Measurements of stable carbon isotopic composition of ethane and propane over the western North Pacific and eastern Indian Ocean: A useful indicator of atmospheric transport process

Stable carbon isotopic composition of ethane and propane over the western North Pacific and eastern Indian Ocean between 31°N and 26°S was investigated from February through March 2004. The isotopic composition of ethane ranged from −28 to −18‰ and showed a gradual increase from north to south. Conversely, that of propane was between −31 and −24‰; it showed no systematic latitudinal variation. Investigation of the ethane/propane ratio indicates that ethane and propane that originated from northern mid-latitude countries in the eastern part of Eurasia were both transported into the western North Pacific region. However, the results of the isotopic analyses indicate the contribution of oceanic emission to the atmospheric propane during transport, although that contribution can not be discerned for ethane. A ship based stationary observation conducted in the western equatorial North Pacific showed that the isotopic composition of ethane varied from −25 to −19‰ and showed clear systematic diurnal variation: propane ranged between −32 to −26‰ and no such isotopic diurnal signal was observed. The diurnal variation for ethane is explained by entrainment of free tropospheric air, whereas the variation for propane was influenced by oceanic emissions as well as the entrainment. The contribution of oceanic emissions to the atmospheric propane inventory was considered from our isotopic observation. Isotopic composition of dissolved propane is estimated to be less than −38‰, and the contribution up to 79% was calculated when the isotopic composition of dissolved propane is assumed to be −40‰. Our study demonstrates that isotopic analysis can be more useful than ratio-based analysis to improve our present understanding of transport processes, especially for impact of the oceanic emissions on the atmospheric distribution of low level C₂–C₅ non-methane hydrocarbons such as propane in the remote marine atmosphere.     

南京北郊气溶胶中多环芳烃的污染特征及来源解析

利用2010年8月采集的南京北郊气溶胶样品,使用GC-MS对美国环保总局推荐的16种优先控制的多环芳烃含量、分布特征进行了研究。在此基础上,用特征比值法、主因子分析法分析得到南京市北郊大气中PAHs的主要来源为车辆尾气、燃煤、天然气和草木秸秆燃烧,并应用绝对因子分析法进一步定量计算主要源对PAHs的浓度贡献率。结果表明:1)大气颗粒物中16种多环芳烃的平均总质量浓度为135.85 ng/m~3,多环芳烃以4环为主,在可吸入颗粒物中的浓度占总浓度的88.7%;2)PM10中多环芳烃呈双模态分布,在9~10μm的粗模态和0.65~1.10μm的积聚模态上各出现一个峰值;3)天然气等对PAHs的贡献率为5.7%~44.1%,燃煤源的贡献率为20.7%~57.8%,汽车尾气的贡献率为4.6%~46.7%,木材燃烧的贡献率为2.9%~38.1%。本地交通排放和燃料燃烧是南京北郊大气颗粒物中PAHs的主要来源,远距离输送也对南京北郊气溶胶中的PAHs有重要贡献。     

Primary Product Distributions from the Reaction of OH with m-, p-Xylene, 1,2,4- and 1,3,5-Trimethylbenzene

