5A分子筛吸附混合溶剂洗脱-气相色谱-同位素质谱分析土壤中正构烷烃单体碳同位素

利用5A分子筛吸附,环己烷-正戊烷混合溶剂洗脱分离富集正构烷烃,用气相色谱法测定正构烷烃含量,气相色谱-气体同位素质谱(GC-C-IRMS)测定土壤样品中正构烷烃单体碳同位素。实验优化了5A分子筛用量和洗脱剂的比例,需要络合的正构烷烃的量与分子筛加入量呈线性关系,络合x mg的正构烷烃,需加入2.75x g分子筛,络合环己烷-正戊烷最佳比例为9∶91。探讨了络合过程中5A分子筛对不同链长正构烷烃的络合规律,短链正构烷烃被5A分子筛优先吸附,长链正构烷烃的络合相对滞后。正构烷烃的络合洗脱回收率为44%～72%,精密度(RSD,n=6)为4%～8%;正构烷烃单体碳同位素分析精度为0.04‰～0.38‰(1σ)。采用5A分子筛净化混合溶剂洗脱方法,分析加油站附近的实际土壤样品,未分峰基本消除,获得良好的净化效果,满足正构烷烃单体碳同位素分析的要求。     

用于单体氢同位素分析的混合溶剂洗脱5分子筛吸附正构烷烃的方法

混合溶剂萃取洗脱5分子筛吸附正构烷烃的方法在单体碳同位素分析研究中已得到了应用。由于5分子筛在长时间加热条件下可能对有机分子的氢交换反应具有一定的催化作用,因此对于该方法能否用于正构烷烃的单体氢同位素分析需要做进一步研究。本文以两种不同类型原油的饱和烃和正构烷烃混合标准样品为对象,采用环己烷-正戊烷溶剂和氢氟酸溶解-正戊烷溶剂洗脱5分子筛吸附的正构烷烃,对比分析两种萃取方式的分离效果,并分别测定了正构烷烃的单体氢同位素比值。结果表明:两种萃取方式都得到了纯化效果良好的正构烷烃组分,氢同位素测定结果的差值总体上小于4‰,在仪器分析误差范围内。经过三次环己烷-正戊烷洗脱方式获得正构烷烃回收率平均值为58%,氢氟酸溶解-正戊烷洗脱方式经过多次萃取操作获得正构烷烃回收率平均值为68%。尽管环己烷-正戊烷洗脱方式提取正构烷烃的效率较低,并且涉及在分子筛条件下多次较长时间的加热过程,但这两个因素没有导致氢同位素发生明显的分馏或交换过程,适合用于正构烷烃分离、纯化以及单体氢同位素测定。     

尿素络合法分离-气相色谱/同位素质谱法分析土壤和植物中低含量(ppm级)正构烷烃的碳同位素

尿素络合法和5A分子筛法是常用的分离富集环境样品中正构烷烃的方法,但由于复杂的处理流程对于低含量正构烷烃的回收率普遍较低。本文通过优化尿素络合法分离富集正构烷烃的实验条件,建立了尿素络合法分离-气相色谱/同位素质谱分析土壤和植物中低含量正构烷烃单体碳同位素的方法。即采用正己烷-丙酮溶解样品,在4℃冰箱中与2 m L尿素-甲醇饱和溶液反应48 h;用去离子水溶解尿素络合物,加入正己烷后分离出有机相和水相,分别用正己烷、丙酮-正己烷萃取有机相和水相中的正构烷烃。中长链正构烷烃的回收率达79%~104%,高于5A分子筛法和已有尿素络合法的富集效果;单体碳同位素的分析精度为0.09‰~0.63‰(1σ)。利用改进的方法分析实际样品,大幅降低了未分峰和共流出物的干扰,提高了实际样品中ppm级中长链正构烷烃的回收率。     

