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1.
生物降解作用下地下水中TCE、PCE迁移转化的数值模拟研究   总被引:8,自引:0,他引:8  
根据室内三氯乙烯(TCE)、四氯乙烯(PCE)运移转化的土柱实验和研究区地下水化学特征,建立了研究区微生物作用下TCE、PCE迁移转化的数学模型,并进行了计算机数值模拟,模拟结果与实测值基本一致,表明本次研究建立的数学模型是正确的,研究区地下水中存在生物降解作用,为下一步有机污染的治理提供了科学依据。  相似文献   

2.
Errors of isotope ratios acquired by double interpolation   总被引:1,自引:0,他引:1  
Kenneth Ludwig   《Chemical Geology》2009,268(1-2):24-26
Measurement of isotope ratios via double interpolation of cyclic peak jumping produces error correlations between time-adjacent ratios which, if ignored, result in underestimated errors of their means. Equations that incorporate the error correlations are derived, and an example given for a typical U–Pb/zircon analysis via ion microprobe showing that isotope-ratio uncertainties for a single spot are usually underestimated by factors of 1.2–1.3.  相似文献   

3.
利用多接收电感耦合等离子体质谱仪(Neptune plus)建立了高精度铅同位素比值MC-ICP-MS测试方法。建立该方法的过程中,重点评估了加入的Tl标准溶液对铅同位素比值测试结果的影响,并最终确定Tl标准溶液的浓度为25 ng/mL,同时样品溶液Pb的浓度应该大于25 ng/mL(即Pb/Tl浓度比应大于1)。利用该方法对铅同位素标准物质SRM 981进行了长期监控(2020年7月—2021年6月),测试结果为:206Pb/204Pb=16.9415±0.0010、207Pb/204Pb=15.4985±0.0009、208Pb/204Pb=36.7204±0.0023,与统计的文献报道值一致。长期监控的全流程空白均小于0.25 ng,能满足地质样品高精度铅同位素比值测试的需要。同时运用该方法,对4个元素含量标样(BCR-2、AGV-2、BHVO-2和BIR-1a)进行了铅同位素比值测试,测试结果与文献报道的测试结果和精度一致,表明建立的方法是准确、可靠的。  相似文献   

4.
《Applied Geochemistry》2000,15(4):501-512
Using a flexible Au bag autoclave and a precision high-pressure liquid chromatography pump to control pressure, the liquid–liquid aqueous solubilities of TCE and PCE were measured as a function of temperature from 294 to 434 K (at constant pressure). The results were used to calculate the partial molal thermodynamic quantities of the organic liquid aqueous dissolution reactions: Δsoln, Δsoln, Δsoln and Δp soln. Calculated values for these quantities at 298 K for TCE are: Δsoln=11.282 (±0.003) kJ/mol, Δsoln=−3.35 (±0.07) kJ/mol, Δsoln=−49.07 (±0.24) J/mol K, and Δp soln=385.2 (±3.4) J/mol K. Calculated values for these quantities at 298 K for PCE are: Δsoln=15.80 (±0.04) kJ/mol, Δsoln=−1.79 (±0.58) kJ/mol, Δsoln=−59.00 (±1.96) J/mol K and Δp soln=354.6 (±8.6) J/mol K. These thermodynamic quantities may be used to calculate the solubility of TCE and PCE at any temperature of interest. In the absence of direct measurements over this temperature range, the Henry's Law constants for TCE and PCE have been estimated using the measured aqueous solubilities and calculated vapor pressures.  相似文献   

