表层岩溶带土壤中多环芳烃分布特征及来源解析

利用气相色谱-质谱联用仪(GC-MS)对表层岩溶泉域土壤中的16种优控的多环芳烃(Polycyclic Aromatic Hydrocarbons, PAHs)含量进行了分析,并对其组成、污染水平和来源进行了探讨。结果表明,16种优控PAHs在表层岩溶泉域土壤中的检出率为100%,其含量介于439.19~3329.72ng/g之间,平均值为1392.44ng/g,7种致癌性PAHs占总量的26%。PAHs的组成特征受地形的控制,随着海拔升高,低环PAHs所占比例升高,高环PAHs比例降低。同分异构体比值分析表明,研究区土壤中的PAHs主要来自于煤、生物质和石油的燃烧排放。研究区土壤中16种PAHs的TEQcarc值介于18.65~501.13ng/g,平均值为140.57ng/g。7种致癌性PAHs占总TEQcarc的比例达到96.8%。研究区表土中,后沟泉域的污染程度最大,次之是兰花沟泉域和柏树湾泉域,水房泉泉域的污染程度最小,但由于柏树湾泉域松针落叶中BaP、PAHs含量较高,松针落叶中PAHs含量分别高达36.36ng/g和2370.1ng/g,土壤生态风险评价中应考虑松针落叶层的潜在影响。      

Petroleum inclusions and residual oils: constraints for deciphering petroleum migration

The analysis of petroleum inclusions (PI) in parallel to residual oils (=bitumens) provided specific constraints for petroleum migration processes in the Prague Basin. Whereas organic geochemical information from bitumens is limited due to alteration, additional high quality information was obtained from C_1–14-range compounds inside crystals. This was obtained by the application of a closed system for the decrepitation and thermal extraction of PI with subsequent gas chromatography (GC) and gas chromatography–mass spectrometry (GC–MS). The resulting data not only show pristine live oils, gases, residual and precipitated bitumens and a broad variation of mixtures of the groups above, but also show that gas migration and fractionation processes played a major role in the Prague Basin.     

Historical records and the sources of polycyclic aromatic hydrocarbons in the East China Sea

The coastal cities are the most advanced regions in China. In the past few decades, the environment changed very significantly due to large scale human activities in the coastal regions. Polycyclic aromatic hydrocarbons (PAHs) in three dated sediment cores from the west coast of the Yellow Sea (core A01), the Yangtze River estuary (YRE; core A02) and the Oujiang River estuary (ORE; core A03) were analyzed to reconstruct the environmental evolutionary process of the east China coastal region over the past century. In the three cores, PAHs concentrations were increased rapidly. Lower concentrations of PAHs were measured in core A02 than in cores A01 and A03. The vertical variation of PAHs in the YRE was dominated by the petrogenic sources. Historical records of PAHs in the ORE were controlled by pyrolytic sources. PAHs on the west coast of the Yellow Sea were contributed by the two sources.     

柴达木盆地北缘中侏罗统石门沟组煤中多环芳烃分布特征及其地质意义

多环芳烃(PAHs)是古环境、古野火以及古气候的重要地质记录,本文通过气相色谱质谱法(GC- MS)研究了柴达木盆地北缘中侏罗统石门沟组煤中多环芳烃分布特征,检测出一系列二环至七环芳烃化合物,包括高等植物衍生多环芳烃(卡达烯、6- 异丙基- 1- 异己基- 2- 甲基萘、惹烯、西蒙内利烯以及二氢惹烯)和燃烧衍生多环芳烃(荧蒽、芘、苯并[a]蒽、、苯并荧蒽、苯并[e]芘、苯并[a]芘、茚并[cd]芘、苯并[ghi]苝和晕苯)等。这些多环芳烃的检出表明石门沟组煤沉积于具有显著陆源高等植物输入的微咸水湖沼环境,成熟度较低(平均随机反射率为056%)。石门沟组煤中高等植物衍生多环芳烃以极高的惹烯含量为特征,且存在较高丰度的西蒙内利烯和二氢惹烯,卡达烯丰度极低,反映出成煤期陆地植被类型以松柏类植物的针叶林为主,气候温暖湿润。同时,煤中丰富的燃烧衍生多环芳烃证实了柴达木盆地北缘中侏罗世存在广泛的陆地古野火,较高的大气氧气浓度(256%)可能是该时期野火频发的一个重要诱因。本次研究为柴达木盆地中侏罗世古野火事件的研究提供了重要的分子化石证据,也是对中侏罗世古环境和古气候研究的有益补充。     

