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1.
TOC Determinations in Ground Water   总被引:2,自引:0,他引:2  
Determinations of total organic carbon (TOC) can provide valuable diagnostic evidence of the extent of ground-water contamination by organic compounds. The usefulness of conventional TOC results in monitoring efforts is limited by the bias introduced during the purging of inorganic carbon prior to analysis. A modified TOC procedure has been evaluated to permit the quantitation of the volatile organic carbon (VOC) fraction in water samples. The methodology consists of trapping the VOC in a manner analogous to commercial purge and trap instruments which are used for specific organic compound separations. The method has been found to be sensitive, accurate and reasonably precise for TOC determinations of standard solutions as well as on ground-water samples. Volatile organic carbon levels can range from 9–50% of the TOC in both uncontaminated and contaminated ground waters. The reporting of the volatile and nonvolatile fractions of the TOC will enhance both monitoring and research efforts, since it permits more complete characterization of the organic carbon content of ground-water samples.  相似文献   

2.
The total organic carbon(TOC)in the marine source rock of the Ordos Basin mostly ranges from 0.2%to 0.5%.The industrial standard commonly states that the TOC value has to be no less than 0.5%(0.4%for high mature or over-mature source rock)to form large petroleum reservoirs.However,gas source correlation indicates that the natural gas in the Jingbian gas field does receive contribution from marine source rocks.In order to determine the effect of carboxylate salts(or called as organic acid salts)on TOC in highly mature source rocks with low TOC value,we sampled the Ordovician marine source rock and the Permian transitional facies source rock in one drilled well in the southern Ordos Basin and performed infrared and GC-MS analysis.It is found that both kerogen-derived organic acids and carboxylate salt-conversed organic acids exist in both marine and transitional facies source rocks.The carboxylate salt-conversed organic acids mainly come from the complete acidification of carboxylate salts,which confirms the presence of carboxylate salts in the marine source rocks.Although the C16:O peak is the main peak for the organic acids both before and after acidification,the carboxylate salt-conversed organic acids have much less relative abundance ahead of C16:O compared with that of the kerogen-based and free organic acids.This observation suggests that the kerogen-based and free organic acids mainly decarboxylate to form lower carboxylic acids,whereas the carboxylate salt-conversed organic acids mainly break down into paraffins.By using calcium hexadecanoate as the reference to quantify the kerogen-derived and carboxylate salt-conversed organic acids,the high TOC(>2.0%)marine source rocks have low carboxylate salt content and the low TOC(0.2%–0.5%)marine source rocks contain high content of carboxylate salt.Therefore,for the marine source rocks with 0.2%–0.5%TOC,the carboxylate salts may be a potential gas source at high maturity stage.  相似文献   

3.
Organic matter has been observed in cores of the Soultz-sous-Forêts granite (Alsace, France) at depths between 2158 and 2160 m, in a highly fractured and altered zone. The granite is overlain by a 1400-m-thick sedimentary cover containing petroleum (Pechelbronn oil field). The Soultz area is devoted to Hot Dry Rock geothermics thanks to a high geothermal gradient (up to 100 °C/km). During drilling operations, an artesian source produced oil in a fractured zone of the sedimentary cover (Buntsandstein). Its gas-chromatography and mass-spectrometry (GC-MS) analysis revealed the presence of normal alkanes (n-alkanes, i.e. linear hydrocarbons) centered on C17, branched alkanes with a major C19 peak, and few unsaturated hydrocarbons. The aromatic fraction is present in small amounts. In the Soultz granite, where it is altered, organic matter is exclusively associated with tosudite (interstratified clay mineral) which crystallized in plagioclase sites during a hydrothermal alteration episode. Organic matter has been later displaced and concentrated along veinlets in which illite and carbonates have crystallized during another hydrothermal alteration stage. The soluble organic matter analyzed by GC-MS is composed of aliphatic acids, n-alkanes with a bimodal C18 and C24-C25 centered distribution, alkylbenzenes and aromatic acids. Organic compounds in the granite would either originate from a single source (immature sediments) or from two sources (immature sediments and migration of the Pechelbronn oil). No real evidence was found to prove which hypothesis is the best one. The presence of organic matter in the granite shows the importance of fluid flows between the sedimentary cover and the granitic basement through major fractures. In addition, the impregnation of plagioclase pseudomorphs with organic matter is made possible due to their high interconnection degree and to the intergranular microfracturation of the granite. The succession of several hydrothermal events with different physico-chemical characteris- tics may also be inferred from the occurrence of organic matter found in association with neoformed clay minerals in the granite.  相似文献   