土壤中多环芳烃单体碳同位素分析的分离净化方法研究

应用单体碳同位素组成追溯多环芳烃（PAHs）类污染物的来源越来越受关注。单体同位素分析中,利用样品预处理减少共流出和未分峰（UCM）,是实现同位素比值准确分析的重要前提。已有分离净化研究较少关注环数小于3的PAHs;或需联合使用高效液相色谱（HPLC）技术,但对实验室条件要求较高。本文期望避免使用HPLC技术,仅通过简单的固相萃取法,实现16种PAHs的分离净化,满足包括低环数在内的PAHs单体碳同位素分析的要求。实验对比了氨基和硅胶两种填料的固相萃取（SPE）小柱,以及正戊烷等10种淋洗溶剂对PAHs的分离净化富集效果。结果表明：氨基小柱中有20%以上的萘和苊不能与烷烃和未分峰完全分离,硅胶SPE小柱除杂效果和分离效果优于氨基小柱。选择1000mg/6mL硅胶SPE小柱,利用6mL正戊烷淋洗UCM和烷烃,5mL正戊烷-二氯甲烷（70：30,V/V）洗脱PAHs。利用气相色谱（GC）对分离净化效果进行初步检验,气体同位素质谱（GC-IRMS）进行单体碳同位素分析。16种PAHs的回收率为79%~128%,相对标准偏差为2%~13%（1σ,n=6）,单体碳同位素比值（δ¹³C）分析精度为0.1‰~0.75‰,大幅降低了其中UCM和共流出对PAH单体碳同位素分析的干扰,尤其减少了对低环数PAHs单体碳同位素分析的影响,而且净化过程没有造成PAHs单体碳同位素分馏,满足PAHs单体碳同位素分析的要求。     

饱和烃经5à分子筛络合前后单体烃碳同位素分析对比研究

通过对自配标准样品(正构烷烃)进行5à分子筛吸附试验,测定了用5分子筛吸附法分离前后正构烷烃、异构烷烃和环烷烃碳同位素值,探讨试验前后碳同位素值的变化。尽管实验过程中样品经过85℃长时间加热回流及吸附样品的5à分子筛用氢氟酸酸化处理,但实验结果经仪器检测,证明该方法对正构烷烃碳同位素值影响因素不大。本文还介绍了原油和煤可溶有机质中饱和烃络合前后的单体烃碳同位素分析方法。并在前人工作的基础上,改进采用微型索氏抽提加热回流实验装置,既提高了样品的回收率,也减少了样品中轻组分的损失。     

饱和烃经5分子筛络合前后单体烃碳同位素分析对比研究

通过对自配标准样品(正构烷烃)进行5分子筛吸附试验,测定了用5分子筛吸附法分离前后正构烷烃、异构烷烃和环烷烃碳同位素值,探讨试验前后碳同位素值的变化。尽管实验过程中样品经过85℃长时间加热回流及吸附样品的5分子筛用氢氟酸酸化处理,但实验结果经仪器检测,证明该方法对正构烷烃碳同位素值影响因素不大。本文还介绍了原油和煤可溶有机质中饱和烃络合前后的单体烃碳同位素分析方法。并在前人工作的基础上,改进采用微型索氏抽提加热回流实验装置,既提高了样品的回收率,也减少了样品中轻组分的损失。     

柴达木盆地原油单体正构烷烃碳同位素研究

利用GC—C—MS技术测定柴达木盆地原油单体正构烷烃碳同位素组成，研究它们的碳同位素组成特征和分布型式，以探究原油的戍因。测试结果表明：柴迭木盆地西部原油的单体正构烷烃碳同位素组成较重，分布在-23．7‰、～-28．5‰之间，分子碳同位素分布曲线呈波浪式，反映原油来自超咸水—咸水的盐湖相沉积环境。柴达木盆地北部原油的单体正构烷烃碳同位素组成为-25．3‰、～-33．4‰，分子碳同位素分布曲线呈U型和波浪式两种型式，根据单体正构烷烃的碳同位素组成和分布型式特征，认为柴迭木盆地北部原油属于煤成油和湖相偏腐泥型、混合型母质成因。     