HPLC fractionation and GC-MS determination of aromatic hydrocarbons from oils and sediments

Normal-phase HPLC using a cyano/amino bonded silica stationary phase can provide reliable and rapid fractionation of total neutral fractions from oils and sediments. Separation of aliphatic from aromatic hydrocarbons is possible, but in addition HPLC is able to fractionate aromatic hydrocarbons according to their number of double bonds.Applications of the HPLC fractionation in organic geochemistry are described and illustrated by GC-FID and GC-MS data from an oil and a recent sediment exhibiting a high degree of petrogenic contamination. Alkylphenanthrenes can be obtained free of alkyldibenzothiophenes, allowing evaluation of the methylphenanthrene index by GC-FID without the need for quantification of co-eluting sulphur compounds by GC-FPD.The choice of capillary GC stationary is also considered, particularly with regard to resolution of aromatic steroidal hydrocarbons and alkylphenanthrenes.     

Ultrasonic wave extraction and simultaneous analysis of polycyclic aromatic hydrocarbons (PAHs) and phthalic esters in soil

A method is developed for detection of polycyclic aromatic hydrocarbons(PAHs) and Phthalic Acid Esters(PAEs) in soil samples. Ultrasonic Wave Extraction under airtight circumstances is adopted to extract the analytes in soil samples with n-hexane–acetone(V:V=1:1) as extraction solvent. This method has several advantages, including high extraction efficiency, short time, convenience and simplicity. It can be used to detect polycyclic aromatic hydrocarbons(PAHs) and Phthalic Acid Esters(PAEs) in soil.     

Vertical transport of polycyclic aromatic hydrocarbons in different particle-size fractions of sandy soils

Vertical transport of selected polycyclic aromatic hydrocarbons (PAHs) in different particle-size fractions of sandy soils was investigated by simulation experiments in soil columns. Tested soil samples were fractionized into three particle-sizes including sand, coarse silt and fine silt (2,000–50, 50–20 and <20 μm). Rainfall simulations were conducted in artificially PAHs contaminated soil columns with 30 cm length and 5 cm diameter in 40 days. PAHs were extracted from soil samples and determined by high performance liquid chromatography (HPLC). Results showed that the residue level of PAHs in fine silt fraction reached 35.85 mg/kg, which was significantly higher than those in sand and coarse silt fraction (16.28 and 11.80 mg/kg, respectively), probably because PAHs in macroporous fractions were prone to volatilize or degrade compared with that in microporous fractions. Linear relationship between the residue levels of individual PAH (R _PAHs) and the value of partition coefficient (log K _oc) was regressed as R _PAHs = 1.55 × log K _oc − 5.86, R ² = 0.91, n = 9. These results indicated that vertical transport of the mixed PAHs in soils were controlled both by the nature of PAHs (i.e. log K _oc, molecular weight), soil particle size and soil organic contents, which could influence the transport of PAHs.     