4.
A sequential selective chemical degradation has been performed on the kerogen from the Nenjiang Formation of the southern Songliao Basin by using a series of mild chemical degradations (alkaline hydrolysis, cleavage of ether-bonds and sulfur-bonds, and ruthenium tetroxide (RuO4) oxidation). Subsequently, the GC-MS analyses are carried out on different degradation products. The results show that chemical degradations can release a great number of GC/MS-determinable biomarkers from insoluble kerogen, such as, alkaline hydrolysis products mainly comprise n-alkanes, fatty acids and alkanols; thiophene compounds are predominantly ether-bound to kerogen matrix; the products from the cleavage of sulfur-sulfur and sulfur-carbon bonds in the kerogen include fatty acids, alkanols and some n-alkanes with high carbon numbers; RuO4 oxidation products are predominantly monocarboxylic acids and α,ω-dicarboxylic acids. The distributions of main degradation products indicate that organic matter in this kerogen is predominantly derived from algae and bacteria, and that small amounts of high plant-derived organic matter are possibly combined into kerogen matrix at the late stage by sulfur bonds and other means. This study will provide an important approach for further discussing sources of organic matter in source rocks and their depositional paleoenvironments.  相似文献   

5.
6.
This research continues a 7-year study of oxygen-containing organic compounds present in groundwater at gasoline and diesel fuel release sites that are quantified as diesel-range “total petroleum hydrocarbons” when measured by methods utilizing solvent extraction and gas chromatography. Two-dimensional gas chromatography with time-of-flight mass spectrometry was used to tentatively identify 1162 compounds (TICs) in 113 groundwater samples from 22 sites. Samples were collected from wells either upgradient of the release, within the source zone, or downgradient of the source but still within the plume of dissolved organics associated with release. The names and formulas of all TICs found in samples from each well type are presented and the results from upgradient and downgradient locations are compared in detail. About 60% of the most frequently detected TICs in downgradient wells were also detected in upgradient wells. A majority of these were saturated straight chain alkyl acids, commonly called fatty acids, or fatty acid esters. Of TICs frequently detected in downgradient wells but not upgradient wells, over half were branched alkyl alcohols. Hierarchical cluster analysis results suggest about 80% of the chemical composition of downgradient samples is more similar to upgradient samples than to source area samples. This similarity is due to the presence of the same types of fatty acids and esters. Principal component analysis indicates a continuum of biodegradation between the source area and downgradient samples with the latter becoming more consistent with upgradient samples. Results suggest some TICs may not be petroleum degradation intermediates but compounds synthesized by microorganisms through secondary production and carbon cycling.  相似文献   

7.
Dissolved high molecular weight organic substances, like humic substances, can be characterized with regard to their molecular weight distribution using gel filtration chromatography (GFC). In addition, the adsorption properties, for example on activated carbon, can be described, if the substances are separated by hydrophobic interaction chromatography (HIC) in different fractions using a chromatographic column with a hydrophobic matrix. The retention time (Rt) of single chemical substances in this column can be used to characterize the hydrophobicity or hydrophility of each compound as well as of the high molecular weight organic matter. The hydrophobic interaction between the matrix of the column and the dissolved chemical compounds also depends on the hydrophobicity of the gel and the composition of the eluent. Relations between retention times, log P-coefficients (octanol/water partition) and K-values of isotherms on activated carbon (Freundlich equation) were found.  相似文献   

