibenzothiophenes (DBE 9)/naphthenodibenzothiophenes (DBE 10) was 1.30 and 1.36 in crude oil and 6 months weathered sample, respectively reflecting its weathering stability. It also showed some differences within other oils. Hence, this ratio can be used as a marker of the studied crude and accordingly may be applied for spilled oil source identification in such instances where the light components have already been lost due to environmental influences.     

Conductive-diamond electrochemical oxidation of chlorpyrifos in wastewater and identification of its main degradation products by LC-TOFMS

The electrochemical transformation of the organophosphorous insecticide chlorpyrifos (CPF) was investigated in wastewater. The oxidation of CPF was carried out in a single-compartment electrochemical flow cell working under batch operation mode, using diamond-based material as anode and stainless steel as cathode. In order to evaluate its persistence and degradation pathway, two different concentration levels (1.0 mg L⁻¹ and 0.1 mg L⁻¹) were studied. Liquid chromatography/mass spectrometry was used for evaluation of the initial and electrolyzed solutions. The identification of CPF transformation products was performed by liquid chromatography-time of flight-mass spectrometry (LC-TOFMS). Results showed that CPF is completely removed at the end of treatment time. Analysis by LC-TOFMS allowed the identification of six degradation products (with Mw 154, 170, 197, 305 321 and 333). Three of the identified intermediates (Mw 170, 305 and 321) were completely removed at the end of electrolysis time. Interestingly, the formation of diethyl 3,5,6-trichloropyridin-2yl phosphate (chlorpyrifos oxon) and 3,5,6-trichloropyridin-2-ol was also found in previous reported degradation pathways using different degradation technologies.     

Multiresidue analysis and evaluation of the matrix effect on 20 pesticides in Brazilian maize (Zea mays L.) flour

Abstract

Maize consists of a cereal widely used in the preparation of different food products. Brazil is one of the world's largest maize producers. Several types of pesticides have been applied in maize crop, which can lead to the contamination of the derived products. The present work aims at the validation of multiresidue method to analyze the matrix effect and level of pesticides in maize flour. Twenty residues were investigated in samples commercialized in the state of Ceará, Brazil. The method was satisfactorily validated, according to parameters recommended by European Union. About 55% of the pesticides had an intense negative matrix effect. Multiresidue analyzes showed the presence of traces of fenitrotion in 20% of maize flour samples. Detected levels were below maximum residue limits recommended for maize. The results indicate that maize products need continuous monitoring to ensure food security.     

木粉/壳聚糖接枝丙烯酸-丙烯酰胺吸附树脂对二元重金属离子溶液中Pb^2＋的吸附

采用自制木粉/壳聚糖接枝丙烯酸-丙烯酰胺吸附树脂R1、R2、R3对二元金属离子Cu2＋/Pb2＋和Zn2＋/Pb2＋溶液中的吸附性能进行了较系统考察。Pb2＋离子溶液中存在竞争离子Cu2＋、Zn2＋时,随竞争离子浓度增加,3种吸附树脂R1、R2、R3对Pb2＋的吸附量明显下降,而竞争离子吸附量显著增加。二元溶液中各金属离子浓度相同时,3种树脂对竞争离子Cu2＋、Zn2＋的吸附量大于对Pb2＋的吸附量;各溶液中分别加入NaCl及NaNO3、尿素后,对Pb2＋离子的吸附量下降迅速。随吸附树脂用量增加,竞争离子Cu2＋、Zn2＋的吸附量逐渐减小,Pb2＋的吸附量在吸附树脂用量0.10 g/L（Zn2＋/Pb2＋溶液）或0.15 g/L（Cu2＋/Pb2＋溶液）时出现最大值。溶液pH值对树脂吸附性能有显著影响。3.0     

炭化柚子皮对废水中双酚A的吸附

采用磷酸二氢钾活化原材料柚子皮，分别在300℃和600℃对活化后柚子皮进行炭化，制得吸附剂（CC300和CC600），通过静态吸附实验研究了炭化柚子皮对双酚A的吸附性能。采用比表面积分析仪对炭化柚子皮进行表征，实验考察了pH值、吸附时间和温度对双酚A吸附的影响，并详细研究了炭化柚子皮对双酚A的吸附行为和机理。结果表明，高温炭化柚子皮（CC600）吸附双酚A能力比低温炭化（CC300）的强，其吸附较好地满足Langmuir和Freundlich等温方程；动力学研究表明，其吸附速率快，在150min内能达到吸附平衡，准二级动力学模型较好地描述该吸附行为，相关系数高达0．99：计算了热力学参数△G、△H和△S的值,△G为负值,说明该吸附过程为自发过程。     

垃圾焚烧飞灰对染料（亚甲基蓝）的吸附性能

以垃圾焚烧飞灰为吸附剂对亚甲基蓝进行了吸附脱色实验。主要探讨了飞灰粒径、用量、温度、pH值和初始浓度等因素对亚甲基蓝吸附的影响，同时分析了吸附上清液中重金属Pb和Cr的浸出毒性。研究结果表明，在25—45℃、pH值2～12、飞灰用量1～5g范围内，经过180min吸附，亚甲基蓝的脱色率都达75％以上，最高可达99．46％。实验还得出，除重金属Pb外，吸附上清液中重金属的浸出量远远低于《危险废物鉴别标准浸出毒性鉴别》的限定值。因此，若能降低重金属Pb的浸出，飞灰将具有应用于处理染料废水的巨大潜力。     

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.     

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.     

介绍一种原子吸收光谱法空心阴极灯的替代用法

用原子吸收光谱法测定Mn、Zn、Cu金属元素的常规监测中，需频繁更换Mn灯、Zn灯和Cu灯等空心阴极灯，耗时费力，增加了时间成本。文章介绍了一种新方法，用Mn灯、Zn灯两种空心阴极灯可作为Cu灯空心阴极灯使用。在实际操作中减少了更换灯的频次和预热次数，使测试工作变得经济而省时，降低了监测成本，提高了工作效率，是一项值得推广的方法改进。