南岭山地湖泊多环芳烃的大气沉降历史记录

高大山脉对大气环流具有阻挡或屏障作用.通过分析测定南岭山地湖泊沉积物中多环芳烃(PAHs)的垂直分布,结合210Pb定年,探讨了大气PAHs污染在南岭山地的沉积历史.结果显示,沉积物中的PAHs主要以低环数化合物为主,其中尤以菲的含量为最高.在剖面深度0～28 cm范围内,总多环芳烃的含量范围为86～778 ng/g.自1970年开始,PAHs含量持续增加,其中20世纪80、90年代中后期PAHs含量略有降低;在2000年后,沉积柱中的PAHs含量呈急剧增加之势态.多环芳烃在大气迁移过程中发生了组成分异,沉积物中相对富集轻组分(低环数)PAHs,与颗粒物结合的大气干湿沉降是PAHs向偏远山地积的主要途径.     

New aromatic biomarkers and possible maturity indicators found in New Albany Shale extracts

Aromatic hydrocarbons from benzene extracts of New Albany Shale were characterized. A biomarker that has a molecular weight of 546 and a structural configuration consistent with that of an alkyl-aromatic hydrocarbon (C₄₀H₆₆) was tentatively identified. It was found that the relative concentrations of the biomarker are indicative of differing levels of thermal maturity of the shale organic matter. A 40-carbon bicyclic carotenoid (C₄₀H₄₈) is proposed as the geochemical precursor of this biomarker. Thermal maturity of the shale organic matter can also be differentiated by observing differences in “fingerprints” as obtained by field-ionization mass spectrometry on the aromatic hydrocarbon fraction. Using this technique, we found that the more mature shale samples from southeastern Illinois contain more low molecular weight extractable aromatic hydrocarbons and the less mature shale samples from northwestern Illinois contain more high molecular weight extractable aromatic hydrocarbons. It was demonstrated that field-ionization and tandem mass spectrometric techniques through fingerprint and individual compound identification, are useful for shale aromatic hydrocarbon fraction characterization and for thermal maturation interpretation.     

东海泥质区表层沉积物中多环芳烃的分布特征及物源

以 GC/MSD内标法定量测定了东海近岸和远岸泥质沉积区 18个表层沉积物中多环芳烃 (PAHs)的含量,探讨了多环芳烃在这些泥质区的分布特征、影响因素及来源.结果显示 ,近岸泥质区多环芳烃含量普遍较高,介于 180.3～ 424.8 ng/g(干重 )之间;冲绳海槽次之,含量为 211.7 ng/g ;济州岛西南泥质区最低,含量介于 117.1～ 211.7 ng/g之间.东海泥质区多环芳烃的分布主要受控于离物源的远近、沉积物粒度、有机碳含量以及东海环流体系.东海泥质区的多环芳烃主要来源于热成因,大气干湿沉降和河流输入是其进入泥质区的主要途径.东海泥质区多环芳烃的污染程度中等.     

Hydrous pyrolysis of sediments: Composition and proportions of aromatic hydrocarbons in pyrolysates

Hydrous pyrolysis (closed vessel autoclaving in the presence of excess water) of organic-rich rocks is said to generate oils which closely resemble natural crude oils in their broad characteristics and composition. However there are only a few accounts of the proportions and compositions of hydrocarbons in hydrous pyrolysates and none of these discuss the aromatic hydrocarbon composition in detail. The present paper presents some data on the latter.Hydrous pyrolysis (3 days) of a dolomitic siltstone (Permian, Marl Slate) at 280, 300,320, 340 and 360°C produced significant amounts of oils in which the aromatic hydrocarbons were one and a half to two times as abundant as the saturated hydrocarbons.The overall composition of the aromatic hydrocarbons was similar to most crude oils; the major components isolated by our methods from natural oils and from pyrolysates were C_1–4 alkylnaphthalenes. At the lowest pyrolysis temperature (280°C) the distributions of the more minor components of the pyrolysates (e.g. alkylphenanthrenes, aromatic steroids) were also generally similar to those found in natural crudes. However, a number of components (e.g. methylanthracenes, Diels' hydrocarbon) which are not usually reported in crudes, were also detected and the relative proportions of these increased at the higher temperatures. Hydrous pyrolysis (340°C) of an organic-rich oil shale (Jurassic, Kimmeridge) and an asphaltic-material containing no minerals produced pyrolysates in which many of these unusual compounds were also present. In addition the pyrolysate of the oil-shale contained higher proportions of organic sulphur compounds. It appears that the formation of the unusual compounds is not simply a function of the type of organic matter or mineralogy but rather of the high temperatures or fast heating rates employed.     