8.
Sediment samples collected from polluted (Augusta Bay) and pristine regions of the Eastern Mediterranean Sea (South Ionian Sea, Thracian Sea) were analyzed for black carbon, aliphatic hydrocarbons and phospholipid ester-linked fatty acids (PLFA). The aim of the study was to investigate the anthropogenic and biogenic inputs into the Eastern Mediterranean Sea and to evaluate the effects of refractory organic matter (e.g. black carbon) and the level of hydrocarbon contamination on benthic microbial community composition. Black carbon, generally considered to be chemically and biologically inert, comprised a significant but highly variable fraction of the sedimentary carbon pool in the analyzed sediments with a ratio to total organic carbon ranging from 0.02 to 0.66. Principal component analysis of the chemical characteristics of the sediments (organic carbon content, black carbon, bioavailable organic carbon, chlorophyll a, phaeopigments, aliphatic hydrocarbons) revealed clustering of samples along a gradient from the most productive and contaminated region of Augusta Bay to the carbon-poor and pristine sediments of the Thracian Sea. PLFA analysis revealed that gram-negative bacteria and microeukaryotes were most abundant in Augusta Bay and in the most impacted station of the Thracian Sea. The high levels of branched and odd-chain fatty acids recorded for these stations is probably linked to the elevated amounts of hydrocarbons at these stations; e.g. microbial communities may have developed the ability to degrade either naturally occurring aliphatic hydrocarbons or hydrocarbons derived from oil contamination.  相似文献   

9.
The effect of light intensity on the release of dissolved organic carbon during photosynthesis on NaH14CO3 was investigated using the phytoplanktonic CyanobacteriumOscillatoria rubescens. The released products were fractionated by molecular size and chemical identifications attempted using combined thin-layer electrophoresis and chromatography, and high pressure liquid chromatography.Within the range of irradiances tested (from 6 to 60 µmole m–2 sec–1), though the upper one inhibited photosynthesis ofO. rubescens, light had little effect on the quantity and composition of the excreted products. The released carbon was always lower than 3% of the incorporated carbon, and mainly composed (62 to 86%) by small molecular weight compounds. The prevailing identified compounds were amino acids which represented more than 20% of the excreted carbon. Among organic acids, glycolic acid accounted for less than 2% of the recovered radioactivity. Glucose was the only identified sugar.Abbreviations EOC excreted organic carbon - DOC dissolved organic carbon - PER percent extracellular release - LMW low molecular weight - HMW high molecular weight - AA amino acids - µmoles m–2 sec–1 = µEinsteins m–2 sec–1  相似文献   

10.
The amino acids β-alanine and γ-aminobutyric acid are known to compose only a very minor proportion of the total amino acid content in living matter. In deep-sea sediments, however, their abundance in high proportions is ubiquitous. The organic material within foraminiferal calcite tests that are recovered from marine sediments has been found to contain no β-alanine and γ-aminobutyric acid. This observation provides a chemical check that can be used to ensure that the tests have been thoroughly cleaned. Such checks are important because the amino acid composition of organic material contained within the test is currently being used to establish schemes for chronology and taxonomy of foraminifera.  相似文献   

11.
Summary Petrophysical properties (susceptibility, intensity of the Natural Remanent Magnetisation (NRM) and bulk density) of 489 meteorite samples from 368 meteorites are discussed. The samples, obtained from Finnish meteorite collections, represent all chemical-petrological meteorite classes and their groups. This meteorite petrophysical database has many potential applications in the geophysical studies of extraterrestrial bodies (planets and their moons, asteroids, meteorite parent bodies, etc.). Here we use the database to classify meteorites rapidly and non-destructively by applying the petrophysical classification scheme developed by Kukkonen and Pesonen [10]. For example, the main classes and many groups form distinct clusters in petrophysical relation diagrams such as susceptibility vs. density or NRM vs. susceptibility. The petrophysical classification method was tested on 24 meteorites from Czechoslovak, 3 from Swedish and one from Australian collections. The chemical-mineralogical classifications of these meteorites were previously known. The subjective classification method was also compared with a mathematical cluster analysis. The subjective classification technique was successful in 64% to 93% of the cases whereas the mathematical analysis was successful in 57% to 82% of the cases. The failures can be attributed to (i) non-uniqueness problems (cluster plots overlap) and (ii) effects of porosity, self-demagnetisation, electrical conductivity and frequency on measured values, or to biasing caused by small sample size.  相似文献   

