Carbon isotopic fractionation in lipids from methanotrophic bacteria II: the effects of physiology and environmental parameters on the biosynthesis and isotopic signatures of biomarkers

Controls on the carbon isotopic signatures of methanotroph biomarkers have been further explored using cultured organisms. Growth under conditions which select for the membrane-bound particulate form of the methane monooxygenase enzyme (pMMO) leads to a significantly higher isotopic fractionation than does growth based on the soluble isozyme in both RuMP and serine pathway methanotrophs; in an RuMP type the delta delta 13Cbiomass equaled -23.9% for pMMO and -12.6% for sMMO. The distribution of biomarker lipids does not appear to be significantly affected by the dominance of one or the other MMO type and their isotopic compositions generally track those of the parent biomass. The 13C fractionation behaviour of serine pathway methanotrophs is very complex, reflecting the assimilation of both methane and carbon dioxide and concomitant dissimilation of methane-derived carbon. A limitation in CH4 availability leads to the production of biomass which is 13C-enriched with respect to both carbon substrates and this occurs irrespective of MMO type. This startling result indicates that there must be an additional fractionation step downstream from the MMO reaction which leads to incorporation of 13C-enriched carbon at the expense of dissimilation of 13C-depleted CO2. In these organisms, polyisoprenoid lipids are 13C-enriched compared to polymethylenic lipid which is the reverse of that found in the RuMP types. Serine cycle hopanoids, for example, can vary anywhere from 12% depleted to 10% enriched with respect to the CH4 substrate depending on its concentration. Decrease in growth temperature caused an overall increase in isotopic fractionation. In the total biomass, this effect tended to be masked by physiological factors associated with the type of organism and variation in the bulk composition. The effect was, however, clearly evident when monitoring the 13C signature of total lipid and individual biomarkers. Our results demonstrate that extreme carbon isotopic depletion in field samples and fossil biomarker lipids can be indicative of methanotrophy but the converse is not always true. For example, the hopanoids of a serine cycle methanotroph may be isotopically enriched by more than 10% compared to the substrate methane when the latter is limiting. In other words, hopanoids from some methanotrophs such as M. trichosporium would be indistinguishable from those of cyanobacteria or heterotrophic bacteria on the basis of either chemical structure or carbon isotopic signature.     

Carbon isotopic fractionation associated with lipid biosynthesis by a cyanobacterium: relevance for interpretation of biomarker records

For the cyanobacterium Synechocystis UTEX 2470, grown photoautotrophically to a logarithmic stage of growth, the total lipid extract is depleted in 13C by 4.8% relative to average biomass. Depletions observed for acetogenic (straight-chain) lipids range from 7.6 (hexadecanoic acid) to 9.9% (a C16 n-alkyl chain bound in a polar-lipid fraction), with a mass-weighted average of 9.1%. Polyisoprenoid lipids fall into two isotopic groups, with phytol, diplopterol, and diploptene depleted by 6.4-6.9% and bishomohopanol (produced from the extracts by the preparative degradation of bacteriohopanepolyol) depleted by 8.4%. Analysis of the pattern of depletions indicates that two carbon positions in each C5 biomonomer leading to polyisoprenoid products are probably depleted in 13C relative to average biomass. The depletion of bacteriohopanepolyol relative to other polyisoprenoids can be ascribed to changes that occur over the life of each cell: (1) the 13C content of carbon flowing to lipid biosynthesis decreases as the cell size increases and (2) a greater proportion of the bacteriohopanepolyol which, unlike other polyisoprenoids, is present mainly in the cytoplasm rather than in membranes and is synthesized when cells are larger. Chlorophyll a is depleted relative to average biomass by O.7%. Given the observed depletion of 13C in phytol, the heteroaromatic, chlorophyllide portion of chlorophyll must be enriched in 13C by 2.7%. This enrichment is large relative to that in chlorophyllides produced by eukaryotes and may be related to a parallel enrichment of 13C in cyanobacterial glutamic acid. As in many previous investigations of cyanobacterial lipids, long-chain n-alkanes (C22-C29) are found in the extracts. They are, however, enriched in 13C relative to biomass and have isotopic compositions suggesting that they are contaminants of petrochemical origin. Available results indicate that cyanobacterial lipids will be depleted relative to dissolved CO2 that has served as a carbon source by 22-30% and that a wider range of depletions will be characteristic of eukaryotic products. The absence of long-chain n-alkanes in cyanobacteria reduces the possibility that petroleum ever formed from pre-eukaryotic sedimentary debris.     