民用煤室内燃烧条件下多环芳烃的排放特征

民用燃煤是我国最大的室外和室内空气污染源.为了研究不同煤种在民用燃烧条件下多环芳烃(PAH)的排放特征,对5种成熟度不同的煤种(4种烟煤和1种无烟煤)以蜂窝煤形式燃烧产生的烟气进行采集,对其中24种PAHs进行定量分析,并与原煤的二氯甲烷(DCM)抽提物进行对比.结果表明,不同煤种的PAH排放因子差别显著,无烟煤的排放因子比烟煤低3个数量级,24种PAHs总和仅为184 μg/kg,烟煤则为136～408 mg/kg;原煤PAH抽提率的情况与之相似,无烟煤为4 mg/kg,烟煤为96～156 mg/kg.各种类型PAH(母体PAH、甲基PAH和含O/S-PAH)所占比例在不同煤种之间存在差异,但在烟气中和原煤抽提物的情况一致,说明民用燃煤前后PAH具有一定的继承性.通过4组毒性当量参数的比较,发现无烟煤燃烧烟气中的PAH毒性当量比原煤抽提物明显减少,而烟煤则表现为不同程度的增加.     

Re-Examination of the Oil and Gas Origins in the Kekeya Gas Condensate Field, Northwest China–A Case Study of Hydrocarbon-Source Correlation Using Sophisticated Geochemical Methods

This work discussed the origins, alteration and accumulation processes of the oil and gas in the Kekeya gas condensate field based on molecular compositions, stable carbon isotopes, light hydrocarbons, diamondoid hydrocarbons and biomarker fingerprints. A comparison study is also made between the geochemical characteristics of the Kekeya hydrocarbons and typical marine and terrigenous hydrocarbons of the Tarim Basin. Natural gas from the Kekeya gas condensate field is derived from Middle–Lower Jurassic coal measures while the condensates are derived from Carboniferous–Permian marine source rocks with a higher maturity. In the study area, both natural gas and condensates have experienced severe water washing. A large amount of methane was dissolved into the water, resulting in a decrease in the dryness coefficient. Water washing also makes the carbon isotopic compositions of the natural gas more negative and partially reverse. Considering that the gas maturities are higher than once expected, gas generation intensity in the study area should be much stronger and the gas related to the Jurassic coal measures could promise a greater prospecting potential. As a result of evaporative fractionation, the Kekeya condensates are enriched in saturates and lack aromatics. Evaporative fractionation disguises the original terrigenous characteristics of the light hydrocarbons associated with the natural gas, making it appear marinesourced. Thus, alteration processes should be fully taken into consideration when gas–source correlations are carried out based on light hydrocarbons. With the condensates discovered in the study area all being "migration phase", the pre-salt Cretaceous and Jurassic reservoirs may promise great exploration potential for the "residual phase" hydrocarbons. This research not only is of significance for oil and gas exploration in the southwest Tarim Basin, but also sheds light on the oil/gas-source correlations in general.     