12.
Microscopic investigations have been done on the chondrites Sena and Nadiabondi (H5, not shocked), Ste. Marguerite en Comines (H4, very slightly shocked), Allegan (H5, slightly shocked). Only in such cases can the matrix be easily observed and compared to those of type 3 chondrites. The <100 μm debris found in types 4 and 5 that we have observed are not the result of the metamorphism of type 3 fines.The abundance of tiny debris is in direct relation with the intensity of the shock though this shock was insufficient to provoke either the induration of the stones or a significant loss of rare gases. The bulk of the fines are the result of local disaggregation of the most brittle parts from chondrules and fragments.A low-temperature matrix has not been observed in these meteorites but only in H3 chondrites, as a coating around the chondrules. The accretion modelists should take into account the absence or the scarcity of fine particles in their calculations.  相似文献   

13.
Stable carbon isotope measurements of the organic matter associated with the carbonate globules and the bulk matrix material in the ALH84001 Martian meteorite indicate that two distinct sources are present in the sample. The delta 13C values for the organic matter associated with the carbonate globules averaged -26% and is attributed to terrestrial contamination. In contrast, the delta 13C values for the organic matter associated with the bulk matrix material yielded a value of -15%. The only common sources of carbon on the Earth that yield similar delta 13C values, other then some diagenetically altered marine carbonates, are C4 plants. A delta 13C value of -15%, on the other hand, is consistent with a kerogen-like component, the most ubiquitous form of organic matter found in carbonaceous chondrites such as the Murchison meteorite. Examination of the carbonate globules and bulk matrix material using laser desorption mass spectrometry (LDMS) indicates the presence of a high molecular weight organic component which appears to be extraterrestrial in origin, possibly derived from the exogenous delivery, of meteoritic or cometary debris to the surface of Mars.  相似文献   

14.
Biodegradation of organic compounds in groundwater can be a significant source of methane in contaminated sites. Methane might accumulate in indoor spaces posing a hazard. The increasing use of ethanol as a gasoline additive is a concern with respect to methane production since it is easily biodegraded and has a high oxygen demand, favoring the development of anaerobic conditions. This study evaluated the use of stable carbon isotopes to distinguish the methane origin between gasoline and ethanol biodegradation, and assessed the occurrence of methane in ethanol fuel contaminated sites. Two microcosm tests were performed under anaerobic conditions: one test using ethanol and the other using toluene as the sole carbon source. The isotopic tool was then applied to seven field sites known to be impacted by ethanol fuels. In the microcosm tests, it was verified that methane from ethanol (δ13C = −11.1‰) is more enriched in 13C, with δ13C values ranging from −20‰ to −30‰, while the methane from toluene (δ13C = −28.5‰) had a carbon isotopic signature of −55‰. The field samples had δ13C values varying over a wide range (−10‰ to −80‰), and the δ13C values allowed the methane source to be clearly identified in five of the seven ethanol/gasoline sites. In the other two sites, methane appears to have been produced from both sources. Both gasoline and ethanol were sources of methane in potentially hazardous concentrations and methane could be produced from organic acids originating from ethanol along the groundwater flow system even after all the ethanol has been completed biodegraded.  相似文献   

