珠江三角洲含N亚硝胺地下水与地区性癌症

肆虐我国南方局部区数百年以鼻咽癌和肝癌为主的恶性肿瘤病,为典型的地区性癌症。本文以珠江三角洲为例,应用流行病学与生态地球化学相结合的调查方法,检出了病区环境水和饮水中存在致癌物质N亚硝胺,研究了癌病区生态系统由地质构造背景、气候、水文和生态条件制约,自然形成水体N亚硝胺的机理。实验改进、优化了环境饮水微量亚硝胺测定方法,新建立的固相萃取气相色谱串联质谱(GC/El-MS/MS)测定纳克级N亚硝胺方法一次可测9种N亚硝胺化合物,检出限达到0.34~2.19 ng/L。在珠江三角洲癌病区环境饮水中首次发现9种亚硝胺化合物,含量为307~0.34 ng/L,总检出率为40%。四会等较低工业污染区古井水、手压井水和自来水的亚硝胺有相近似的含量统计特点:亚硝基二甲胺和亚硝基二正丁胺的均值和峰值为不高的超标值,均值分别为21.77和15.54 ng/L。这批水样大多采自0~20 m深度井水,属本区代表性特殊地质构造和气候生态环境中形成的地下水,也是研究区生产和生活开发最多的水源层;所含超标亚硝胺可能是本区数百年高发癌症的主因。近年工业发展带来的亚硝胺污染源的叠加,增高了该区环境饮水亚硝胺超标率及癌症发病率。文中分析了珠江三角洲土壤和地下水富氮营养化现象和区域氮的来源。     

Simultaneous Analysis of Natural Free Estrogens and Their Sulfate Conjugates in Wastewater

Natural estrogens from humans increasingly attract attention because of their strong endocrine disrupting potency. The discharge of sewage water is considered as the most important source of these endocrine disrupting chemicals (EDCs) in the environment. Therefore, a GC‐MS method was developed for the simultaneous analysis of six natural free estrogens and their sulfate conjugates in municipal wastewater, in which natural free estrogens and sulfate conjugates were successfully separated from an Oasis HLB solid phase extraction (SPE) cartridge with two different eluents, and the sulfate conjugates were then transformed to their corresponding free estrogens by acid solvolysis. Before the analysis with GC‐MS, samples were derivatized by N,O‐bis (trimethylsilyl) trifluoroacetamide (BSTFA) plus 1% trimethylchlorosilane (TMCS) at 80°C for 40 min. Satisfactory recoveries ranging from 64 to 112.3% were obtained by spiking ultra‐purified water, raw, and treated municipal wastewater with the six estrogens at 50, 100, and 50 ng/L, respectively. The method was successfully applied to wastewater samples from one WWTP, which suggested that E1 was the dominant natural estrogens in effluent and E3‐3S was one of the conjugates possibly occurring in the effluent.     

Simultaneous Analysis of Natural Free Estrogens and Their Conjugates in Wastewater by GC‐MS

A solid‐phase extraction (SPE)‐gas chromatography (GC)‐mass spectrometry (MS) analytical method was developed for the simultaneous analysis of natural free estrogens and their conjugates in wastewater samples. Natural free estrogens and their conjugates in wastewater were successfully separated by the oasis hydrophilic‐lipophilic balance solid phase extraction (Oasis HLB SPE) method, and the conjugates were initially enzyme hydrolyzed by β‐glucuronidase or arylsulfatase from Helix pomatia prior to derivatization. N‐methyl‐N‐(tert‐butyldimethylsilyl)trifluoroacetamide (MTBSTFA) plus 1% tert‐butyldimetheylchlorosilane (TBDMCS) was chosen as the derivatization reagent, and the most appropriate conditions of derivatization were determined to be at 95°C for 90 min. The recovery ratios of nine target chemicals were determined by spiking them in 1 L of ultra‐purified water or the influent of a wastewater treatment plant (WWTP). The recovery ratios of six out of nine for the analytes ranged from 73.3–114.9% with relative standard deviations (RSD) from 1.6–19.9%. The established method was successfully applied to environmental wastewater samples which were collected from one municipal wastewater treatment plant (WWTP) in Osaka, Japan, for the determination of natural free estrogens and their conjugates. In the influent sample, E1, E2, E1‐3S, E3‐3S, and E1‐3G were detected at concentrations of 16.6, 9.6, 8.2, 21.9, and 3.2 ng L^–1, respectively. However, only E1 was detected at a high concentration of 44 ng L^–1 in the effluent sample, suggesting that it is the dominant natural free estrogen in the effluent.     

The petroleum geochemistry of the Termit Basin,Eastern Niger

Sixty crude oils from the Termit Basin (Eastern Niger) were analysed using biomarker distributions and bulk stable carbon isotopic compositions. Comprehensive oil-to-oil correlation indicates that there are two distinct families in the Termit Basin. The majority of the oils are geochemically similar and characterized by low Pr/Ph (pristane to phytane ratios) and high gammacerane/C₃₀ hopane ratios, small amounts of C₂₄ tetracyclic terpanes but abundant C₂₃ tricyclic terpane, and lower δ¹³C values for saturated and aromatic hydrocarbon fractions. All of these geochemical characteristics indicate possible marine sources with saline and reducing depositional environments. In contrast, oils from well DD-1 have different geochemical features. They are characterized by relatively higher Pr/Ph and lower gammacerane/C₃₀ hopane ratios, higher amounts of C₂₄ tetracyclic terpane but a low content of C₂₃ tricyclic terpane, and relatively higher δ¹³C values for saturated and aromatic hydrocarbon fractions. These geochemical signatures indicate possible lacustrine sources deposited under freshwater, suboxic-oxic conditions. This oil family also has a unique biomarker signature in that there are large amounts of C₃₀ 4α-methylsteranes indicating a freshwater lacustrine depositional environment.The maturity of the Termit oils is assessed using a number of maturity indicators based on biomarkers, alkyl naphthalenes, alkyl phenanthrenes and alkyl dibenzothiophenes. All parameters indicate that all of the oils are generated by source rocks within the main phase of the oil generation stage with equivalent vitrinite reflectance of 0.58%–0.87%.     