珠江广州河段重污染沉积物中多环芳烃赋存状态初步研究

对珠江广州河段重污染沉积物进行粒度分级 (>500 μm、500～ 220 μm、220～ 63 μm、63～ 22 μm和 < 22 μm),每个粒级的样品进行重液分离,收集轻组分 (有机质 )和重组分 (主要为无机矿物及无定型有机质 ).在显微镜下对沉积物中不同粒径轻重组分的吸附剂进行鉴定,对其中的多环芳烃进行定量分析,结果表明,白鹅潭样品中有机质占总质量的 9.10%,富集了 81.55%的多环芳烃,无机矿物和无定型有机质占 90.92%,富集了 18.45%的多环芳烃;黄埔样品中有机质占总质量的 8.95%,富集了 56.50%的多环芳烃,无机矿物和无定型有机质占 91.15%,富集了 43.50%的多环芳烃.轻组分中的有机吸附剂对多环芳烃的富集能力比重组分无机矿物和无定型有机质高 1～ 2个数量级,轻组分有机吸附剂中焦碳和碳黑富集能力较高,植物碎屑较低.总有机碳和碳黑的含量与多环芳烃的富集能力没有明显的相关性.     

Vertical profile of polycyclic aromatic hydrocarbons in a sediment core from a reservoir in Osaka City

Concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured in a dated sediment core from a reservoir at Osaka City, Southwest Japan. The sediment core consisted of deposits collected over a period of almost 70 years whose PAH content would serve as a historical record of atmospheric environment at Osaka City. Total PAH concentrations varied from 4.2 to 26 mg kg⁻¹ dry wt, and peaked in the 1940s, reflecting the occurrence of a large fire due to air attacks during World War II. The results indicated that warfare had the largest impact on atmospheric environment in Osaka City. Total PAH concentrations decreased in the post-war period except for a small peak. In the 1950s, there was a downward trend from the 1970s to the present. These trends can be ascribed to the growth of industrial activities and the regulation of atmospheric pollutant emissions, respectively.     

Spatial distribution and source diagnosis of polycyclic aromatic hydrocarbons in soils from Chengdu Economic Region,Sichuan Province,western China

Surface soils from the Chengdu Economic Region (CER) were analyzed for sixteen United States Environment Protection Agency priority polycyclic aromatic hydrocarbons (PAHs) to study the spatial distribution and to identify the sources of PAHs. Relatively high concentrations (more than 1500 ngg^− 1) of high molecular weight PAHs were found in Chengdu Plain, in the middle of CER, while high concentrations (more than 500 ng g^− 1) of low molecular weight PAHs were detected in the surrounding mountains. The concentrations of ∑₁₆-PAHs in topsoil samples from CER (12.52–75,431.47 ngg^− 1, average value was 3233.92 ngg^− 1) were higher than that from the southern China (21.91–3077 ngg^− 1, average value was less than 500 ngg^− 1), and they were comparable to concentrations in soils from the northern China (366–254,080 ngg^− 1, mean value was more than 3000 ngg^− 1). The concentrations from CER were also much higher than the concentrations of some world clean regions such as Antarctic (34.9–171 ngg^− 1), European high mountains (9–11,000 ngg^− 1, mean value was 158 ngg^− 1) and some Europe residential (736 ngg^− 1) and arable soils (60–145 ngg^− 1, mean value was 66 ngg^− 1). The ratio of tracer compounds (BaA/(BaA + Chr), Flo/(Flo + Pyr), and IcdP/(IcdP + BghiP)) indicated that the high concentrations of PAHs in soils were mainly derived from fossil fuels combustion in mountain region and from the incomplete combustion of petroleum in developed plain area (such as Chengdu and Deyang). From the above distribution characteristics and ratios of tracer compounds, we inferred the reasons for the distribution pattern of PAHs in CER were the domestic heating, emissions, and the physicochemical properties of PAHs.     

Study on the mechanism of isotope fractionation in soil water during the evaporation process under equilibrium condition

In this study, with the method of vacuum extraction, two evaporative processes of soil water and free water under equilibrium condition were simulated. For each sample, water vapor was condensed by liquid nitrogen and was collected in four time intervals. From the analysis of hydrogen and oxygen isotopic compositions of the water collected at different times, it was discovered that the isotope fractionation of soil water also follows the mode, which is just the same as the evaporative process of free water. The relationship between the stable hydrogen and oxygen isotopes in residual water showed that the simulative evaporation line was close to the global meteoric water line (GMWL) under the equilibrium condition at about 20°C. Comparison of the two types of evaporative processes indicated that the isotope fractionation and evaporation velocity of soil water were only slightly modified by the Van der Waals force.     