5.
High precision Sr-Nd isotope ratios together with Pb isotope ratios corrected for mass fractionation using a double spike are reported for an extensive suite of late Quaternary to Recent lavas of Iceland, the Kolbeinsey and Reykjanes Ridges, and a small number of basalts from further south on the Mid-Atlantic Ridge. Compared with global MORB, the Icelandic region is distinguished by having low 207Pb/204Pb for any given 206Pb/204Pb, expressed by negative Δ207Pb (−0.8 to −3.5) in all but four Icelandic samples. Most samples also have elevated 208Pb/204Pb (strongly positive Δ208Pb), which combined with their negative Δ207Pb is very unusual in MORB worldwide. The negative Δ207Pb is interpreted as a consequence of evolution in high-μ mantle sources for the last few hundred Ma. The region of negative Δ207Pb appears to correspond with the region of elevated 3He/4He, suggesting that both lithophile and volatile elements in melts from the whole region between 56 and 70°N are dominantly sourced in a plume that has incorporated recycled Palaeozoic ocean crust and unradiogenic He, probably from the deep mantle. At least four mantle components are recognized on Iceland, two with an enriched character, one depleted and one that shows some isotopic affinities to EM1 but is only sampled by highly incompatible-element-depleted lavas in this study. Within restricted areas of Iceland, these components contribute to local intermediate enriched and depleted components that display near binary mixing systematics. The major depleted Icelandic component is clearly distinct in Pb isotopes from worldwide MORB, but resembles the depleted mantle source supplying the bulk of the melt to the Kolbeinsey and southern Reykjanes Ridges. However, an additional depleted mantle source is tapped by the northern Reykjanes Ridge, which with very negative Δ207Pb and less positive Δ208Pb is distinct from all Icelandic compositions. These components must mostly mix at mantle depths because a uniform mixture of three Icelandic components is advected southward along the Reykjanes Ridge.Despite strong covariation with isotope ratios, incompatible trace element ratios of Icelandic magmas cannot be representative of old mantle sources. The observed parent-daughter ratios in depleted and enriched Icelandic lavas would yield homogeneous Sr, Nd, Hf and 206Pb isotope signatures ∼170 Ma ago if present in their sources. The heterogeneity in 207Pb/204Pb is not however significantly reduced at 170 Ma, and the negative present day Δ207Pb cannot be supported by the low μ observed in depleted lavas from Iceland or the adjacent ridges. Since μ is higher in melts than in their sources, it follows that all the depleted sources must be residues from <170 Ma partial melting events. These are thought to have strongly affected most incompatible trace element ratios.  相似文献   

6.
氩同位素用于库车坳陷天然气主力气源岩判识   总被引:7,自引:0,他引:7  
稀有气体是天然气中指示其地球化学特征的重要组分,放射成因氩( Arr)的年代积累效应广泛应用于同位素定年和天然气的气源对比.本文系统地讨论了 40Ar的形成机理及其运移进入气藏的过程,利用 40Ar的母体元素 K在煤和煤系泥岩中的丰度差异,分析了以煤和煤系泥岩为母源的天然气 40Ar/36Ar同位素组成上的不同,并利用这种差异对煤系中煤岩或煤系泥岩为源岩的天然气藏的主力源岩进行了判识,继而建立了利用氩同位素组成判识煤系烃源岩主力源岩的方法.利用此方法对塔里木盆地库车坳陷三叠系-侏罗系煤与煤系泥岩互层的烃源岩进行了探讨, 数学计算结果表明该区主力源岩为煤系泥岩, 煤对天然气藏的贡献较小.  相似文献   

7.
Silicon isotope ratios (δ30Si) of bulk mineral materials in soil integrate effects from both silicon sources and processing. Here we report δ30Si values from a climate gradient of Hawaiian soils developed on 170 ka basalt and relate them to patterns of soil chemistry and mineralogy. The results demonstrate informative relationships between the mass fraction of soil Si depletion and δ30Si. In upper (<1 m deep) soil horizons along the climate gradient, Si depletion correlates with decreases of residual δ30Si values in low rainfall soils and increases in high rainfall soils. Strong positive correlation between soil δ30Si and dust-derived quartz and mica content show that both trends are largely controlled by the abundance of these weathering-resistant minerals. The data also lend support to the idea that fractionation of Si isotopes in secondary phases is controlled by partitioning of silicon between dissolved and precipitated products during the initial weathering of primary basalt. Secondary mineral δ30Si values from lower (>1 m deep) soil horizons generally correlate with the isotope fractionation predicted by a study of dissolved Si in basalt-watershed rivers and driven by preferential 28Si removal from the dissolved phase during precipitation. In contrast, after correcting for the influence of dust, secondary mineral Si depletion and δ30Si values in shallow (<1 m deep) soil horizons showed evidence of biocycling induced Si redistribution and substantially lower δ30Si values than predicted. Low δ30Si values in shallow soil horizons compared to predictions can be attributed to repeated fractionation as secondary minerals undergo additional cycles of dissolution and precipitation. Primary mineral weathering, secondary mineral weathering, dust accumulation, and biocycling are major processes in terrestrial Si cycling and these results demonstrate that each can be traced by δ30Si values interpreted in conjunction with mineralogy and measures of Si depletion.  相似文献   