A study was conducted to examine the OH-initiated degradation products of the four title compounds in the presence of sub-part-per-million levels of NO_x. The oxidation was conducted in a dynamic reactor to minimize the conversion of the aromatic compounds. The experiments were designed to represent reaction pathways that occur in the atmosphere at ambient NO₂ concentrations. A wide range of ring-retaining and ring-cleavage products having widely varying yields were measured during the study. For m-xylene, the major primary products observed (with molar yields) were methyl glyoxal (0.40), 4-oxo-2-pentenal (0.12), glyoxal (0.079), and m-tolualdehyde (0.049). For p-xylene, the major primary products were p-tolualdehyde (0.103), 2,5-dimethylphenol (0.13), cis-3-hexene-2,5-dione (0.176), trans-3-hexene-2,5-dione (0.045), 2-methyl-butenedial (0.071), glyoxal (0.394), and methylglyoxal (0.217). Several other reaction products were measured at yields less than 3%. The primary products for OH + 1,2,4-trimethylbenzene were found as follows: methylglyoxal (0.44), glyoxal (0.066), cis-3-hexene-2,5-dione (0.13), trans-3-hexene-2,5-dione (0.031), biacetyl (0.114), 3-methyl-3-hexene-2,5-dione (0.079), and 2-methyl-butenedial (0.045). Six other (ring retaining) products were measured at yields less than 3%. The primary products for OH + 1,3,5-trimethylbenzene were methylglyoxal (0.90), 3-methyl-5-methylidene-5(2H)-furanone (0.1), 3,5-dimethyl-3(2H)-2-furanone (0.1), 3,5-dimethyl-5(2H)-2-furanone biacetyl (0.08), and 2-methyl-4-oxo-2- pentenal (0.05). Three other products were detected at molar yields less than 5%. In some cases, the yields for the ring fragmentation products could only be based on calibrations from surrogate compounds. Yields for several of the unsaturated dicarbonyl compounds have not been reported previously while yields for methylglyoxal, glyoxal, and biacetyl are largely consistent with previous reports. Some of the primary furanone products are the identical to those reported as secondary products in aromatic systems.     

“雪龙号”2003北极航次气相多环芳烃纬度分布观测

2003年“雪龙号”北极科学考察期间,对沿途海洋大气进行采样,分析其中气相多环芳烃的空间分布。结果显示,气相中主要是2-4环的多环芳烃,其中菲为主要的化合物,平均占到总多环芳烃的55.1%。在整个航程的广泛区域尺度内,气相总多环芳烃浓度在1043.9-92993.1pg/m3。空间分布上,远东亚的海面>北太平洋海面>北极圈以内海面;总多环芳烃的浓度随纬度升高呈现显著降低的趋势。通过Clausius-Clapeyron方程对浓度和温度相互关系的分析表明,温度是控制气相多环芳烃长距离传输的主要因素。     

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.     

Pyrolysis of immature Torbanite and of the resistant biopolymer (PRB A) isolated from extant alga Botryococcus braunii. Mechanism of formation and structure of torbanite

Immature Torbanite and the resistant biopolymer (PRB A) isolated from extant B. braunii were previously compared using bulk spectroscopic methods. In the present work, analysis of 400°C pyrolysis products and pyrolysis residues provided further information on their structure and possible relationships. It appears that such polymers are based upon unbranched, saturated, cross-linked hydrocarbon chains up to C₃₁. In addition to these bridging structures, a substantial part of the alkyl chains is singly bound, as esters of unbranched, saturated or cis unsaturated, even fatty acids. These esters are sterically protected, against chemical degradations, by the network of the bioand geopolymer.Quantitative and qualitative observations derived from 400°C pyrolysis confirm that the chemical structure of PRB A and immature Torbanite are closely related. The pyrolysis residues show a similar evolution and numerous common features are noted, with respect to the nature and the distribution of the major constituents of the pyrolysates (hydrocarbons and fatty acids). Accordingly, Botryococcus provides what seems to be the first example of a close structural relationship between a biopolymer produced in large amounts by an extant alga and the geopolymer of an immature kerogen. The essential role of PRB A in Torbanite formation is ascertained. Moreover, it is found that the resistant biopolymer does not undergo important structural changes during the first stages of diagenesis. Thus, owing to steric protection, the esters of immature Torbanite show a distribution quite close to the one of PRB A esters, with exclusively even constituents and a large contribution of unsaturated acids.Recent observations pointed to the possible genesis of some algal kerogens principally by selective preservation of resistant macromolecules. Such a type of formation is clearly predominant in Torbanite, where the bulk of the fossil organic matter corresponds to a selectively preserved and weakly altered, resistant biopolymer, while incorporation of lipids into the kerogen structure during diagenesis seems to play a minor role.     

