共查询到20条相似文献，搜索用时 265 毫秒
1.
Diamondoids are commonly found in petroleum and sediments and have an inherent resistance to thermal and biological destruction, which means they can provide useful information in situations where conventional biomarkers cannot. Here, we present the results of an investigation of the effects of atmospheric evaporation on the concentration and distribution of low molecular weight diamondoids in four petroleum fractions (gasoline, condensate, diesel and fuel oil). These experiments indicate that both adamantanes and diamantanes evaporate with the other light hydrocarbons from oils and that variations in the concentrations of these compounds during evaporation are controlled by the type of petroleum fraction, the extent of evaporation and the boiling point of the diamondoid compounds within the oil. Evaporation has a significant effect on adamantane concentration ratios, whereas no changes in diamantane concentration ratios occur, suggesting that diamantane-based concentration and distribution indices can be used for the correlation of oils and determination of maturity even if oils have undergone evaporation. Some diamondoid concentration ratios, such as adamantane/1-methyladamantane, 1-methyladamantane/2-methyladamantane, 1-methyladamantane/1-ethyladamantane, 1-methyladamantane/4-methyldiamantane, adamantane/diamantane and 1,3-dimethyladamantane/4,9-dimentyldiamantane, progressively decrease with ongoing evaporation and are independent of petroleum fraction type, indicating that given the original unaltered index value, these indices can be used to deduce the relative extent of oil evaporation. The study also indicates that slight to moderate evaporation of oils leads to an increase in diamantane concentrations that is nearly proportional to the extent of oil evaporation, indicating that these compounds can be used as indices to estimate the extent of oil evaporation. 相似文献
2.
Maria F. Gazulla Marta Rodrigo Monica Orduña Carmen M. Gómez 《Geostandards and Geoanalytical Research》2012,36(2):201-217
This article describes a series of methods developed for the determination of total carbon (CTotal), organic carbon (Corg), hydrogen, nitrogen and sulfur. The following elemental analysers were used: LECO model RC‐412 for the determination of organic carbon, total carbon and hydrogen; LECO model CS‐200 for the determination of total carbon and sulfur; LECO model TN‐400 for the determination of nitrogen; and LECO model TruSpec CHNS for the determination of organic carbon, total carbon, hydrogen, nitrogen and sulfur. Uncertainty and limits of detection and quantification were calculated for each method, as well as the running costs to define the most effective instrument for each material and each analyte. Accuracy was checked by the application of the Sutarno–Steger test. Finally, a compilation of the results obtained in the determination of CTotal, Corg, H, N and S in forty‐nine reference materials is presented. 相似文献
3.
Diamondoids are hydrocarbons with a carbon skeleton that is superimposable on the diamond lattice. Adamantane is the cage-shaped primary unit of diamondoids and occurs widely in sediments and petroleum. The first report of adamantane isolated from petroleum extends back seven decades, but the precursors and reaction mechanisms for the formation of adamantane and related diamondoids in sediments has remained unclear. We report the formation of alkyl adamantanes by heating β-ionone with activated carbon in closed system pyrolysis experiments in the range 170-320 °C. In addition, hydrogen exchange, demethylation, methyl transfer and isomerisation reactions were observed when the model compounds adamantane and 1,3-dimethyladamantane were heated at moderate temperature with activated carbon. A reaction pathway for the formation and reactions of alkyl adamantanes is proposed on the basis of ring isomerisation of adamantane to protoadamantane on the activated carbon surface. The carbonaceous surface reactions described help account for the occurrence and distribution of alkyl adamantanes in petroleum basins, as evidenced by the strong linear relationships between compound pairs related by isomerisation and demethylation for a set of crude oils from the Carnarvon Basin, Western Australia. 相似文献
4.
The various sources of pyrogenic and coalified carbon (black carbon, BC) in soil have considerable structural heterogeneity, making the quantification of BC a challenge. This study was aimed at evaluating the capability of different detection procedures to recover different types of BC from soil. We added defined quantities of urban dust (UD, NIST SRM1649a), diesel particulate matter (DPM, NIST SRM2975), charcoal, lignite, bituminous coal and wood to four topsoil samples. Mixtures were analyzed by way of chemo-thermal oxidation (CTO), thermal gradient oxidation (ThG), the benzene polycarboxylic acid method (BPCA) and mid-infrared spectroscopy (MIRS). CTO returned good quantification of soot BC in the pure DPM, yet the recovery of soot BC from soil was unsatisfactory (18–270%). ThG gave good precision but lower values for pure soot BC. It severely overestimated the BC content for all soil-standard mixtures. The BPCA method gave a low return for soot BC, but for the spiked soil it reliably detected charcoal and coalified C (69–107% avg. recovery) but underestimated soot BC (52–90% recovery of DPM). Linear coherence in specific MIR vibrations was found in one component soil-BC mixtures for each BC type. Applying these standard calibrations to multi-component mixtures allowed detecting charcoal and a quantification of soot BC (88% avg. recovery) via MIRS, but ignored the presence of diagenetic C. We see the greatest potential in differentiating soot from charcoal in soil by employing a combination of chemical and thermal oxidation and MIRS, while the differentiation from diagenetic C is not possible yet. 相似文献
5.