水中氯代烃单体碳同位素分析中预富集方法进展

高精度准确测定氯代烃单体碳同位素对示踪污染物来源,了解污染物的生物降解过程具有重要意义。在环境转化过程中,有机污染物的同位素组成可能是稳定不变的,也有可能发生改变。若污染物的同位素组成在迁移转化过程中不变,根据其同位素组成可以示踪污染物的来源;若同位素组成变化,根据同位素分馏结果,可以评价环境中有机污染物降解发生的可能性和程度。本文综述了固相微萃取、静态顶空进样、吹扫-捕集、多级串联技术等前处理方法与气相色谱-燃烧-同位素比值质谱仪(GC-C-IRMS)联用分析水中氯代烃单体碳同位素的研究进展,比较了分析方法的优缺点。液-液萃取较少用于水中氯代烃的单体同位素分析。静态顶空进样、固相微萃取、吹扫-捕集都是无溶剂富集技术,与GC-C-IRMS联用分析水中氯代烃单体同位素过程中不存在或存在小且恒定的可校正的同位素分馏,分析精度一般优于1‰,没有二次污染,降低了杂质干扰,提高了GC-C-IRMS的分辨率和分析精度,降低了检测限。从静态顶空进样、固相微萃取、吹扫-捕集,到多级串联等技术与GC-C-IRMS联用分析水中氯代烃单体同位素比值,检测限逐渐降低。目前,吹扫-捕集-GC-C-IRMS在分析水中氯代烃中应用最广泛,重现性好、检测限低。针内微萃取、管内微萃取、搅动棒吸附萃取和顶空进样吸附萃取等前处理方法与GC-C-IRMS仪联用具有一定的应用前景。     

青海湖地区生物中正构烷烃及其氢同位素组成与影响因素

青海湖是我国最大的内陆咸水湖泊。本文应用GC-MS和GC-TC-IRMS同位素分析技术,对青海湖水生生物和周围地区陆生生物中正构烷烃及其氢同位素进行了分析,研究了生物中正构烷烃及其同位素组成。结果显示了不同生物中正构烷烃碳数分布范围在C1 5~C33之间,呈单峰型分布;主峰碳数是水生生物(除海韭菜外)相对较低,主要为C23和C25,陆生木本植物次之,为C27;陆生草本植物较高,为C27和C29;CPI值分布在4.0~29.7之间;ACL值为26.0~29.6,分布与植物类型有关。青海湖水生生物中正构烷烃氢同位素组成分布在-209.8‰~-85.6‰之间,平均值为-169.2‰~-121.2‰;陆生植物的正构烷烃δD值为-196.7‰~-84.3‰之间,平均值为-173.0‰~-108.6‰。青海湖不同水生生物和不同陆生生物之间的正构烷烃氢同位素组成差别显著。研究发现,湖泊的含盐量对水生植物的正构烷烃氢同位素具有显著影响,环境湿度和降水量明显影响了陆生植物的正构烷烃氢同位素组成;植物的正构烷烃平均氢同位素组成随着其ACL值增加,具有变轻的趋势;不同种类植物的正构烷烃合成期间具有不同的氢同位素分馏效应,与陆生植物相比较,水生植物的正构烷烃相对于环境水更富集轻氢同位素,并且随着ACL值增加,环境水和正构烷烃之间的氢同位素分馏增大。     

辽河油田生物降解原油沥青质热解产物中单体化合物碳同位素组成

生物降解原同在我国分布广泛并且在重油资源中占有一定的比例。本文通过采用单体化合物碳同位素分析技术对取自辽河油田西部凹陷的重油以及它们沥青质组分的热解产物进行单体碳同位素测定,来研究原油沥青质热解产物中正构烷烃单体碳同位素的组成及其一物降解油的指示意义。研究结果表明,沥青质热解产物中正构烷烃组分的单体碳同位素组成可用于生物降解较严重的重油样品进行油／油相比,并且与原油中的正构烷烃单体碳同位素组成的对     

Breakage assessment through cluster analysis of joint set orientations of exposed benches of opencast mines

Summary This paper substantiates, through three different case studies, that the breakage assessment of opencast bench blasting can be made scientifically through the analysis of joint set orientations of different exposed benches in association with the corresponding face direction. Joint orientations, dip and strike of bedding planes have a significant influence on rock breakage. They can have decelerating effects on blasting performance, which may be rectified by geological mapping, and subsequently modifying the blast design parameters.     