8.
The Mushandike Sanctuary, near Masvingo (Fort Victoria), Zimbabwe, contains well-preserved, but metamorphosed stromatolitic limestones of Archaean age. Despite the metamorphism, textural preservation is excellent to a scale as fine as c. 100–200μ. Cores recovered from the stromatolites have δ18O = ?15‰ (PDB), approximately, and δ13C = 0.0 to 0.5‰ (PDB), in less weathered samples. The results are consistent with a metamorphic history involving volatile loss at 200°C or less, from an original source rock which may have been isotopically similar to the Cheshire stromatolites, Belingwe.  相似文献   

9.
Fresh submarine basalt glasses from Galapagos Ridge, FAMOUS area, Cayman Trough and Kilauea east rift contain 22 to 160 ppm carbon and 0.3 to 2.8 ppm nitrogen, respectively, as the sums of dissolved species and vesicle-filling gases (CO2 and N2). The large range of variation in carbon content is due to combined effect of depth-dependency of the solubility of carbon in basalt melt and varying extents of vapour loss during magma emplacement as well as in sample crushing. The isotopic ratios of indigenous carbon and nitrogen are in very narrow ranges,?6.2 ± 0.2% relative to PDB and +0.2 ± 0.6 %. relative to atmospheric nitrogen, respectively. In basalt samples from Juan de Fuca Ridge, however, isotopically light carbon (δ13C = around ?24%.) predominates over the indigenous carbon; no indigenous heavy carbon was found. Except for Galapagos Ridge samples, these ocean-floor basalts contain 670 to 1100 ppm sulfur, averaging 810 ppm, in the form of both sulfide and sulfate, whereas basalts from Galapagos Ridge are higher in both sulfur (1490 and 1570 ppm) and iron (11.08% total iron as FeO). The δ34S values average +0.3 ± 0.5%. with average fractionation factor between sulfate and sulfide of +7.4 ± 1.6%.. The sulfate/sulfide ratios tend to increase with increasing water content of basalt, probably because the oxygen fugacity increases with increasing water content in basalt melt.  相似文献   

10.
Large variations are reported in the B concentrations and isotopic ratios of river and thermal spring waters in Guadeloupe, Lesser Antilles. Rivers have δ11B values around 40‰ and B concentrations lower than 30 μg/L, while thermal springs have δ11B of 8–15‰ and B concentrations of 250–1000 μg/L. River samples strongly impacted by hydrothermal inputs have intermediate δ11B and B contents. None of these surface water samples have δ11B comparable to the local unweathered volcanic rocks (around 0‰), implying that a huge isotopic fractionation of 40‰ takes place during rock weathering, which could be explained by preferential incorporation of 10B during secondary mineral formation and adsorption on clays, during rock weathering or in the soils. The soil-vegetation B cycle could also be a cause for such a fractionation. Atmospheric B with δ11B of 45‰ represents 25–95% of the river B content. The variety of the thermal spring chemical composition renders the understanding of B behavior in Guadeloupe hydrothermal system quite difficult. Complementary geochemical tracers would be helpful.  相似文献   