In mine soil, quantification of soil organic carbon (OC) derived recently from biomass decomposition is complicated by the presence of fossil (geogenic) C derived from coal, oil shale, or similar material in the overburden. The only reliable method for such measurement is 14C analysis (i.e. radiocarbon dating) using instrumentation such as accelerator mass spectrometry, which is too expensive for routine laboratory analysis. We tested two previously used and two new methods for recent C quantification and compared them with 14C AMS radiocarbon dating as a reference using a set of soil samples (n = 14) from Sokolov, Czech Republic: (i) 13C isotope ratio composition, (ii) cross polarization magic angle spinning 13C nuclear magnetic resonance (CPMAS 13C NMR) spectroscopy, (iii) near infrared spectroscopy (NIRS) coupled with partial least squares regression and (iv) Rock–Eval pyrolysis. Conventional methods for OC determination (dry combustion, wet dichromate oxidation, loss-on-ignition) were also compared to quantify any bias connected with their use. All the methods provided acceptable recent carbon estimates in the presence of mostly aliphatic fossil C from kerogen. However, the most accurate predictions were obtained with two approaches using Rock–Eval pyrolysis parameters as predictors, namely (i) S2 curve components and (ii) oxygen index (OI). The S2 curve approach is based on the lower thermal stability of recent vs. fossil organic matter. The OI approach corresponded well with 13C NMR spectra, which showed that samples rich in recent C were richer in carboxyl C and O-alkyl C. These two methods showed the greatest potential as routine methods for recent C quantification. 相似文献
6.
《Chemie der Erde / Geochemistry》2014,74(4):653-660
This work demonstrates that a Fe-exchanged zeolitic volcanic tuff from Cepari (Fe/CV) (Bistrita-Nasaud County, Romania) is suitable for the amperometric detection of H2O2, using new modified carbon paste electrodes based on this material (Fe/CV-CPEs). The physical-chemical characterization of natural (CV) and modified (Fe/CV) forms was realized using chemical analysis, optical microscopy, scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD), energy dispersive X-ray spectroscopy (EDX) and Fourier transformed infrared (FTIR) spectroscopy. The resulting electrodes (Fe/CV-CPEs) were investigated using cyclic voltammetry and chronoamperometry measurements. The new electrodes showed good electrocatalytic activity toward H2O2 reduction. The calibration curve for H2O2 determination was linear up to 0.1 mM, with a detection limit (signal to noise ratio of 3) of 20 μM. 相似文献
7.
Ling HuangShuichang Zhang Huitong WangXiaofang Fu Wenlong ZhangYirui Xu Caiyun Wei 《Organic Geochemistry》2011,42(5):566-571
A novel, effective and simple method based on adsorption chromatography on silica gel, adsorption on molecular sieves, and inclusion in β-cyclodextrin (β-CD) was developed to separate and enrich diamondoids directly from crude oil. In this method, diamondoids ranging from adamantanes to triamantanes were purified and isolated from the branched/cyclic hydrocarbon fraction of crude oil for further accurate analysis of stable carbon isotope ratios (δ13C) by gas chromatography-isotope ratio mass spectrometry (GC-irMS). A 5 mg/ml solution of β-CD stirred for 2 h was found to be sufficient for the inclusion of diamondoids and the inclusion complex completely breaks down by acidolysis in 1 mol/l hydrochloric acid at 80 °C for 16 h. The recovery of diamantanes was higher than that of other diamondoids. Our major finding is that the specific inclusion effect between β-CD and diamondoids can be utilized to isolate and concentrate diamondoid compounds from crude oil in a fast and effective way. It is a potential method to yield the diamondoid fraction amenable for compound-specific isotope analysis (CSIA), which markedly improves accuracy of molecular isotopic proxies of oil-oil and oil-source correlation. 相似文献
8.
土壤中25种有机氯农药和多氯联苯的气相色谱分析方法研究 总被引：6，自引：5，他引：1
研究了土壤中17种有机氯农药和8种多氯联苯组分的气相色谱分析方法。采用加速溶剂萃取技术提取,优化了萃取条件。提取液用固相萃取技术进行净化,采用20 mL含3%(体积分数)甲苯的正己烷-乙酸乙酯(体积比8∶2)进行淋洗,得到很好的净化效果。方法检出限在0.06~0.27μg/kg,线性范围在1.38~55.2 ng/mL,目标化合物的平均添加回收率在65%~97%,相对标准偏差(RSD,n=6)小于17.11%。方法快速、灵敏、准确,适合批量样品的分析。 相似文献
9.
