全二维气相色谱-电子捕获检测器测定复杂基质土壤中24种有机氯和拟除虫菊酯类农药

目前针对环境样品中有机氯和拟除虫菊酯类农药的检测方法主要有气相色谱法和气相色谱-质谱法（GC-MS）,由于气相色谱法采用电子捕获检测器从而具有较高的灵敏度,在污染物的环境行为研究中得到广泛应用,GC-MS法的定性效果好,但检测灵敏度相对偏低。本文研究了2018年土壤详查江苏地区样品中有机氯农药和拟除虫菊酯的残留状况,结果显示,即使经过多次净化仍有20%的样品存在假阳性或基质干扰现象。为了提高定性准确度,同时保证检测灵敏度,实验建立了复杂基质土壤中20种有机氯农药和4种拟除虫菊酯的全二维气相色谱-电子捕获检测器检测方法,最终选择中等极性的TG-35MS为第一色谱柱,非极性的（DB-1）为第二色谱柱,将鲜样与无水硫酸钠混合均匀后,以正己烷-丙酮（1：1,V/V）为提取剂进行索氏提取,采用全二维气相色谱-电子捕获检测器进行检测,外标法定量。各物质的质量浓度均在1.0~500μg/L内与其峰面积呈线性关系,相关系数均大于0.995,检出限为0.02~0.17μg/kg。用标准加入法进行回收实验,测得回收率为80.7%~103.5%,测定值的相对标准偏差（n=6）为1.84%~10.12%。本方法将高灵敏度检测器与全二维色谱相结合,在保证检测灵敏度的同时增加了峰容量,有效去除了基质干扰。相比2018年土壤详查参考方法HJ 835—2017的检出限0.02~0.09mg/kg（全扫模式）,本方法检出限显著降低,且操作简单,可为复杂基质样品中的痕量超痕量检测提供参考。     

气相色谱-串联质谱技术分析地质调查植物样品中持久性有机污染物的优势

对于复杂基质的样品,采用气相色谱法、气相色谱-质谱法( GC - MS)不能满足当前痕量水平分析的要求,串联质谱已发展成一种有机分析测试的成熟技术可应用于地质调查样品分析.本文建立了气相色谱-串联质谱技术( GC - MS - MS)分析植物样品中有机氯农药及多氯联苯的方法,通过对植物样品(圆白菜、菠菜、胡萝卜、橘子)分析,系统比较了GC- MS-MS与气相色谱-电子捕获检测器(GC-ECD)和气相色谱-选择离子-质谱( GC - SIS - MS)三种分析技术的检出限、定性定量分析结果,确认了分析方法的适用性.GC- MS-MS方法的检出限为0.03～0.29 ng/g,大部分化合物均低于GC -ECD的检出限,是GC - SIS -MS检出限的0.4倍.GC- MS-MS分析表明,圆白菜不含反式-氯丹,排除了GC-ECD的假阳性检出;检测胡萝卜等基质复杂、净化困难的样品,GC- MS-MS也表现出良好的定性定量能力;检出低含量水平样品菠菜含有0.26 ng/g六氯苯,而气相色谱未检出,表明GC- MS-MS显著提高了分析灵敏度,能够对样品中低含量的化合物进行准确定量.在三种分析技术中,GC- MS-MS在样品的准确定性、复杂基质样品分析灵敏度、低含量水平准确定量等方面都具有独特的优势,同时能够应用于复杂样品检测结果的确证.     

加速溶剂萃取-气相色谱/质谱法同时测定土壤中拟除虫菊酯类等18种农药残留

采用正己烷-丙酮-磷酸混合溶剂为提取剂,在萃取温度100℃、压力10.3 MPa条件下,用快速溶剂萃取仪提取土壤样品,石墨碳黑氨基固相萃取柱净化,PTV大体积进样,气相色谱-质谱联法同时检测六六六(HCHs)、滴滴涕(DDTs)和10种拟除虫菊酯类农药(联苯菊酯、甲氰菊酯、氯氟氰菊酯、氯菊酯、氯氰菊酯、氟氯氰菊酯、氟氨氰菊酯、氰戊菊酯、氟氰戊菊酯、溴氰菊酯)共18种农药残留。在10～20μg/kg的添加浓度下,目标化合物平均回收率为82.84%～96.33%,相对标准偏差(RSD,n=6)为3.21%～7.34%;在20～40μg/kg的添加浓度下,目标化合物平均回收率为80.55%～103.76%,RSD(n=6)为2.56%～5.78%;在40～80μg/kg的添加浓度下,目标化合物平均回收率81.56%～95.38%,RSD(n=6)为2.19%～5.88%。方法检出限为0.11～3.40μg/kg,实际样品检测的RSD(n=3)为4.94%～8.74%。方法简单快速、灵敏度高、准确度好,可以满足土壤中HCHs、DDTs和拟除虫菊酯类农药残留的实际检测需要。     

