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。     

柱色谱分离-分子筛络合洗脱过程中正构烷烃单体碳同位素分馏研究

应用气相色谱-气体同位素质谱(GC-C-IRMS)分析正构烷烃单体碳同位素之前,需要对饱和烃样品中正构烷烃和异构烷烃进行预分离、富集,在预分离和富集过程中正构烷烃单体碳同位素是否发生分馏是高精度分析正构烷烃单体碳同位素比值(δ~(13)C)的关键。本文以正构烷烃混合溶液为对象,利用柱色谱、5■分子筛络合、环己烷-正戊烷混合溶剂两次洗脱,GC-C-IRMS分析正构烷烃单体碳同位素,研究前处理过程中正构烷烃单体碳同位素是否发生分馏。结果表明:使用柱色谱分离前后,多数正构烷烃单体碳同位素比值相差-0.2‰～0.2‰;当5■分子筛不完全络合时,未络合的正构烷烃单体碳同位素比值偏重约0.7‰,可能发生了微弱的碳同位素分馏,但并未影响洗脱后的正构烷烃单体碳同位素比值;使用环己烷-正戊烷混合溶剂洗脱前后,碳同位素比值相差-0.2‰～0.5‰,以同样方式洗脱第二次,获得的正构烷烃单体碳同位素比值与模拟样品相差-0.3‰～0.2‰。分析不同回收率(20%)正构烷烃的单体碳同位素比值,处理前后的差值基本在0.3‰以内,可见当正构烷烃回收率低至20%左右时,其单体碳同位素仍未发生明显分馏。柱色谱分离-5■分子筛络合-混合溶剂洗脱方法适用于回收率大于20%的正构烷烃单体碳同位素分析。     

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。     

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。     

低纬度淡水湖沉积物中正构烷烃氢同位素组成特征及其有机质源和环境指示意义

为认识低纬度亚热带地区湖泊沉积物中正构烷烃氢同位素组成特征及其与母源输入和生态环境的关系,本文利用气相色谱-高温热转变-同位素比值质谱议(GC-TC-IRMS),对系统采集的抚仙湖沉积物样品中正构烷烃氢同位素进行了测定。抚仙湖沉积正构烷烃δD值分布在-219.3‰~-142.5‰之间,样品中平均值为-208.1‰~-154.5‰,并且奇碳数正构烷烃δD值明显地将样品划分为两种类型。类型Ⅰ样品中正构烷烃平均δD值明显地高于类型Ⅱ样品,反映了它们生物源存在明显差别。沉积物与水生植物和陆生植物中正构烷烃氢同位素组成对比结果指示了沉积C_(17)、C_(21)~C_(25)奇碳数正构烷烃来自水生植物,C_(27)和C_(29)奇碳数正构烷烃主要来自木本植物,C31和C33正构烷烃来自水生和陆生草本植物的混合。对比研究结果表明,湖泊地区生态环境是控制湖泊沉积正构烷烃氢同位素组成的重要因素之一,在利用沉积正构烷烃氢同位素研究古水文学特征时,还要考虑研究区古生态环境对沉积正构烷烃氢同位素的影响,并且结合沉积正构烷烃ACL值和Qw值,才能对沉积有机质中正构烷烃氢同位素组成及变化作出合理的解释。     

柴达木盆地北缘原油中单体正构烷烃的碳、氢同位素组成研究

以柴达木盆地北缘不同构造带代表性原油作为研究对象,采用GC-TC-IRMS技术对原油中正构烷烃单体碳、氢同位素进行测定。利用样品正构烷烃单体碳、氢同位素组成特征及分布模式,进行原油成因类型划分和对比分析。研究结果表明,正构烷烃可溶有机质的δ13C分布在-36‰～-25‰,δD分布在-180‰～-110‰。对比发现,不同构造带原油中正构烷烃单体碳、氢同位素组成特征上存在着比较明显的差别。以-30‰（δ13C）和 -140‰（δD）作为分界,结合同位素曲线的分布型式,可以划分为不同的分布模式判识生烃母质和沉积环境。     

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。     

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。     

松辽盆地南部上白垩统烃源岩和原油中正构烷烃的氢同位素组成研究

以松辽盆地南部上白垩统的烃源岩及原油为研究对象,对烃源岩抽提物和原油中正构烷烃的单体氢同位素组成进行了测定。生物标志化合物和正构烷烃的碳氢同位素组成特征表明,在未成熟—成熟阶段正构烷烃的单体氢同位素组成受热成熟度的影响不明显,可以作为油源对比的一个有用的辅助指标。氢同位素组成在母源判识以及重建古沉积环境方面可以提供更多的信息,与碳同位素组成结合应用具有一定的优势。     

青藏高原东北部尕海湖沉积物中正构烷烃及其氢同位素组成与有机质源指示意义

系统采集了位于青藏高原东北部的尕海湖淡水湖泊沉积物,对沉积物中正构烷烃及其氢同位素进行了分析,研究了沉积物中正构烷烃及其氢同位素组成,探讨了它们的来源。研究结果表明,尕海湖沉积物中正构烷烃分布反映了它们来自水生和陆生植物。尕海湖沉积正构烷烃氢同位素组成平均值为-221.9‰~-190.5‰。C_(21)~C_(33)奇碳数正构烷烃δD值明显地将样品划分为两种类型。类型Ⅰ样品的C_(21)~C_(33)奇碳数正构烷烃平均δD值明显地高于类型Ⅱ样品。类型Ⅰ沉积正构烷烃δD值分布特征反映了它们主要来自尕海湖水生植物;类型Ⅱ沉积物中正构烷烃δD值特征指示了它们主要来自研究区陆生草本植物。提出了具有δD值低、丰度高和CPI值低的中等链长正构烷烃起源于改造陆源草本植物的细菌。研究成果证实了沉积正构烷烃δD值可以作为指示有机质源的地球化学指标。     

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.     

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。     

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     

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。