11.
The Klyuchevskoy group of volcanoes in the Kamchatka arc erupts compositionally diverse magmas (high-Mg basalts to dacites) over small spatial scales. New high-precision Pb isotope data from modern juvenile (1956–present) erupted products and hosted enclaves and xenoliths from Bezymianny volcano reveal that Bezymianny and Klyuchevskoy volcanoes, separated by only 9 km, undergo varying degrees of crustal processing through independent crustal columns. Lead isotope compositions of Klyuchevskoy basalts–basaltic andesites are more radiogenic than Bezymianny andesites (208Pb/204Pb = 37.850–37.903, 207Pb/204Pb = 15.468–15.480, and 206Pb/204Pb = 18.249–18.278 at Bezymianny; 208Pb/204Pb = 37.907–37.949, 207Pb/204Pb = 15.478–15.487, and 206Pb/204Pb = 18.289–18.305 at Klyuchevskoy). A mid-crustal xenolith with a crystallization pressure of 5.2 ± 0.6 kbars inferred from two-pyroxene geobarometry and basaltic andesite enclaves from Bezymianny record less radiogenic Pb isotope compositions than their host magmas. Hence, assimilation of such lithologies in the middle or lower crust can explain the Pb isotope data in Bezymianny andesites, although a component of magma mixing with less radiogenic mafic recharge magmas and possible mantle heterogeneity cannot be excluded. Lead isotope compositions for the Klyuchevskoy Group are less radiogenic than other arc segments (Karymsky—Eastern Volcanic Zone; Shiveluch—Northern Central Kamchatka Depression), which indicate increased lower-crustal assimilation beneath the Klyuchevskoy Group. Decadal timescale Pb isotope variations at Klyuchevskoy demonstrate rapid changes in the magnitude of assimilation at a volcanic center. Lead isotope data coupled with trace element data reflect the influence of crustal processes on magma compositions even in thin mafic volcanic arcs.  相似文献   

12.
利用MC-ICPMS对水样中硼同位素比值的测定   总被引:2,自引:0,他引:2  
采用Amberlite IRA-743硼特效树脂进行水溶液中硼的分离,对洗脱液温度、体积以及树脂动态交换容量等进行了实验.它的动态交换容量为4.2 mg/g,在室温条件下,用5 mL 2%HNO3可定量从树脂柱上洗脱被吸附的硼.采用Neptune型MC-ICPMS进行硼同位素组成的测定,1 μg/g浓度的硼标准溶液获得放大的信号强度约为0.7V,硼的化学分离过程有效避免了质量歧视效应.实验结果表明,MC-ICPMS对硼存在严重的记忆效应,通过采用5%HNO3-(1%HNO3 0.1%HF)-H2O-20%NH3H2O-H2O的交替清洗方法,可在约1 h内消除硼的记忆效应.在最佳仪器条件下,对含有250 ng硼的水样,可以快速测定硼的同位素组成,占δ11B测定的绝对偏差为0.4‰-0.5‰(SD).  相似文献   

13.
We introduce the use of Nd isotopes as a high‐precision technique that can be used in conjunction with visual, petrographic, and trace element analyses to source indistinct felsitic debitage. This approach allows sourcing of debitage from southeastern New England, including samples that previously could not be constrained to one source. Combined with trace element data, isotopic data also provide the possibility of sourcing debitage to a particular quarry site within a volcanic complex, and even to a particular ash flow within a quarry site. Determining the origin of debitage so precisely is important for understanding acquisition, trade, and exchange networks in southeastern New England, where distances separating quarry sites within an individual volcanic complex (Lynn–Mattapan) are greater than distances between different volcanic complexes (Lynn–Mattapan, Blue Hill, and Wamsutta). The sourcing of debitage to Mattapan quarries suggests that Middle Archaic populations in the northwest part of the Boston Basin obtained nonlocal lithic material primarily from sources south of the basin. © 2000 John Wiley & Sons, Inc.  相似文献   

