环境空气中醛酮类化合物检测方法优化与初步应用

环境空气中的醛酮类化合物是当今大气环境科学领域的研究热点.醛酮类化合物因反应活性较高、性质不稳定,导致检测较为困难.为准确测定环境空气中的醛酮类化合物,针对环境空气中质量浓度较高或活性较强的18种醛酮类化合物的采样和分析方法进行研究,并采用优化的方法于2018年5月对北京市典型城区环境空气中的醛酮类化合物进行了检测.结果表明:①与手动采样器同时同地点采样数据相比,自行制作的醛酮类化合物自动采样器能够实现连续采样,数据基本一致（R2为0.999 7）,其采样流速最大不超过0.8 L/min;醛酮类化合物采样管中杂质含量最高的乙醛为0.01 μg/管,小于我国HJ 683-2014《环境空气醛、酮类化合物的测定高效液相色谱法》标准限值（0.10 μg/管）.②采用所确定的二醛类化合物衍生化方法与质谱扫描条件可以成功检测乙二醛和甲基乙二醛两种二醛类化合物,建立了18种醛酮类化合物的标准曲线且标准曲线相关系数R2均大于0.995 0.③采用该优化方法得到北京市典型城区环境空气中18种醛酮类化合物质量浓度的日变化范围为17.73~88.42 μg/m3.      

城市自来水光催化氧化深度净化效果

在玻璃纤维网上制得ＴｉＯ２催化膜．用相应的固定膜光催化氧化装置进行了城市自来水的深度净化研究．ＧＣ／ＭＳ分析表明，在水中输入能量８７Ｗ／Ｌ的低光照强度下，经１ｈ的处理，自来水中有机物总量去除率在６０％以上．１９种优先污染物有５种消失，另２１种有害物质中１０种浓度降至仪器检测限以下．与此同时，水中各种有机物的浓度均显著下降．中间产物中基本不含有害的物质．光催化氧化对城市自来水中有机污染物有令人满意的去除效果．     

Diverse molecular compositions of dissolved organic matter derived from different composts using ESI FT-ICR MS

Dissolved organic matter (DOM) derived from various composts can promote significant changes of soil properties. However, little is known about the DOM compositions and their similarities and differences at the molecular level. In this study, the molecular compositions of DOM derived from kitchen waste compost (KWC), green waste compost (GWC), manure waste compost (MWC), and sewage sludge compost (SSC) were characterized by electrospray ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS). The molecular formulas were classified into four subcategories: CHO, CHON, CHOS, and CHONS. The KWC, MWC, and SSC DOM represented the highest fraction (35.8%-47.4%) of CHON subcategory, while the GWC DOM represented the highest fraction (68.4%) of CHO subcategory. The GWC DOM was recognized as the nitrogen- and sulfur-deficient compounds that were less saturated, more aromatic, and more oxidized compared with other samples. Further analysis of the oxygen, nitrogen-containing (N-containing), and sulfur-containing (S-containing) functional groups in the four subcategories revealed higher organic molecular complexity. Comparison of the similarities and differences of the four samples revealed 22.8% ubiquitous formulas and 17.4%, 11.1%, 10.7%, and 6.3% unique formulas of GWC, KWC, SSC, and MWC DOM, respectively, suggesting a large proportion of ubiquitous DOM as well as unique, source-specific molecular signatures. The findings presented herein provide new insight into the molecular characterization of DOM derived from various composts and demonstrated the potential role of these different compounds for agricultural utilization.     

固相萃取-LC-MS法检测水中痕量雌激素

研究了乙腈 /水、乙腈 /甲醇 /水、甲醇 /水三种不同流动相的条件下 ,LC MS分析雌酮 ,雌二醇 ,雌三醇 ,炔雌醇四种对象物质的灵敏度 ,发现流动相对灵敏度影响较大 ,不同流动相的对象物质的仪器检出限分别为 :330— 75 0ng·l- 1 ,1 0 0— 30 0ng·l- 1 ,5 0— 1 0 0ng·l- 1 .用固相萃取 LC MS检测杭州地区河水 ,在 8个采样点中 ,有 7个检测出了炔雌醇 ,其浓度范围在 1 1 7— 3 35ng·l- 1 之间 ,一个采样点检测出雌二醇 ,其浓度为 0 32ng·l- 1 .     

Perfluoroalkane acids in human milk under the global monitoring plan of the Stockholm Convention on Persistent Organic Pollutants (2008–2019)

