浅析高效液相色谱-质谱/质谱法测定饮用水中的灭草松和2,4-D

利用高效液相色谱-质谱/质谱法,同时测定饮用水中灭草松和2,4-D,水样经0.45μm微孔滤膜过滤后直接上机,经高效液相色谱分离后,采用质谱/质谱法测定。结果表明,灭草松和2,4-D分别在0.25~8.00μg/L和1.00~30.0μg/L范围内线性良好,相关系数分别为0.9987和0.9980,检出限为0.002μg/L和0.004μg/L,相对标准偏差(RSD)分别为7.5%~8.0%和2.9%~4.8%,加标回收率分别在73.6%~90.4%和90.3%~103.0%之间。完全满足饮用水中灭草松和2,4-D的测定。     

高效液相色谱法同时测定地表水中四种醛类化合物

甲醛、乙醛、丙烯醛和三氯乙醛均为环境中常见的醛类化合物,对人的皮肤和粘膜有刺激作用,且有致癌危险。在现行的国家标准《地表水环境质量标准》中,测定甲醛采用分光光度法,乙醛、丙烯醛和三氯乙醛则采用气相色谱法,方法复杂且不统一。本研究建立了2,4-二硝基苯肼(DNPH)衍生,高效液相色谱法同时测定地表水中甲醛、乙醛、丙烯醛和三氯乙醛的分析方法。考察溶液温度、酸度、反应时间对2,4-二硝基苯肼与水中醛类化合物反应的影响,探讨高效液相色谱三元梯度法分离后测定4种腙类化合物的条件。在温度为40℃、pH=3的条件下,水样与2,4-二硝基苯肼反应1 h后用二氯甲烷萃取,采用高效液相色谱三元梯度法分离后测定,4种化合物的回收率为73.1%～115%,相对标准偏差为0.71%～5.3%,检出限为3.50～28.6μg/L。本方法能够同时测定地表水中甲醛、乙醛、丙烯醛和三氯乙醛。     

气相色谱法测定地下水中拟除虫菊酯有机氯百菌清等24种农药残留

拟除虫菊酯类、有机氯、百菌清等农药均属于电负性强化合物,采用气相色谱-电子捕获检测器(GC-ECD)检测具有较高的灵敏度,但由于拟除虫菊酯类农药分子量较大,其灵敏度显著低于有机氯,使得各类化合物进行分类检测的流程长、分析效率低。本文通过优选分析色谱柱和进样口温度等条件,利用气相色谱的色谱柱程序升压功能实现了多类别24种农药残留的快速、准确测定。实验中以正己烷为溶剂进行液液萃取,Florisil固相萃取柱净化,选择有机氯专用色谱柱(RTX-CLPesticides 2)进行分析,GC-ECD仪器在0.5~6000 ng/mL浓度范围内呈线性,方法检出限为1.00~12.00 ng/L,低、中、高三个浓度水平的加标回收率分别为80.3%~116%、79.9%~117%、85.7%~102%,相应的精密度(RSD,n=7)为1.5%~6.8%、1.3%~7.6%、1.1%~6.8%。本方法选用的有机氯专用色谱柱(RTX-CLPesticides 2)对多组分、多类别目标化合物有更好的分辨率,较通用型色谱柱(DB-5MS)更具分析优势;采用的色谱柱程序升压技术解决了拟除虫菊酯类化合物在气相色谱柱中停留时间过长而导致的低灵敏度、峰拖尾等技术难题。此方法灵敏、经济,分析通量高,可有效地同时分析多种类农药残留物质。     

原位生成离子液体分散液液萃取-高效液相色谱法测定水样中的莠去津

本文引入绿色溶剂离子液体作为萃取剂,建立了超声辅助-原位生成离子液体分散液液微萃取水样中莠去津的方法。即处理5 m L水溶液样品,以80μL的[HMIM]Cl为萃取剂,加入400μL配对离子交换剂双三氟甲磺酰亚胺锂盐(Li NTf2),通过原位生成的疏水性离子液体[HMIM]NTf2,对水中莠去津进行液液微萃取,经辅助超声10 min后4000 r/min离心8 min,结合高效液相色谱测定莠去津。莠去津的检出限为0.01mg/L,方法线性范围为0.01~0.5 mg/L,加标回收率(100.4%~106.7%)显著优于直接离子液体分散液液萃取法(67%)。这种原位生成离子液体微萃取技术有望应用于更广泛的有机污染物分析检测中。     