Reconstructing the migration patterns of late Pleistocene mammals from northern Florida, USA

We used analyses of the strontium isotope (⁸⁷Sr/⁸⁶Sr) ratios of tooth enamel to reconstruct the migration patterns of fossil mammals collected along the Aucilla River in northern Florida. Specimens date to the late-glacial period and before the last glacial maximum (pre-LGM). Deer and tapir displayed low ⁸⁷Sr/⁸⁶Sr ratios that were similar to the ratios of Florida environments, which suggest that these taxa did not migrate long distance outside of the Florida region. Mastodons, mammoths, and equids all displayed a wide range of ⁸⁷Sr/⁸⁶Sr ratios. Some individuals in each taxon displayed low ⁸⁷Sr/⁸⁶Sr ratios that suggest they ranged locally, while other animals had high ⁸⁷Sr/⁸⁶Sr ratios that suggest they migrated long distances (> 150 km) outside of the Florida region. Mastodons were the only taxa from this region that provided enough well-dated specimens to compare changes in migration patterns over time. Pre-LGM mastodons displayed significantly lower ⁸⁷Sr/⁸⁶Sr ratios than late-glacial mastodons, which suggests that late-glacial mastodons from Florida migrated longer distances than their earlier counterparts. This change in movement patterns reflects temporal changes in regional vegetation patterns.     

Palaeobotany of Gondwana basins of Orissa State, India: A bird's eye view

Gondwana basins of Orissa State constitute a major part of the Mahanadi Master Basin. These Gondwana sediments, ranging from Asselian to Albian in age, contain remnants of three basic floral assemblages i.e. Glossopteris Assemblage, Dicroidium Assemblage and Ptilophyllum Assemblage which can be recognized through the Permian, Triassic and Early Cretaceous, respectively. The megafloral assemblages of different basins of this state are discussed briefly. This report mainly deals with the plant species diversification in different lithological formations and the development of flora in the Gondwana basins of Orissa. A number of successive megafloras are recognized. Among those, leaves are the dominant part of the preserved flora, followed by fruits and roots. No wood parts are preserved in the major basins. These pre-angiospermic floras have been systematically analyzed to depict the evolutionary trends, and palaeofloristics of these basins. The distribution of plant fossils in different formations of these basins depicts provincialism in Gondwana flora within the Orissa.     

Palaeoecology and taxonomy of Pentoxylales from the Albian of Antarctica

Reproductive pentoxylalean material from the Albian Triton Point Formation, Fossil Bluff Group of Alexander Island, Antarctica is the youngest record of this group globally. Leaves are referred to Taeniopteris daintreei McCoy, ovulate reproductive organs to Carnoconites cranwelli Harris, and stem material to Pentoxylon sp. Occurring in leaf litter layers on palaeosol surfaces the sedimentology suggests that pentoxylalean plants grew upon areas of the floodplain distal to the river channel, where they covered the forest floor in a similar habit to modern brambles. The forest floor was shared with Equisetales and liverworts, an abundance of ferns [Cladophlebis Brongniart, Gleichenites Goeppert, Phyllopteroides Medwell, Sphenopteris (Brongniart) Sternberg], as well as angiosperms. Bennettitales, Ginkgoites Seward and Nilssonia Brongniart were rare within these communities, as were coniferous trees.     

Occurrence of Cordaitales from lower Gondwana sediments of Ib-River Coalfield, Orissa, India: An Indian scenario