微量金化学光谱法标准系列配制及活性炭处理的改进 总被引：2，自引：0，他引：2
对微量金化学光谱法中活性炭自理及标准系列配制的方法进行了探索,改进了微量金化学光谱法活性炭处理及标准系列配制。将该法配制的标准系列应用于微量金化光谱测定,提高了分析结果的准确度。用标准试样分析及原子吸收（ＡＡＳ）法验证,结果与标准值及ＡＡＳ法相符。 相似文献
10.
沉积物中元素碳的提取、鉴定及其古气候环境意义 总被引：1，自引：0，他引：1
通过化学氧化方法提取沉积物中元素碳物质,采用拉曼光谱对其进行分析鉴定,实验结果表明:元素碳是介于单晶石墨碳和无定形碳之间的一系列物质,是一种操作上的定义;化学氧化法提取沉积物中元素碳是可靠的,控制好氧化条件和时间,则能有效去除有机碳,保留元素碳成份。鉴于目前不同工作者由于不同的实验条件和方法下得到了不同结果,我们认为确定标准样及其浓度,统一实验方法是亟待解决的问题,进而统一这种碳微粒的名称,明确其定义,以利于相关研究的横向对比和深入。而在纵向研究方面,我们利用该实验流程提取灵台黄土剖面长时间序列黄土—古土壤样的元素碳,并进行元素碳含量的测定,结果表明元素碳记录能有效揭示古气候环境变化。在不同时间尺度上,元素碳记录有不同的气候指示意义,并且与其他气候环境指标能进行较好的对比,元素碳记录为古气候环境变化提供一新的指标。 相似文献
11.
Heavy metals are toxic elements that have hazardous effect on the environment. They cause soil pollution as a result of their toxicity, potential reactivity, and mobility in soils. There are so many methods for the measurement of heavy metal concentrations in soils and aquatic systems. The traditional methods used for detecting heavy metal distribution in soil involve laboratory analysis and raster sampling. Both of them are expensive and time-consuming for large areas. Remote sensing techniques are used for obtaining the earth’s surface information, and these techniques have been used in the investigations of heavy metal distributions in preliminary analysis of soils as a rapid method. Today, near-infrared reflectance spectroscopy (NIRS) of soil characteristics has been of interest as a significant object. The present investigation is focused on the detection of heavy metals in contaminated soils by the application of reflectance spectroscopy in the spectral range of 350 to 2500 nm. This study also discusses the circumstances of the applied current methods for the detection and estimation of arsenic (As), cadmium (Cd), nickel (Ni), and lead (Pb) in contaminated agricultural soils. In the first part of laboratory spectroscopy, estimations were done using heavy metal reflectance spectroscopy and partial least square regression (PLSR) approaches, while in the second part, the heavy metal estimations were done using soil organic carbon reflectance spectroscopy through the PLSR approaches. Similar to the tasks above, estimations of As, Cd, Ni, and Pb by using Landsat 8 images were done in the forms of direct and indirect methods and the distribution of heavy metals in the study area was determined. Finally, the results obtained using direct and indirect methods were compared with the wet chemical measurements of heavy metals and organic carbon. It was found that although the direct detection of heavy metals using the images of Landsat 8 produced more accurate results than the indirect detections, the results obtained from laboratory spectroscopy corresponded more with the results from atomic adsorption spectroscopy. On the other hand, based on the fact that the soil has a complex content, the use of nonlinear methods, such as artificial neural networks in predicting soil heavy metal contents, could be regarded as a trusted method. 相似文献
12.
Large scale environmental monitoring schemes would benefit from accurate information on the composition of soil organic matter (SOM), but so far routine procedures for describing SOM composition remain a chimera. Here, we present the initial assessment of a two step strategy for expeditious determination of SOM composition that involves: (i) building infrared fingerprints from near and mid infrared spectroscopies, two rapid and cheap yet reliable technologies; and (ii) calibrating such infrared fingerprints with multivariate chemometrics from a molecular mixing model based on the more expensive and time consuming 13C nuclear magnetic resonance technique, which discriminates five biochemical components: carbohydrate, protein, lignin, lipid and black carbon. We show fair to excellent predictive ability of the calibrated infrared fingerprints for four out of these five biochemical components, with cross-validated ratios of performance to inter-quartile distance from 3.2 to 8.3, on a small set of 23 soil samples with a wide range of organic carbon content (12–500 g/kg). Multivariate calibration models were highly selective (<2% of infrared data were used for all models). However, the specificity to one particular biochemical component of the infrared wavebands automatically selected by each model was relatively low, except for lipid. Achieving direct predictions of SOM composition on unknown soil samples with infrared spectroscopy alone will require further independent validation and a larger number of samples. Overall, the implementation of our strategy at a broader scale, based on available 13C nuclear magnetic resonance soil libraries, could provide a cost effective solution for the routine assessment of SOM composition. 相似文献
13.