鄱阳湖龙口地区沉积物中有机氯农药的垂向分布特征

采用电子捕获检测器气相色谱仪(GC-ECD)测定鄱阳湖龙口地区4个沉积物柱样中有机氯农药含量。结果表明,4个沉积物柱样间有机氯农药含量差异显著,总有机氯农药(∑OCPs)含量为7.78~93.7ng/g,总六六六(∑HCHs)含量为0.73~39.6ng/g,总滴滴涕(∑DDTs)的含量为2.44~49.4ng/g。与国内其他同类样品相比,研究区各化合物的含量水平明显偏高;沉积物中总有机碳(TOC)和OCPs有较好的相关关系;与沉积物风险评估值对比,鄱阳湖龙口地区的有机氯农药存在一定的生态风险。     

气相色谱-质谱法同时测定河流沉积物中多环芳烃和有机氯农药

建立了用加速溶剂萃取,气相色谱-质谱法同时测定河流沉积物中16种多环芳烃和19种有机氯农药的分析方法,优化了萃取溶剂、萃取温度和时间、凝胶渗透色谱收集时间、固相萃取洗脱溶剂和洗脱体积等条件。16种多环芳烃的方法检出限在0.15~0.59 ng/g,加标回收率为82%~102%,相对标准偏差(RSD,n=5)为1.1%~4.5%。19种有机氯农药的方法检出限在0.14~2.23 ng/g,加标回收率为71%~108%,相对标准偏差(RSD,n=5)为1.0%~4.5%。实际样品的测定结果表明,该方法分离效果较好,能够满足沉积物样品中多环芳烃和有机氯农药的分析要求。     

气相色谱法测定地下水中15种有机氯农药

通过优化色谱分离条件,建立了一种以正己烷为液-液萃取溶剂,气相色谱法(电子捕获检测器)检测地下水中15种有机氯农药组分的分析方法。采用内标法降低了系统误差,定量分析结果更加准确。加标20ng/L时测定回收率为84.8%～101.0%,相对标准偏差(RSD,n=7)为1.9%～5.6%;基于5ng/L加标样品计算的检出限为0.6～1.4ng/L。方法适用于地下水中有机氯农药的检测。     

圆盘固相萃取富集-气相色谱法测定地表水中有机氯和有机磷农药

采用环境友好的圆盘固相萃取新技术富集水体中有机氯农药和有机磷农药,分别用微池电子捕获检测器(μECD)和火焰光度检测器(FPD)气相色谱法检测,实现了水中有机氯和有机磷农药残留物的测定。结果表明,16种有机氯农药的平均回收率为64.7%~102%,精密度(RSD,n=6)为2.9%~15%;13种有机磷农药的平均回收率为65.9%~104%,精密度(RSD,n=6)为1.7%~17%。方法快速、灵敏、低污染,可用于水体中多种有机氯农药和有机磷农药的残留分析。     

地质调查样品中有机氯农药分析存在的困难和解决方法

9种有机氯农药(六氯苯、α-HCH、β-HCH、γ-HCH、δ-HCH、p,p′-DDE、p,p′-DDD、o,p′-DDT和p,p′-DDT)是国土资源地质大调查项目中水和土壤样品必测的有机污染物。有机氯农药自身结构和性质的特殊性以及地质调查样品的差异性,在采用气相色谱电子捕获检测器(GC-ECD)分析有机氯农药过程中仍然存在许多困难。文章结合大量地质调查样品中有机氯农药分析的实践经验,从溶剂与待测物响应值的关系、基质效应的表现、样品前处理以及仪器日常维护四个方面,介绍了针对不同样品和分析要求正确选择进样溶剂、判断和解决基质效应,并通过良好的仪器日常维护习惯确保地质调查样品中有机氯农药检测灵敏度达到要求。     