青岛海域浒苔中挥发油成分分析

将青岛海域采集的浒苔在挥发油测定器中通过水蒸气蒸馏法提取,用 GC/MS 进行分离和检测,得到35种化合物。采用色谱峰面积归一法在MSD化学工作站下进行数据处理得到相对含量,其中主要成分及其含量为：棕榈酸(hexadecanoic acid,29.676%),顺-9,12,15-十八碳三烯-1-醇(9,12,15- Oc-tadecatrien-1-ol,(ZZZ)-,6.957%),鲨烯(Squalene ,5.567%),顺-11-十六碳烯酸(Z-11-Hexadecenoic acid ,4.494%),顺-7-十六碳烯酸(Z-7-Hexadecenoic acid,3.997%),9,12-十八碳二烯酸甲酯(9,12-Octade-cadienoic acid, methyl ester ,3.144%),十七碳酸(Heptadecanoic acid ,2.827%),邻苯二甲酸双庚酯(1,2-Benzenedicarboxylic acid, diheptyl ester,2.531%),二十碳烷(Eicosane,2.483%),十六碳酸甲酯(Hexadecanoic acid, methyl ester,2.468%),异植醇(Isophytol,2.183%),邻苯二甲酸单(2-乙基己基)酯(1,2-Benzenedicarboxylic acid, mono(2-ethylhexyl) ester,1.885%),油酸(Oleic acid,1.479%),14-甲基十七酸甲酯(Heptadecanoic acid,14-methyl-, methyl ester,1.473%)。这35种化合物占总检出量的82.199%。     

北京市西北城区大气可吸入颗粒物中饱和烃的分布特征

利用气相色谱、气相色谱-质谱分析法从北京市西北城区四个季节大气可吸入颗粒物（PM10）中检测出种类丰富的饱和烃,主要包括正构烷烃、萜烷及甾烷等系列化合物。利用饱和烃的多项参数（如主峰碳数、碳优势指数CPI、藿烷22S/(22S+22R)比值等）对大气PM10中可溶有机物的来源及分布作了探讨。北京市西北城区PM10中正构烷烃的主峰碳数均介于23和27之间,而CPI值介于1和3之间,表明北京市西北城区PM10中的饱和烃均不同程度地受到了高等植物等现代生物和化石燃料（石油、煤等）不完全燃烧产物两种来源的影响,其中在春、夏季以高等植物、花粉、微生物等生物来源占比重较大,而在秋、冬季,尤其在冬季,化石燃料的不完全燃烧造成的污染比较明显。萜烷类物质的检出,表明北京市西北城区四个季节PM10中部分饱和烃来自于石油等化石燃料的不完全燃烧。甾烷类物质的检出,表明北京市西北城区四个季节PM10中部分饱和烃是来自于车辆释放的机油等。     

锰钾矿处理高浓度含酚废水研究

对人工合成锰钾矿氧化降解高浓度含酚废水的特性进行了研究。结果表明,体系酸度和矿物用量是影响废水处理效果的重要因素。加酸量为0.12 mol/L,矿物用量20 g/L,温度70℃,反应时间3 h时效果最佳,废水总酚含量由1269 mg/L降低至268 mg/L,同时CODCr与TOC去除率为31.2%和70.5%。经GC/MS测定,水中酚类物质为苯酚、甲基苯酚、二甲基苯酚,最佳条件下,酚类物质浓度已低至检测限以下,水中残余吲哚、长链烷烃、喹啉及其衍生物等难降解有机物。     

气相色谱—质谱联用技术测定岩芯样品中的苯系化合物

利用气相色谱／普联用技术测定了同一井位、不同深度岩芯样品中的苯、甲苯、乙苯和二甲苯化合物。采用脂肪抽提器法和柱层析分析方法对岩芯样品进行进行预处理,得以岩芯施组分中的芳烃组合。以选择离子扫描模式,建立了标准样品的定量分析方法。方法对苯系化合物各待测组分的最小检出限均为０．５ｍｇ／Ｌ,加标回收率在９３．６％～１０９．５％。给出了岩芯样品的分离色谱图和实测结果,苯和甲苯含量在１．４～１１１．７ｎｇ／ｇ     

决策树算法在雷达反射率因子质控中的应用

基于决策树算法，利用2020年武汉多普勒天气雷达探测资料，分析决策树算法对反射率因子的质控效果，得到以下主要结论：（1）决策树算法能有效滤除湖北东部地区由于山脉和城市建筑所导致的固定地物回波和超折射地物回波。（2）对于降水回波而言，决策树算法不改变雷达近距离范围内回波的位置、形状和强度，而远距离处（≥160 km）回波则存在一定程度的过度质控，主要是由于雷达波束随距离增加而抬高以及回波垂直梯度较大导致。（3）决策树算法对辐射状和弧状杂波的质控能力较好，其滤除率达到95%以上。