固相萃取-液相色谱/质谱法测定地下水中三嗪类和酰胺类除草剂残留

固相萃取-液相色谱/质谱法是三嗪类和酰胺类除草剂常用的检测方法。本文针对现有分析方法仪器分析时间较长的缺点,以HLB柱为固相萃取柱,二氯甲烷-丙酮混合液(V∶V=4∶1)为洗脱剂,氟罗里硅土柱为净化柱,采用快速液相色谱柱,建立了固相萃取-液相色谱/质谱法快速测定地下水中14种三嗪类和2种酰胺类除草剂的方法。实验考察了固相萃取柱、定量离子扫描时间、富集柱洗脱溶剂、净化柱等因素对三嗪类和酰胺类除草剂测定的影响。通过延长定量离子的扫描时间,可以降低大部分目标化合物的相对标准偏差,提高仪器的稳定性;富集柱洗脱溶剂的极性对目标化合物回收率有较大影响,使用较强极性的二氯甲烷-丙酮(V∶V=4∶1)洗脱剂可以获得较高的目标化合物回收率;采用氟罗里硅土柱对萃取液进行净化,可除去干扰物,降低基体效应的影响。研究结果表明,14种三嗪类除草剂和2种酰胺类除草剂的检出限均小于0.40μg/L,在低、中、高三种添加浓度下,回收率均满足要求。本方法虽然色谱峰重叠较多,但仪器分析时间为5.10 min,与现有方法的仪器分析时间(15 min以上)相比,分析时间短,检出限低,能够满足日常环境水样中农药残留分析检测的需要。     

固相萃取-气相色谱法测定海水中狄氏剂和多氯联苯

狄氏剂与多氯联苯均是海洋环境中毒性大、难降解的有机污染物,建立海水中狄氏剂与多氯联苯快速、灵敏、准确的检测方法,具有重要意义。本文采用聚苯乙烯/二乙烯基苯（Cleanert PS）固相萃取柱对海水样品中的狄氏剂与7种多氯联苯进行分离富集,建立了气相色谱-电子捕获检测器（GC-μECD）的分析方法。实验了萃取流速、洗脱液、水样盐度与pH等实验条件对萃取效率的影响,确定样品以5.0 mL/min的流速经Cleanert PS固相萃取柱富集,真空抽干后用5.0 mL丙酮洗脱,挥干洗脱液,用1.0 mL正己烷定容,在选定的色谱条件下进行分析。方法精密度（RSD）为0.9%~4.4%,与《海洋监测规范》GB 17378.4—2007的RSD指标相比,精密度良好;加标回收率为82.1%~123.9%。狄氏剂的检出限（0.0088 μg/L）低于文献的检出限（0.05 μg/L）,7种多氯联苯的检出限（0.0012~0.0067 μg/L）低于文献的检出限（0.147~0.289 μg/L）。该方法适合于海水中痕量狄氏剂与多氯联苯的快速分析,具有一定的实用价值。     

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。     

柱前衍生-气相色谱法同时测定水中醛酮类和硝基苯类化合物

建立了柱前衍生-气相色谱法同时测定水样中醛酮类及硝基苯类化合物含量的检测方法。对影响衍生效率的因素如溶液的酸度、反应温度和时间、衍生试剂2,4-二硝基苯肼(DNPH)的用量等因素进行了试验,确定了DNPH与醛酮类化合物反应生成腙的最佳条件为pH=3时40℃恒温水浴反应1h。利用二氯甲烷萃取反应生成的腙和硝基苯类化合物,旋转蒸发仪浓缩,氮吹转换甲醇相,使用电子捕获检测器的气相色谱仪测定目标化合物。各化合物的质量浓度与其色谱峰峰面积的线性相关系数均在0.9989以上,方法检出限为0.01～0.03μg/L,相对标准偏差(RSD,n=6)均低于6.0%,回收率在89.5%～110.2%。方法简便、经济、回收率高,可用于水质中醛酮类及硝基苯类化合物的检测。     

离子对色谱法同时测定水中多种氯代酸性除草剂

建立了离子对色谱法同时测定水中DCPA二元酸、4-硝基苯酚、麦草畏、苯达松、2,4-二氯苯乙酸、2-甲基-4-氯苯氧乙酸(MCPA)、2-(4-氯苯氧基-2甲基)丙酸(MCPP)、3,5-二氯苯甲酸、2,4-滴丙酸9种氯代酸性除草剂。通过加入离子对试剂使多种极性强、保留弱的酸性除草剂在普通的反相色谱柱上同时分离。采用Shim-pack VP-ODS色谱柱,流动相为V(1-辛烷三乙磷酸铵溶液)∶V(乙腈)∶V(甲醇)=6∶3∶1,流速1.8 mL/min,不同组分全流程方法检出限范围为0.03~0.15μg/L,相对标准偏差在10%以下。建立的方法可将9种除草剂完全分离,与高效液相色谱法和气相色谱-质谱法相比,具有操作简单、分离效果好、回收率高、干扰少的优点,能够满足不同水质的检测要求。     

全国地下水调查中12种半挥发性必检组分的测定

经过优化组合建立了适用于全国地下水调查中六六六、滴滴涕、苯并[a]芘等12种必检组分测定的分析流程。方法利用正己烷液-液萃取,以气相色谱法(电子捕获检测器)检测11种有机氯组分,高效液相色谱法(紫外、荧光检测器)检测苯并[a]芘。建立了分析过程的质量控制流程程序与质量管理指标范围,确保检测数据达到允许的范围之内。所建分析方法检测限低、精密度好,方法简便、准确,适用于批量样品分析。方法报出限在1.00~1.50 ng/L,8次测定相对标准偏差为2.52%~6.07%,加标回收率为85.3%~106.0%,满足了全国地下水调查评价规范的要求。     

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