Cu isotopic fractionation in the supergene environment with and without bacteria

The isotopic composition of dissolved Cu and solid Cu-rich minerals [δ⁶⁵Cu (‰) = (⁶⁵Cu/⁶³Cu_sample/⁶⁵Cu/⁶³Cu_std) - 1)*1000] were monitored in batch oxidative dissolution experiments with and without Thiobacillus ferrooxidans. Aqueous copper in leach fluids released during abiotic oxidation of both chalcocite and chalcopyrite was isotopically heavier (δ⁶⁵Cu = 5.34‰ and δ⁶⁵Cu = 1.90‰, respectively, [±0.16 at 2σ]) than the initial starting material (δ⁶⁵Cu = 2.60 ± 0.16‰ and δ⁶⁵Cu = 0.58 ± 0.16‰, respectively). Isotopic mass balance between the starting material, aqueous copper, and secondary minerals precipitated in these experiments explains the heavier isotopic values of aqueous copper. In contrast, aqueous copper from leached chalcocite and chalcopyrite inoculated with Thiobacillus ferrooxidans was isotopically similar to the starting material. The lack of fractionation of the aqueous copper in the biotic experiments can best be explained by assuming a sink for isotopically heavy copper present in the bacteria cells with δ⁶⁵Cu = 5.59 ± 0.16‰. Consistent with this inference, amorphous Cu-Fe oxide minerals are observed surrounding cell membranes of Thiobacillus grown in the presence of dissolved Cu and Fe.Extrapolating these experiments to natural supergene environments implies that release of isotopically heavy aqueous Cu from oxidative leach caps, especially under abiotic conditions, should result in precipitates in underlying enrichment blankets that are isotopically heavy. Where iron-oxidizing cells are involved, isotopically heavy oxidized Cu entrained in cellular material may become associated with leach caps, causing the released aqueous Cu to be less isotopically enriched in the heavy isotope than predicted for the abiotic system. Rayleigh fractionation trends with fractionation factors calculated from our experiments for both biotic and abiotic conditions are consistent with large numbers of individual abiotic or biotic leaching events, explaining the supergene chalcocites in the Morenci and Silver Bell porphyry copper deposits.     

Carbon isotope fractionation in phospholipid fatty acid biomarkers of bacteria and fungi native to an acid mine drainage lake

This study identifies isotope signatures associated with autotrophic and heterotrophic microbial communities that may provide a means to determine carbon cycling relationships in situ for acid mine drainage (AMD) sites. Stable carbon isotope ratios (δ¹³C) of carbon sources, bulk cells, and membrane phospholipids (PLFA) were measured for autotrophic and heterotrophic microbial enrichment cultures from a mine tailings impoundment in northern Ontario, Canada, and for pure strains of the sulfur oxidizing bacteria Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. The autotrophic enrichments had indistinguishable PLFA distributions from the pure cultures, and the PLFA cyc-C_19:0 was determined to be a unique biomarker in this system for these sulfur oxidizing bacteria. The PLFA distributions produced by the heterotrophic enrichments were distinct from the autotrophic distributions and the C_18:2 PLFA was identified as a biomarker for these heterotrophic enrichments. Genetic analysis (16S, 18S rRNA) of the heterotrophic cultures indicated that these communities were primarily composed of Acremonium fungi.Stable carbon isotope analysis revealed that bulk cellular material in all autotrophic cultures was depleted in δ¹³C by 5.6–10.9‰ relative to their atmospheric CO₂ derived carbon source, suggesting that inorganic carbon fixation in these cultures is carbon limited. Individual PLFA from these autotrophs were further depleted by 8.2–14.6‰ compared to the bulk cell δ¹³C, which are among the largest biosynthetic isotope fractionation factors between bulk cell and PLFA reported in the literature. In contrast, the heterotrophic bulk cells were not significantly fractionated in δ¹³C relative to their carbon source and heterotrophic PLFA ranged from 3‰ enriched to 4‰ depleted relative to the isotopic composition of their total biomass. These distinct PLFA biomarkers and isotopic fractionations associated with autotrophic and heterotrophic activity in this laboratory study provide potential biomarkers for delineating autotrophic and heterotrophic carbon cycling in AMD environments.     