● Perfluorooctanesulfonic acid and perfluorooctanoic acid highest in human milk. ● All other perfluoroalkane substances had median values of zero (101 samples). ● Branched PFOS recommended to be analyzed separately from linear isomer. ● PFOS and PFOA showed differentiated regional and income distribution. ● Human health risk assessment values not yet available at global level. Within the global monitoring plan (GMP) established by article 16 of the Stockholm Convention on Persistent Organic Pollutants, perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA), and perfluorohexane sulfonic acid (PFHxS) are recommended for analysis in core matrices to assess occurrence and changes geographically and with time. In 101 samples consisting of 86 national pools and 15 pools from States in Brazil obtained between 2008 and 2019, PFHxS was detected in 17% of the national pools and none in Brazil. PFOA and PFOS had a detection frequency of 100% and 92%, respectively. Other perfluoroalkane substances (PFAS) had either low detection frequencies and median values of zero (carboxylic acids C₄–C₁₁; except PFOA) or could not be quantified in any sample (sulfonic acids, C₄–C₁₀, and long-chain carboxylic acids, C₁₂–C₁₄). Correlation between PFOA and PFOS was moderately (r = 0.58). Whereas median values were almost identical (18.9 pg/g f.w. for PFOS; 18.6 pg/g f.w. for PFOA), PFOS showed larger ranges (< 6.2 pg/g f.w.–212 pg/g f.w.) than PFOA (< 6.2 pg/g f.w.–63.4 pg/g f.w.). It was shown that wealthier countries had higher PFOA concentrations than poorer countries. No difference in concentrations was found for samples collected in countries having or not having ratified the Stockholm Convention amendments to list PFOS or PFOA. The goal to achieve 50% decrease in concentrations within ten years was met by Antigua and Barbuda, Kenya, and Nigeria for PFOS and by Antigua and Barbuda for PFOA. In a few cases, increases were observed; one country for PFOS, four countries for PFOA.     

Analysis of dioxins and furans in environmental samples by GC-ion-trap MS/MS

The work aims to characterise PCDDs/Fs in environmental matrices by high resolution gas chromatography coupled to low resolution quadrupole ion-trap mass spectrometry (GC-QITMS/MS). In particular, the study was mainly focused in different environmental samples such as sewage sludge, soils, and sediments and in combustion residues as fly ashes. Previous experiences have already detected and quantified PCDDs/PCDFs in all matrices studied. Moreover, isomer-specific analysis of 2,3,7,8-PCDDs/Fs compounds corroborated good correlation between GC-QITMS/MS and a well-established technique such as high resolution mass spectrometry (HRMS). Finally, QC measures included the participation in intercalibration exercises. Successful results were achieved using GC-QITMS/MS in the analysis of fly ashes, soils and sediment materials. In general, GC-QITMS/MS constitutes an interesting alternative for routine analysis of dioxins in such as matrices.     

Identification of various laccases induced by anthracene and contribution to its degradation in a Mediterranean coastal pine litter

Mediterranean coastal ecosystems are known to be highly subject to natural and anthropic environmental stress. In this study, we examine the effects of anthracene as a common pollutant on the total microbial communities from a Pinus halepensis litter of a typical Mediterranean coastal site (Les Calanques, Marseille). The main objective was to identify the microbial factors leading the resilience of this ecosystem. Two questions were addressed: (i) how lignin-degrading enzymes (Laccase, Lignin-peroxidase and Mn-peroxidase) are affected by the presence of this molecule, (ii) whether the indigenous consortia are involved in its degradation in mesocosms under favorable incubation conditions (25 °C, 60% WHC) and after different time intervals (1 and 3 month(s)). We found a strong increase in laccase production in the presence of anthracene after 3 months, together with anthracene degradation (28% ± 5). Moreover 9,10-anthraquinone is detected as the product of anthracene oxidation after 3 months. However neither lignin-peroxidase activity nor Mn-peroxidase activity is detected. Laccase proteins directly extracted from litter were sequenced via Nano-LC-MS/MS and reveal twelve different peptide sequences induced by the presence of anthracene in the mesocoms. Our study confirms the major detoxification role of this enzymatic system and highlights the high degradation potential of fungal species inhabiting P. halepensis litter, a factor in the resilience of Mediterranean ecosystems.     

空气中挥发性有机物(VOCs) 的监测方法研究

建立了热脱附仪和气相色谱-质谱联用测定室内空气和环境空气中35种挥发性有机污染物的分析方法,方法的最低检出限为0.1～0.9μg/m3, 20μg/m3挥发性有机物标准经6次的重复测定,其相对标准偏差小于8.4%.该方法已用于室内空气和环境空气的测定,取得令人满意的结果.     

地表水体中同时分析18种糖皮质激素方法的建立

建立了一种采用固相萃取-超高效液相色谱串极质谱联用系统(UPLC-MS/MS)同时测定地表水体中18种糖皮质激素的高灵敏分析方法.样品经过HLB固相萃取柱富集净化、V(乙腈)/V(乙酸乙酯)=1∶1,洗脱后,用UPLC-MS/MS测定.流动相为甲醇和0.1%乙酸水溶液(体积比),采用梯度洗脱,实现了18种目标物质的基线分离,线性范围为1.0~1 000μg·L-1.实际水样的加标回收率为65%~108%.整个分析的方法检出限(MDL)除醋酸可的松和醋酸氢化可的松为10 ng·L-1外,其他均在0.10 ng·L-1和1.0 ng·L-1之间.应用此方法于北京地表水体5个样品,检测到8种糖皮质激素,浓度范围0.20~476ng·L-1,其中曲安西龙、曲安奈德、醋酸氢化可的松和丙酸氯倍他索在地表水中首次检出,证明了该方法的有效性.     

广州街道空气中挥发烃类特征和来源分析

采用固相吸附－热脱附－色谱／质谱检测器联用的方法分析了广州市街道空气中的发挥有机物。样品采自广州市区街道的３２个采样点,主要探讨了其中单环芳烃和正构烷烃的特征和可能来源;选取１３种烃类化合物进行进一步的因子分析,结果表明,这些挥发烃类可能主要来自汽油机车、工业和柴油机车的排放。多元线性回归分析表明３种源对所选挥发烃类的平均贡献分别为６４％、２３％和１３％。