15.
The temporal variations of the superficial (0–1 cm) sedimentary organic matter were studied at a depth of 26 m on the continental shelf of the Gulf of Lions (northwestern Mediterranean). The samples were analyzed for total organic carbon, coarse organic carbon (>40 μm), hydrolyzable organic carbon, nitrogen, total amino acids, total and individual sugars (HPLC), lignin-derived compounds (HPLC) and kerogens (acid-soluble, humic substances and humin). Seasonal variations of the organic compounds are related to the sedimentological, hydrodynamical and physico-chemical environmental conditions.The mean annual values of the different organic compounds analyzed show the low quantities and their evolved character at the sediment-water interface: 0.5% total org C (TOC) (d.w.), 0.049% N (d.w.), CN: 11.2, coarse org C (COQ: 62% of TOC, hydrolyzable org C: 45% TOC. The labile compounds represent a low percentage of the total organic matter (TOM), amino-acids: 12% of TOM and sugars: 5% of TOM. The relative proportions of soluble (humic) and insoluble kerogens (humin), respectively 6% and 94% of TOC are typical of a highly evolved organic matter. The large contribution of plant remains confirmed by the high proportion of COC, corresponds to a low proportion of humic substances and a high degree of condensation (HC = 1.3). The infrared spectroscopy determination of the functional groups of the humic substances permits us to confirm both autochtonous (marine) and allochtonous (terrestrial) sources of organic matter in the Têt prodeltaïc accumulation area. Numerous functional groups identified reveal the fresh quality of the organic inputs at the sediment-water interface. Aliphaticity is well marked and nitrogenous compounds (1 and 2 amines) correspond to autochtonous production (in spring: phyto- and zoo-planktonic blooms in the euphotic zone; in summer: primary production under the thermocline and phytobenthic blooms). Sugars are well represented, but from two origins: phytoplanktonic, and issue from terrestrial high plants (ligno-cellulosic complexes). The aromatic functional groups are well identified (aromatic ether, phenol) as are the markers of a large contribution of terrestrial organic matter.The active hydrodynamical (resuspension) and biological, (consumption, bioturbation) events participate in the frequent reworking of the superficial deposits (muddy-silts) and, consequently, the active degradation (oxidization) of the organic matter. The more labile organic matter is rapidly consumed by the intense biological benthic activity. The organic C content is low (0.5% d.w.) except during the autumnal input (2.5% d.w.). This input (8 cm thick) disappears one month later, because of the resuspension induced by littoral currents. This same phenomenon induces during all the year the reworking of the first centimeter of the deposit. In terms of budget of the carbon cycle in the coastal area, this active hydrodynamical environment shows the supremacy of the carbon degradation over its burial.  相似文献   

16.
Analytical methods and their application on the river Rhine for the identification and determination of refractory organic compounds are reported. 18 hydrocarbons, 32 chlorinated hydrocarbons, 13 organic nitro compounds, 14 ethers, 4 alcohols, 9 phenols, 6 esters and 21 other organic compounds have been identified. In view of the tedious methods which have to be applied, a technique for determining the ratio of persistent to biodegradable organic compounds has to be found. Requirements and perspectives of microbiological assays are discussed and rules for the survey of waste discharges are proposed.  相似文献   

17.
A manual SPME method is presented for the analysis of organic compounds in industrial wastewater. 24 compounds commonly found in the wastewater of a chemical plant in northern Germany have been selected as reference compounds. Precision, linearity, and detection limits have been determined. Moreover, the effect of methanol content, pH value, salt content, and an excess of compounds on the extraction process have been studied. Several compounds have been investigated for their applicability as internal standards to quantify the compounds of interest. Since the method will later be transferred to a fully automated SPME-GC system, which will be operated directly on-site at an industrial wastewater purification plant, special attention has been paid to the analysis of real wastewater samples. In this context, the fibre stability has been studied by performing 53 extraction/desorption cycles from one wastewater sample. Neither a decrease in fibre performance nor in precision has been observed indicating that the proposed method is suitable for the analysis of real wastewater.  相似文献   