14.
Anomalous Pb isotope ratios measured by Inductively Coupled Plasma Mass Spectrometry in terrigenous marine sediments (<63 μm fraction) from the Gulf of Carpentaria originated from depositional mixing of clay/silt with average modern crustal Pb isotope ratios and detrital monazite with high 208Pb/206Pb and low 207Pb/206Pb. This interpretation is supported by strong correlations between Pb isotope ratio and Th, U and light rare‐earth element concentrations in the sediments as well as by monazite compositional data. A likely source of the detrital monazite is the western portion of the Georgetown Inlier of mainly Proterozoic S‐type granitic rocks. A clear distinction between Pb isotope ratios in sediments deposited from the Norman and Bynoe Rivers in the southeast Gulf of Carpentaria and the persistence of catchment‐specific Pb isotope ratios 45 km offshore suggest that Pb isotope data are useful in tracing the provenance of terrigenous offshore sediments when the source rocks of catchments show sufficient chemical and/or mineralogical variation.  相似文献   

15.
《Applied Geochemistry》1995,10(5):547-552
Stable Cl and C isotope ratio results for 3 selected chlorinated solvents, perchloroethylene (PCE), trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA) provided by 4 different manufacturers are presented. The isotope ratio for all compounds range between −3.5 and +6.0‰ forδ37Cl and from −37.2 to −23.3%. forδ13C. The greatest37Cl difference between manufacturers is observed in the TCE samples which showδ37CI values of −2.5%o for PPG, +2.43‰ for ICI and +4.4‰ for DOW. TCAs show a smaller range (−2.4 to +2.0‰), while the TCEs have slightly different37Cl contents. The13C data show the most distinctδ13C values for PCEs (−23.3 for DOW, −24.1 for Vulcan, −33.8 for PPG and −37.2‰ for ICI) while both TCEs and TCAs show a smallerδ13C range, but still distinct differences. These preliminary data suggest that each manufacturer and solvent type may have distinctiveδ637Cl andδ13C values. These results show that by using a combination of37Cl and13C, there is a potential to indicate a specific source of chlorinated solvents, as well as an ability to delineate contamination episodes caused by these compounds in groundwaters.  相似文献   

16.
《Applied Geochemistry》2006,21(4):547-562
Reducing the concentration of dissolved organic C (DOC) in water is one of the main challenges in the process of artificial groundwater recharge. At the Tuusula waterworks in southern Finland, surface water is artificially recharged into an esker by pond infiltration and an equal amount of groundwater is daily pumped from the aquifer. This groundwater study was conducted to consider the role of redox processes in the decomposition of DOC. The isotopic composition of dissolved inorganic C (δ13CDIC) in the recharged water was used as a tracer for redox reactions. The isotopic composition of O and H in water was determined in order to calculate mixing ratios between the local groundwater and the infiltrated surface water. Three distinct processes in the reduction of the DOC content were traced using isotopic methods and concentration analyses of DIC and DOC: (1) the decomposition of DOC, (2) adsorption of DOC on mineral matter, and (3) the dilution of artificially recharged water by mixing with local groundwater. The largest decrease (44%) in the DOC content occurred during the early stage of subsurface flow, within 350 m of the infiltration ponds. The reduction of DOC was accompanied by an equal increase in DIC and a significant drop in δ13CDIC. This change is attributed to the oxidative decomposition of DOC. A further 23% decrease in DOC is attributed to adsorption and a final drop of 14% to dilution with local groundwater.  相似文献   

17.
The δ O18 and δ Si30 analyses of the Luna 20 soil sample are +6.18 and +0.22, respectively, relative to the SMOW and Rose Quartz standards. However, an anomalous δ O18 value of +8.13 was obtained on one aliquot of the Luna 20 sample. Possible reasons for this apparently erroneous result are discussed.  相似文献   

18.
陈云如  田军 《第四纪研究》2016,36(3):587-597
植物利用周围环境中的水分进行光合作用合成有机质, 其叶蜡氢同位素记录了源水中的氢同位素组成, 被认为是重建古水循环的替代性指标。然而从源水(降水)到合成叶蜡脂类化合物, 降水中的氢同位素会发生多步分馏作用。本文综述了对氢同位素分馏造成影响的因素及其校正方法, 通过有效的数据处理, 叶蜡氢同位素可以比较直接地反映降水的氢同位素组成。由于在热带地区降水氢同位素受"雨量效应"影响较大, 所以可以较好地反映降水量变化, 在非洲大陆常被用于重建水循环和气候变化; 在东亚大陆,"雨量效应"不再那么显著, 水汽的来源可能在影响降水氢同位素组成的过程中也起到了重要作用。  相似文献   