沈阳郊区表层土壤有机氯农药残留特征及风险评价

利用GC-ECD定量测定了沈阳郊区21个表层土壤样品中有机氯农药(OCPs)的含量,并对其残留特征、可能来源及生态风险进行了分析。结果表明,研究区表层土壤中OCPs的检出率达到95.2%,残留量最高值达到111.67 ng·g-1,平均值26.91 ng·g-1,其中以六六六(HCHs)和滴滴涕(DDTs)为主。与国内其他城市土壤中OCPs含量相比,沈阳郊区表层土壤HCHs和DDTs残留属于较低水平,但HCB残留属于较高水平。研究区OCPs的来源解析表明OCPs主要来自环境中的早期残留和近期林丹的使用,六氯苯(HCB)的来源还应包括工业生产。相关性分析说明土壤中总有机碳和水溶盐含量是影响OCPs残留的重要因素。生态风险评价显示表层土壤中DDTs类有机氯农药对该区生物可能仍存在生态风险。     

福建兴化湾水体有机氯农药污染状况

利用气相色谱-电子检测器对福建兴化湾河水和海水中的19种有机氯农药(HCHs、DDTs等)进行的分析结果表明,几种有机氯农药尽管已停止生产多年,但在河水及海水中仍有残留.二者的有机氯农药的质量浓度分别为10.96～56.31,5.78～161.64 ng/L ,同国内外其他港口海区及河流相比,其污染程度相对较低.丰水期河水中DDT的降解产物主要为DDE,而海水中DDT的降解产物主要为DDD.同时,对有机氯农药现状的分析表明,近年来仍有有机氯农药污染的输入,其农药的使用主要集中在六六六和滴滴涕上.     

The terrestrial fauna of the Late Triassic Pant-y-ffynnon Quarry fissures,South Wales,UK and a new species of Clevosaurus (Lepidosauria: Rhynchocephalia)

Pant-y-ffynnon Quarry in South Wales yielded a rich cache of fossils in the early 1950s, including articulated specimens of new species (the small sauropodomorph dinosaur Pantydraco caducus and the crocodylomorph Terrestrisuchus gracilis), but no substantial study of the wider fauna of the Pant-y-ffynnon fissure systems has been published. Here, our overview of existing specimens, a few described but mostly undescribed, as well as freshly processed material, provides a comprehensive picture of the Pant-y-ffynnon palaeo-island of the Late Triassic. This was an island with a relatively impoverished fauna dominated by small clevosaurs (rhynchocephalians), including a new species, Clevosaurus cambrica, described here from a partially articulated specimen and isolated bones. The new species has a dental morphology that is intermediate between the Late Triassic Clevosaurus hudsoni, from Cromhall Quarry to the east, and the younger C. convallis from Pant Quarry to the west, suggesting adaptive radiation of clevosaurs in the palaeo-archipelago. The larger reptiles on the palaeo-island do not exceed 1.5?m in length, including a small carnivorous crocodylomorph, Terrestrisuchus, and a possible example of insular dwarfism in the basal dinosaur Pantydraco.     

Définition d'une limite multicritère ; stratigraphie du passage Campanien–Maastrichtien du site géologique de Tercis (Landes,SW France)Definition of a multi-criteria boundary; stratigraphy of the Campanian–Maastrichtian interval of the geological site at Tercis (Landes,SW France)

Lithostratigraphy, physicochemical stratigraphy, biostratigraphy, and geochronology of the 77–70 Ma old series bracketing the Campanian–Maastrichtian boundary have been investigated by 70 experts. For the first time, direct relationships between macro- and microfossils have been established, as well as direct and indirect relationships between chemo-physical and biostratigraphical tools. A combination of criteria for selecting the boundary level, duration estimates, uncertainties on durations and on the location of biohorizons have been considered; new chronostratigraphic units are proposed. The geological site at Tercis is accepted by the Commission on Stratigraphy as the international reference for the stratigraphy of the studied interval. To cite this article: G.S. Odin, C. R. Geoscience 334 (2002) 409–414.     