18.
Geomorphological controls and catchment sediment characteristics control the formation of floodplains and affect their capacity to sequester carbon. Organic carbon stored in floodplains is typically a product of pedogenic development between periods of mineral sediment deposition. However, in organically-dominated upland catchments with a high sediment load, eroded particulate organics may also be fluvially deposited with potential for storage and/or oxidation. Understanding the redistribution of terrestrial carbon laterally, beyond the bounds of river channels is important, especially in eroding peatland systems where fluvial particulate organic carbon exports are often assumed to be oxidised. Floodplains have the potential to be both carbon cycling hotspots and areas of sequestration. Understanding of the interaction of carbon cycling and the sediment cascade through floodplain systems is limited. This paper examines the formation of highly organic floodplains downstream of heavily eroded peatlands in the Peak District, UK. Reconstruction of the history of the floodplains suggests that they have formed in response to periods of erosion of organic soils upstream. We present a novel approach to calculating a carbon stock within a floodplain, using XRF and radiograph data recorded during Itrax core scanning of sediment cores. This carbon stock is extrapolated to the catchment scale, to assess the importance of these floodplains in the storage and cycling of organic carbon in this area. The carbon stock estimate for the floodplains across the contributing catchments is between 3482-13460 tonnes, equating on an annualised basis to 0.8-4.5% of the modern-day POC flux. Radiocarbon analyses of bulk organic matter in floodplain sediments revealed that a substantial proportion of organic carbon was associated with re-deposited peat and has been used as a tool for organic matter source determination. The average age of these samples (3010 years BP) is substantially older than Infrared Stimulated Luminesence dating which demonstrated that the floodplains formed between 430 and 1060 years ago. Our data suggest that floodplains are an integral part of eroding peatland systems, acting as both significant stores of aged and eroded organic carbon and as hotspots of carbon turnover. © 2019 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd.  相似文献   

19.
Lake sediments are valuable natural archives to reconstruct paleoclimate and paleoenvironmental changes which consist of inorganic and organic sediment compounds of allochthonous origin from the catchment and of autochthonous production in the lake. However, for robust paleo-reconstructions it is important to develop a better understanding about sedimentation processes, the origin of inorganic and organic sediment compounds and their distribution within the lake. In this context, modern process studies provide important insights, although environmental and anthropological changes can affect the spatial distribution of sediment compounds through time. Therefore, in this study the spatial distribution of grain size and geochemical proxies in 52 surface sediment samples from Lake Khar Nuur, a small high-altitude lake in the Mongolian Altai with a small and anthropogenically used hydrological catchment, is investigated. The results show a distinct sediment focussing in the two deep basins of the lake, which therefore act as accumulation zones. In those accumulation zones, total organic carbon (TOC), total nitrogen (N) and their isotopic composition (δ13CTOC, δ15N) as well as n-alkanes indicate that organic sediment compounds are a mixture of both allochthonous and autochthonous origin. While the recent catchment vegetation consists of grasses/herbs and the shrub Betula nana (L.) with distinct differences in their n-alkane homologue patterns, those differences are not reflected in the sediment surface samples which rather indicates that grass-derived n-alkanes become preferentially incorporated in the lake. Extensive anthropogenic activity such as grazing and housing in the southern part of the catchment causes soil erosion which is well reflected by high TOC, N and sulphur (S) contents and 15N depleted δ15N values at the central southern shore, i.e. increased allochthonous sediment input by anthropogenically-induced soil erosion. Overall, the surface sediments of Lake Khar Nuur origin from allochthonous and autochthonous sources and are focussed in the accumulation zones of the lake, while their distribution is both environmentally and anthropogenically driven.  相似文献   

20.
Soil-gas surveys are becoming more widely accepted as a tool for the preliminary determination of the extent of soil and ground water contamination by volatile organic compounds (VOCs). The interpretation of the results of published soil-gas surveys has been necessarily limited and qualitative due to a lack of adequate models. There has been considerable effort in the recent past to characterize the transport and fate of pesticides in soil. However, the behavior of pesticides generally differ substantially from those of VOCs.
This paper presents a computer model developed to simulate the diffusive transport of VOC vapor through unsaturated soils using a two-dimensional, finite-difference, solution to Fick's second law of diffusion. An effective diffusion coefficient that incorporates the effects of tortuosity, moisture content, and soil organic carbon content is computed. Although the model has not been validated due to the unavailability of adequate field or laboratory data, nevertheless, sensitivity analyses demonstrate the importance of soil moisture and, secondarily, organic matter content in controlling the migration of VOC vapor through the unsaturated zone. The interpretation of soil-gas surveys can be complicated by unknown spatial heterogeneities in soil moisture and organic carbon content, temporal variations in moisture content, extent of contaminant migration as a non-aqueous phase liquid and by the unknown extent of VOC liquid and contaminated ground water.  相似文献   

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