冀北—辽西早白垩世沉积有机质特征与古气候环境演变

本文对冀北—辽西地区早白垩世沉积盆地富有机质沉积岩进行了初步有机地球化学分析研究。结果显示,冀北—辽西沉积盆沉积有机质特征在时间和空间上存在很大差异,代表白垩系早期沉积的滦平盆地大北沟组有机质丰度低,这不仅显示其所代表的沉积相带不利于有机质的聚集,也反映了当时生物不够繁盛;大店子组时期沉积相带发生了变化,有机质类型随着发生了变化,丰度有所增高,但总体上显示环境条件不利于生物的发育和繁盛。到了桥头组和义县组沉积岩有机质丰度大幅升高,表明生物界非常繁盛,古气候环境有利于有机质的大量生成和堆积,总体上反映了温湿的气候条件;但同时也存在较为频繁或交替性寒冷气候波动,具体的古气候环境状态尚需进一步深入研究。     

Predominance of archaea-derived hydrocarbons in an Early Triassic microbialite

We investigated the distribution of lipids in Lower Triassic sedimentary rocks (252–247 myr) from South China, including a shallow water microbialite in the uppermost section of the outcrop. Archaeal derived hydrocarbons were the major constituents of the microbialite from the latest Early Triassic. Among these, we detected (i) abundant C₄₀ acyclic and monocyclic biphytanes (possibly derived from glycerol dialkyl glycerol tetraether lipids) and their degradation products, C_30–39 pseudohomologues and (ii) a C₂₅ head-to-tail linked (regular) isoprenoid hydrocarbon [possibly derived from dialkyl glycerol diether lipids (DGDs)] and its degradation products, C_21–24 pseudohomologues and abundant pristane and phytane. Through combination of compound-specific stable carbon isotope analysis of isoprenoid hydrocarbons, which had average δ¹³C values of −35‰ to −30‰, and their molecular distribution, it was not possible to unambiguously define the archaeal source for the biphytanes in the microbialite. The δ¹³C values for pristane and phytane were similar to those for head-to-tail linked C_21–25 isoprenoids; potential source organisms for these compounds were halophilic archaea. Except for methane seep microbialites, no other ancient or recent phototrophic microbialites have been reported to contain predominantly archaeal isoprenoid hydrocarbons. Our findings suggest the presence of a new type of microbialite.     

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。     

Accumulation of petroleum hydrocarbons and heavy metals in clams （Ruditapes philippinarum） in Jiaozhou Bay, China

Accumulation and distributions of aliphatic and polyaromatic hydrocarbons (PAHs) and heavy metals were measured in tissues of the clam Ruditapes philippinarum collected from 5 sites in Jiaozhou Bay, Qingdao, China. The concentrations of total aliphatic hydrocarbon and PAHs ranged from 570 to 2 574 ng/gdw (gram dry weight) and from 276 to 939 ng/gdw, in the most and least polluted sites, respectively. The bio-accumulation of hydrocarbons and PAHs in the clams appeared to be selective. Aliphatic hydrocarbons were predominantly represented by short chain (<nC₂₃) n-alkanes, suggesting that petroleum hydrocarbons were likely the major contamination source. The selective uptake of 3 and 4 ring PAHs, such as naphthalene, fluorene, phenanthrene, fluoranthene and pyrene, by the clams was probably related to the physiological and bio-kinetic processes that were energetically favorable for uptake of compounds with fewer rings. Accumulation of the metals Cd, Cu, Zn, Pb, Cr, Hg, and As in the clam tissues also showed high variability, ranging from 0.043 to 87 μg/gdw. Among the 7 detected metals, Zn, Cd, Cu, and As had a particularly high potential of accumulation in R. philippinarum. In general, a positive correlation was found between the tissue concentrations and sediment concentrations of hydrocarbons and of some metals. Our study suggests that moderate contamination with polyaromatic hydrocarbons, and low to moderate contamination with metals, currently exists for clam R. philippinarum in Jiaozhou Bay, in comparison with other regional studies. A long-term monitoring program is certainly needed for assessment of the potential ecological influence and toxicity of these contaminants of R. philippinarum in Jiaozhou Bay.