19.
For modelling isotopic variations in oils it is convenient to differentiate the effects of oil generation ( 100–150°C) from the effects of oil to gas cracking ( 150–180°C). During generation, δ13C of kerogen may increase by up to 1% due to release of isotopically light oil and gas, although most kerogens show little or no chan δ13C of the generated oil increases by between 0 and 1% (av. 0.5%) due to mixing of isotopically heavy oil with an initial isotopically light unbound fraction, possibly of bacterial origin. The change occurs mostly over the first 20% of generation. During oil to gas cracking, kinetic isotope effects become important and the effect on δ13C of the remaining oil can be modelled as a Rayleigh process. δ13C increases by 1.5% by 50% cracking. Insufficient data are available to calibrate the effects at higher levels of cracking, and modelling these variations is hindered by a lack of understanding of the mechanism of pyrobitumen formation. However, increases greater than about 4% are unlikely to be observed. With increasing maturity, the low molecular weight fractions become isotopically heavy faster than the high molecular weight fractions. As a result, any separation of the low molecular weight fraction into a gas phase (“condensate formation”) will produce an isotopic difference between oil and condensate that depends on maturity. In the early stages of generation the condensate may be up to 1% lighter than the remaining oil. With increasing maturity, this difference at first decreases and then increases in the opposite sense. By half way through oil to gas cracking the condensate may be 1.5% heavier than the residual liquid. More subtle rearrangement reactions may result in small, but significant, changes to the shape of the isotope “type-curves” when different oil fractions are compared.  相似文献   

20.
Eighteen basalts and some volcanic gases from the submarine and subaerial parts of Kilauea volcano were analyzed for the concentration and isotope ratios of sulfur. By means of a newly developed technique, sulfide and sulfate sulfur in the basalts were separately but simultaneously determined. The submarine basalt has 700 ± 100 ppm total sulfur with δ34SΣs of 0.7 ± 0.1 ‰. The sulfate/sulfide molar ratio ranges from 0.15 to 0.56 and the fractionation factor between sulfate and sulfide is +7.5 ± 1.5‰. On the other hand, the concentration and δ34SΣs values of the total sulfur in the subaerial basalt are reduced to 150 ± 50 ppm and ?0.8 ± 0.2‰, respectively. The sulfate to sulfide ratio and the fractionation factor between them are also smaller, 0.01 to 0.25 and +3.0‰, respectively. Chemical and isotopic evidence strongly suggests that sulfate and sulfide in the submarine basalt are in chemical and isotopic equilibria with each other at magmatic conditions. Their relative abundance and the isotope fractionation factors may be used to estimate the ?o2 and temperature of these basalts at the time of their extrusion onto the sea floor. The observed change in sulfur chemistry and isotopic ratios from the submarine to subaerial basalts can be interpreted as degassing of the SO2 from basalt thereby depleting sulfate and 34S in basalt.The volcanic sulfur gases, predominantly SO2, from the 1971 and 1974 fissures in Kilauea Crater have δ34S values of 0.8 to 0.9%., slightly heavier than the total sulfur in the submarine basalts and definitely heavier than the subaerial basalts, in accord with the above model. However, the δ34S value of sulfur gases (largely SO2) from Sulfur Bank is 8.0%., implying a secondary origin of the sulfur. The δ34S values of native sulfur deposits at various sites of Kilauea and Mauna Loa volcanos, sulfate ions of four deep wells and hydrogen sulfide from a geothermal well along the east rift zone are also reported. The high δ34S values (+5 to +6%.o) found for the hydrogen sulfide might be an indication of hot basaltseawater reaction beneath the east rift zone.  相似文献   

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