Distribution and Geochemical Implication of Aromatic Hydrocarbons across the Meishan Permian-Triassic Boundary

INTRODUCTIONThe Permian-Triassic ( Tr/P) boundary , datedto be (251 .4±0 .3) Ma ago ,is marked by the mostdrastic mass extinction of organisms in the Phanero-zoic .In order to explore the pattern and the cause ofthe mass extinction,extensive research has been fo-cused on biostratigraphy , isotopic chronostratigra-phy , event stratigraphy , ecostratigraphy and se-quence stratigraphy (Payne et al .,2004 ; Reichowetal .,2002 ; Yin et al .,2001 ;Jin et al .,2000 ;Zhanget al .,1996 ,1995 ;…     

石油中饱合烃类的喇曼特征

本文试通过一些饱合烃类标样的喇曼分析,总结出石油中饱和烷烃组分的最大喇曼特征是在2700~2970 cm-1区域有一系列强烈的喇曼效应,有三种情况:1)直链烷烃类是以—CH3链基对称喇曼效应(约2872 cm-1)最强;2)带异构骨架链烷烃类是以—CH链基喇曼效应(约2911 cm-1)最强;3)环烷烃类是以—CH2链基对称喇曼效应(约2857 cm-1)最强。另外异构骨架在748 cm-1处有一强的喇曼效应,烷烃环基在804 cm-1处有一个强的喇曼效应。并发现不同的烃或烃混合物,若结构基团相同,喇曼谱图也相同;在混合烃组分(或烃类包裹体)的喇曼谱图中2905~2921 cm-1间喇曼峰应是—CH基团,而不能单作甲烷存在的证据。     

应用单体碳同位素分析技术探析农田土壤中多环芳烃的植物降解过程

长期以来,研究者在探讨土壤中多环芳烃(PAHs)的降解及修复过程中,缺乏简便有效的手段对化合物的降解动态进行定量研究。前人尝试用投加实验、对比采用降解措施前后污染物的浓度变化、模型计算等方法研究PAHs的降解过程,其结果常互相矛盾,或不能真实反映复杂的实际环境。本文应用单体碳同位素技术对农田土壤中多环芳烃的植物降解过程进行定量表征,采集了某地农田表土作为供试土壤,选择玉米作为供试作物,开展了作物对土壤中PAHs降解及消除过程的研究。气相色谱-质谱分析结果表明,培养所用的玉米原始土及分4批收集的空白土、根际土、非根际土样品中16种PAHs的浓度总和(∑PAHs)平均分别为380.8 ng/g、(281.5±34.7) ng/g、(272.2±11.6) ng/g和(299.8±37.9) ng/g;玉米生长期间,各土壤样品 的∑PAHs均比原始土壤有所下降,但除3环化合物(苊烯、苊、芴、菲、蒽)外,其他化合物并未随玉米的生长表现出显著趋势。与玉米根、叶倾向于富集低环PAHs化合物相对应,可以判断植物对土壤中的低环化合物去除作用最为显著。各采样时期玉米根际土、非根际土和空白土壤样品中多环芳烃单体化合物的碳同位素分馏值(δ¹³C)在-34.31‰~-23.95‰之间,且除芘外的其他化合物的δ¹³C值随时间呈现逐步变轻的趋势,波动值位于-0.6‰~-9.0‰之间;本文对于PAHs单体化合物,尤其是4、5环化合物,在玉米降解过程中的碳同位素分馏与浓度变化之间未发现明显关系。考虑3环以下的PAHs化合物更倾向于被降解和清除,且其碳、氢同位素分馏情况更容易被观察到,因此稳定同位素分析更有助于探明该类单体多环芳烃污染物在环境中的迁移、转化规律。