Factors controlling the distribution of anaerobic methanotrophic communities in marine environments: Evidence from intact polar membrane lipids

Three distinct types of microbial consortia appear to mediate the anaerobic oxidation of methane with sulfate as electron acceptor in marine sediments and are distributed ubiquitously. These consortia consist of ANerobic MEthanotrophic (ANME) archaea of the ANME-1, ANME-2 and ANME-3 clades and their sulfate-reducing bacterial partners either of the Desulfosarcina-Desulfococcus (ANME-1/DSS and ANME-2/DSS) or Desulfobulbus spp. (ANME-3/DBB) branches. Frequently one consortium type dominates the community, but the selective factors are not well constrained. Here we analyzed patterns in the composition of intact polar lipids extracted from bacterial and archaeal communities of different marine seep environments. Further, we investigated if different environmental and geographical factors were responsible for the observed patterns, and hence could be important in the selection of seep communities. Intact polar lipids (IPLs) provide a more robust distinction of the composition of extant communities than their less polar derivatives. In ANME-1/DSS-dominated communities, glycosidic- and phospho-glyceroldialkylglyceroltetraethers were abundant, while ANME-2/DSS and ANME-3/DBB-dominated communities showed abundant archaeol-based IPLs, either with glycosidic and phospho-headgroups or only phospho-headgroups, respectively. The relative proportion of bacterial IPLs varied widely from 0% to 93% and was generally lower in samples of the ANME-1 type, suggesting lower bacterial biomasses in the respective communities. In addition to these lipid signatures, distinctive features were related to the habitat characteristics of these communities: lower amounts of phosphate-based IPLs were generally observed in communities from calcified microbial mats compared to sediments, which may reflect phosphate limitation. Based on statistical analyses of IPLs and environmental data this study constrained for the first time the occurrence of three environmental factors controlling the distribution of different ANME-associated communities in a wide range of hydrocarbon seep systems. Habitats dominated by ANME-1/DSS communities were characterized by high temperature and low oxygen content in bottom waters (or even anoxia), while ANME-2/DSS and ANME-3/DBB-dominated sediments were located in settings with lower temperatures and higher oxygen content in bottom waters. Furthermore, ANME-2/DSS communities were particularly prominent in environments in which a relatively high supply of sulfate was sustained.     

Mineralogical investigations in the interpretation of heavy-mineral geochemical results from till

Heavy-mineral geochemistry and its use in prospecting are based on the fact that some ore minerals (e.g. cassiterite, scheelite, wolframite, chromite, pyrochlore and columbite-tantalite) have a higher specific gravity than the common rock-forming silicates and are highly resistant to weathering in the secondary environment. Till, the most common type of surficial deposit in Finland, is relatively homogeneous and thus constitutes an appropriate sampling material for heavy-mineral geochemical studies. This is especially true in reconnaissance prospecting.The present work concentrates on the interpretation of heavy-mineral anomalies by reference to mineralogical and mineral chemistry data. Tetrabromoethane and a Frantz Isodynamic Separator were used to divide the heavy-mineral samples into subfractions, after which the minerals present were identified by light microscopy, scanning electron microscopy combined with energy-dispersive X-ray spectrometry, electron microprobe techniques and X-ray diffraction.Applications of the methods at three tin anomaly sites in southern Finland are described. The results successfully predicted the presence of a greisen in one area and a pegmatite in another. Those for the third area were somewhat contradictory, the mineralogical composition of the samples suggesting a greisen source for the tin while the composition of the cassiterite pointed to a pegmatite or granite source.     

The geochemical and isotopic record of evaporite recycling in spas and salterns of the Basque Cantabrian basin, Spain