The effect of water on accessory phase solubility in subaluminous and peralkaline granitic melts

The solubilities of columbite, tantalite, wolframite, rutile, zircon and hafnon were determined as a function of the water contents in peralkaline and subaluminous granite melts. All experiments were conducted at 1035 °C and 2 kbar and the water contents of the melts ranged from nominally dry to approximately 6 wt.% H₂O. Accessory phase solubilities are not affected by the water content of the peralkaline melt. By contrast, solubilities are affected by the water content of the subaluminous melt, where the solubilities of all the accessory phases examined increase with the water content of the melt, up to 2 wt.% H₂O. At higher water contents, solubilities are nearly constant. It can be concluded that water is not an important control of accessory phase solubility, although the water content will affect diffusivities of components in the melt, thus whether or not accessory phases will be present as restite material. The solubility behaviour in the subaluminous and peralkaline melts supports previous spectroscopic studies, which have observed differences in the coordination of high field strength elements in dry vs. wet subaluminous granitic glasses, but not for peralkaline granitic glasses. Lastly, the fact that wolframite solubility increases with increasing water content in the subaluminous melt suggests that tungsten dissolved as a hexavalent species.     

Late Wuchiapingian (Late Dzhulfian,early Late Permian) limestone olistolites within the Tertiary flysch of Glypia Unit (Mount Parnon,central–eastern Peloponnesus,Greece)

Some olistolites reworked in a Tertiary flysch of Mount Parnon (Peloponnesus, Greece) exhibit a Late Permian assemblage, dominated by Paradunbarula (Shindella) shindensis, Hemigordiopsis cf. luquensis and Colaniella aff. minima. This association corresponds to the Late Wuchiapingian (=Late Dzhulfian), a substage whose algae and foraminifera are generally little known. Contemporaneous limestones crop out in the middle part of the Episkopi Formation in Hydra, but they are rather commonly reworked in Mesozoic and Cainozoic sequences. The palaeobiogeographical affinities shared by the foraminiferal markers of Greece, southeastern Pamir, and southern China, are very strong (up to the specific level), and are congruent with the Pangea B reconstructions. To cite this article: E. Skourtsos et al., C. R. Geoscience 334 (2002) 925–931.     

PALEONTOLOGY

正20141596 Liu Yunhuan(School of Earth Sciences and Resources,Chang’an University,Xi’an 710054,China);Shao Tiequan Early Cambrian Quadrapyrgites Fossils of Xixiang Boita in Southern Shaanxi Province(Journal of Earth Sciences and Environment,ISSN1672-6561,CN61-1423/P,35(3),2013,p.39-43,3 illus.,20 refs.)     

GEOCHEMICAL EXPLORATION

正20141719 Chen Zhijun(State Key Laboratory of Geological Processes and Mineral Resources,China University of Geosciences,Wuhan 430074,China);Chen Jianguo Automated Batch Mapping Solution for Serial Maps:A Case Study of Exploration Geochemistry Maps(Journal of Geology,ISSN1674-3636,CN32-1796/P,37(3),2013,p.456-464,2 illus.,2 tables,10 refs.)     

MICROPALAEONTOLOGY

正20140962 Chen Fenning(Xi’an Institute of Geology and Mineral Resources,Xi’an710054,China);Chen Ruiming Late Miocene-Early Pleistocene Ostracoda Fauna of Gyirong Basin,Southern Tibet(Acta Geologica Sinica,ISSN0001-5717,CN11-1951/P,87(6),2013,p.872-886,6illus.,56refs.)     

PETROLOGY

正1.IGNEOUS PETROLOGY20142008Cai Jinhui(Wuhan Center,China Geological Survey,Wuhan 430205,China);Liu Wei Zircon U-Pb Geochronology and Mineralization Significance of Granodiorites from Fuzichong Pb-Zn Deposit,Guangxi,South China(Geology and Mineral Resources of South China,ISSN1007-3701,CN42-1417/P,29(4),2013,p.271-281,7illus.,     

ENVIRONMENTAL GEOLOGY

正20141205Cheng Weiming(State Key Laboratory of Resources and Environmental Information System,Institute of Geographic Sciences and Natural Resources Research,CAS,Beijing 100101,China);Xia Yao Regional Hazard Assessment of Disaster Environment for Debris Flows:Taking Jundu Mountain,Beijing as an     

PROSPECTING EXPLORATION

正20141266Fan Chaoyan(Guangdong Provincial Key Laboratory of Mineral Resources and Geological Processes,Guangzhou 510275,China);Wang Zhenghai On Error Analysis and Correction Method of Measured Strata Section with Wire Projection Method(Journal of