The Ib-River Coalfield in Orissa State is a part of Mahanadi Master Basin. Recent extensive investigations were conducted in this Coalfield to locate fossiliferous beds in the Lower Gondwana deposits and as a result a large cache of plant fossils were recovered from Lower Permian sediments (Barakar Formation) exposed in Jurabaga and Lajkura Collieries. The complete flora includes 23 genera representing nine orders viz., Lycopodiales, Equisetales, Sphenophyllales, Filicales, Cordaitales, Coniferales, Ginkgoales, Cycadales and Glossopteridales. Only the Cordaitales, represented by four genera i.e., Noeggerathiopsis, Cordaites, Euryphyllum and Kawizophyllum are discussed in this paper. Cordaitalean leaves are described for the first time from this coalfield; the remaining plant groups will be considered in a subsequent publication. Cordaitalean leaves attributable to Noeggerathiopsis hislopii, Noeggerathiopsis minor, Euryphyllum whittianum, Euryphyllum maithyi, Kawizophyllum dunpathriensis and Cordaites sp. constitute about 13.90% (111 specimens) of the total plant assemblage collected from this Coalfield. Of the cordaitaleans, N. hislopii is most abundant (47.75%; 53 specimens) followed by E. whittianum (40.54%; 45 specimens). A summary of the distribution of Cordaitales throughout the Indian Gondwana is also presented. Floristic composition varies stratigraphically at the two Barakar exposures (Lajkura and Jurabaga Collieries). Cordaitales are preserved only in the lowermost (4th) horizon (lower floral zone). Strata in these collieries have been assigned to the lower and upper Barakar Formation based on floristic content and an Early Permian (Artinskian) age is assigned.     

吉林省大布苏国家重点化石产地的猛犸象-披毛犀动物群

猛犸象-披毛犀动物群是晚更新世时期北半球最具代表性的典型哺乳动物群,该动物群的化石在中国东北地区广泛分布,其演化、发展乃至灭绝与古人类文明的发展有密切的关系。综述猛犸象-披毛犀动物群的概况,从动物组合、古地理分布、古生态环境等方面介绍了该生物群之全貌。以吉林省大布苏国家重点化石产地为例,对该产地出土的猛犸象-披毛犀动物群化石标本进行了最新的统计(分属6目13科21属23种),对其化石组合特征进行了分析,并对在东北地区深入开展该动物群研究的意义进行了探讨。     

A history of the ‘Zambian copper flower'', Becium centraliafricanum (B. homblei)

This contribution is a short history of the Zambian copper flower, Becium homblei (recently renamed B. centraliafricanum that has attracted attention as a plant associated with Cu-rich soils. It has a peculiar discontinuous distribution in Central Africa which has been explained in terms of biotype depletion. A field investigation into the ecology of the species shows that it is able to tolerate soil Cu concentrations of up to 15,000 μg/g (ppm), and soil nickel concentrations of nearly 5000 μg/g. B. homblei is also found on areas where soil metals are in trace quantities, and where soil bases, particularly Ca, are low. In spite of its tolerance to a wide range of edaphic conditions, the distribution of the species is very restricted in Zimbabwe, and this is almost certainly due to severe interspecific competition with a closely related species, B. obovatum, which is common on soils not unusually enriched in heavy metals. Pioneering work on geobotanical prospecting by use of Becium homblei was carried out by the late G. Woodward and others in the 1950s and 1960s. This species was used successfully for geobotanical prospecting for Cu. This present report is a brief history of these pioneering studies     

The oldest barnacle from the Caribbean is a rudist bivalve (Maastrichtian, Jamaica)

Four new specimens of Euscalpellum? coatesi Donovan and Davis-Strickland from the Maastrichtian of Jamaica are described; two of these occur in association with the right valve of the rudistid bivalve Chiapasella radiolitiformis (Trechmann). This demonstrates that E.? coatesi is not a barnacle, but rather represents an unusual preservational state of the left valve of C. radiolitiformis retaining only the cellular inner part of the shell.     

滇中川街盆地中侏罗世弓鲛(软骨鱼类)化石新材料

云南禄丰县川街盆地中侏罗统产出弓鲛鱼类化石后甸弓鲛(Hybodus houtienensis Young)、新庄弓鲛(新种)(Hybodus xinzhuangensis Sun)、川街弓鲛(新种)(Hybodus chuanjieensis Sun)。后甸弓鲛(Hybodus houtienensis Young)是中国发现最早的弓鲛鱼类之一,正型标本为破碎的鳍棘,副型标本为一枚牙齿齿冠。依据在川街盆地相同层位发现的新化石材料,对后甸弓鲛副型标本进行了增补,补充了描述,建立了2个弓鲛新种:新庄弓鲛与川街弓鲛,丰富了"后甸弓鲛带"弓鲛类群,并讨论了弓鲛属的生物地层、生活的古环境和地理分布特征。