银是高纯铟的常检痕量元素,由于银含量低,一般的分析方法难以达到期望的检出限。本研究样品用硝酸溶解,强酸性阳离子交换树脂分离,试液蒸发浓缩后用石墨炉原子吸收光谱法测定高纯铟中痕量银。通过溶样方法、离子交换分离条件和仪器测定条件实验,结果表明,以0.7 mol/L硝酸作为淋洗液进行分离,样品中痕量砷、铝、铁、锡及大量的铟可被分离除去;铜、镉、镁、镍、锌、铅、硅和铊不能与银分离,但对测定无影响。方法线性范围为0～50 pg,相对标准偏差(RSD,n=8)小于10%,银的检出限为0.3 pg,测定下限为0.8ng/g,比文献方法的0.02～1μg/g中最低者低2个数量级,加标回收率为93.3%～110.0%。本方法由于分离了基体铟,避免了铟对银测定的影响,兼之将试液浓缩,有效地降低了检出限,且测定时无需使用基体改进剂,成本低,灵敏度较高,适合于高纯铟中痕量银的分析。 相似文献
14.
Core drilling of near surface seams near Wakefield NSW has provided high volatile bituminous coal samples that have been subject to varying degrees of natural in situ oxidation. Five levels of oxidation have been defined, mainly on visual evidence, ranging from unoxidised coal to highly oxidised material. Samples of each oxidation level have been investigated by chemical analysis, Fourier transform infrared spectroscopy (FTIR) and solid state carbon-13 nuclear magnetic resonance spectroscopy (NMR) with cross-polarization and magic angle spinning.The results show that mineral matter, moisture and oxygen content increase with oxidation, whereas carbon, hydrogen and specific energy decrease. Moisture determination is suggested as a quick, facile method for indicating the oxidation level for a coal sample from this seam. FTIR showed a marked loss of aliphatic C-H groups with increasing oxidation, and an increase in carbonyl and carboxylate groups. Aromatic C-H groups were much less affected by oxidation. Solid state carbon-13 NMR showed increasing carbon aromaticity with oxidation, but showed substantial carbonyl carbon only at the highest oxidation level. No evidence was found for an increase in aromatic substituents during oxidation; if anything, there is a small decrease in substituents. 相似文献
15.
16.
高效液相色谱法同时测定地表水中四种醛类化合物 总被引：1，自引：0，他引：1
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。 相似文献
17.
以炭粉、K_2S_2O_7、Al_2O_3、Na F等为缓冲剂,Ge为内标,直读发射光谱法测算地球化学样品中的Cu。方法的检出限为0.78μg/g,方法的精密度(RSD,n=12)为4.95%~7.88%.测定了国家一级标准物质,测定结果和标准值相符。 相似文献
18.
G. N. Gordadze V. Yu. Kerimov A. V. Gaiduk M. V. Giruts M. A. Lobusev S. G. Serov N. B. Kuznetsov T. V. Romanyuk 《Geochemistry International》2017,55(4):360-366
This study presents geochemical data on organic-rich rock samples collected from Riphean—Lower Paleozoic strata (potential source rocks) of the southern Siberian Platform and compositional data on hydrocarbon biomarkers (steranes, terpanes, n-alkanes, 12- and 13-methylalkanes, isoprenanes) and diamondoid hyrocarbons from core samples collected from the Kulindinskaya-1 well, which was drilled by RN-Exploration in 2012 within the Katanga saddle. 相似文献
19.
用气相色谱-电子捕获法(GC-ECD)检测地下水中百菌清、丙环唑、己唑醇、嘧菌酯和高效氯氰菊酯。样品用乙酸乙酯-正己烷(体积比1∶1)液-液提取,提取液经无水硫酸钠去水后、浓缩、并定容至1.0 mL,最后用微池-电子捕获检测器(GC-μECD)进行检测。方法准确度、灵敏度高。2.0 ng/L添加水平所有待测物回收率≥68.8%,相对标准偏差(RSD,n=3)≤14.6%,百菌清、己唑醇、丙环唑、高效氯氰菊酯和嘧菌酯的方法检测限分别为0.50 ng/L、2.0 ng/L、2.0 ng/L、2.0 ng/L和2.0 ng/L。 相似文献
20.
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 总被引：2，自引：1，他引：1
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。 相似文献