Evaporite outcrops are rare in the Basque Cantabrian basin due to a rainy climate, but saline springs with total dissolved solids ranging from 0.8 to 260 g/L are common and have long been used to supply spas and salterns. New and existing hydrochemistry of saline springs are used to provide additional insight on the origin and underground extent of their poorly known source evaporites. Saline water hydrochemistry is related to dissolution of halite and gypsum from two evaporitic successions (Triassic “Keuper” and Lower Cretaceous “Wealden”), as supported by rock samples from outcrops and oil exploration drill cuttings. The δ³⁴S value of gypsum in the Keuper evaporites and sulfate in the springs is δ³⁴S_SO4 = 14.06 ± 1.07‰ and δ¹⁸O_SO4 = 13.41 ± 1.44‰, and the relationship between Cl/Br ratio of halite and water shows that waters have dissolved halite with Br content between 124 and 288 ppm. The δ³⁴S value of gypsum in the Wealden evaporites and sulfate in the springs is δ³⁴S_SO4 = 19.66 ± 1.76‰, δ¹⁸O_SO4 = 14.93 ± 2.35‰, and the relationship between Cl/Br ratio of halite and water shows that waters have dissolved halite with Br content between 15 and 160 ppm. Wealden evaporites formed in a continental setting after the dissolution of Keuper salt. Gypsum δ³⁴S_SO4 and δ¹⁸O_SO4 modification from Keuper to Wealden evaporites was due mainly to bacterial SO₄ reduction in an anoxic, organic matter-rich environment. Saline springs with Wealden δ³⁴S_SO4 values are present in a 70 × 20 km wide area. Saline water temperatures, their δ²H_H2O and δ¹⁸O_H2O values, and the geological structure defines a hydrogeological model, where meteoric water recharges at heights up to 620 m above spring levels and circulates down to 720 m below them, thereby constraining the height range of evaporite dissolution. Groundwater flow towards saline springs is driven by gravity and buoyancy forces constrained by a thrust and fault network.     

Observations of Li isotopic variations in the Trinity Ophiolite: Evidence for isotopic fractionation by diffusion during mantle melting

The Trinity peridotite (northern CA) contains numerous lithologic sequences consisting of dunite to harzburgite to spinel lherzolite to plagioclase lherzolite. Previous workers have documented geochemical gradients in these sequences consistent with melt-rock reaction processes occurring around dunites, interpreted to reflect conduits for melt ascent. We have undertaken a study of Li isotope compositions of clinopyroxene and some olivine within these sequences using ion probe techniques to test the hypothesis that the geochemical gradients are related to diffusive fluxing of alkali elements into or away from the melt conduit.Results show large variations in ⁷Li/⁶Li occurring in a consistent pattern across three transects from dunite to plagioclase lherzolite within the Trinity peridotite. Specifically, measurements of average δ⁷Li for single thin sections along the traverse reveal a low in δ⁷Li in the harzburgite adjacent to the dunite returning to higher values farther from the dunite with a typical offset of ∼10 per mil in the low δ⁷Li trough. This pattern is consistent with a process whereby Li isotopes are fractionated during diffusion through a melt either from the dunite conduit to the surrounding peridotite, or from the surrounding peridotite into the dunite conduit. The patterns in ⁷Li/⁶Li occur over a length scale similar to the decrease in REE concentration in these same samples. Explaining both the trace element and Li isotopic gradients requires a combined process of alkali diffusion and melt extraction.We develop a numerical model and examine several scenarios of the combined diffusion-extraction process. Using experimentally constrained values for the change in Li diffusion coefficient with isotope mass, large changes in δ⁷Li as a function of distance can be created in year to decade timescales. The addition of the melt extraction term allows larger Li concentration gradients to be developed and thus produces larger isotopic fractionations than diffusion only models. The extraction aspect of the model can also account for the observed decrease in rare earth element concentrations across the transects.     

Origins of non-equilibrium lithium isotopic fractionation in xenolithic peridotite minerals: Examples from Tanzania

Olivine, clinopyroxene and orthopyroxene in variably metasomatised peridotite xenoliths from three lithospheric mantle sections beneath the East African Rift in Tanzania (Lashaine, Olmani, Labait) show systematic differences in their average Li concentrations (2.4 ppm, 2.0 ppm and 1.5 ppm, respectively) and intermineral isotopic fractionations, with olivine being heaviest (δ⁷Li = + 2.3 to + 13.9‰, average + 5.0‰), followed by orthopyroxene (? 4.1 to + 6.5‰, average + 0.8‰) and clinopyroxene (? 6.7 to + 4.1‰, average ? 1.6‰). These features are ascribed to the effects of kinetic Li isotope fractionation combined with different Li diffusivities in mantle minerals.Two main mechanisms likely generate diffusion-driven kinetic Li isotope fractionation in mantle xenoliths (1) Li diffusion from grain boundary melt into minerals during recent metasomatism or entrainment in the host magma and (2) subsolidus intermineral Li-redistribution. The latter can produce both isotopically light (Li-addition) and heavy (Li-loss) minerals and may occur in response to changes in pressure and/or temperature.Modelling shows that non-mantle-like δ⁷Li in clinopyroxene (< + 2‰), combined with apparent equilibrium olivine-clinopyroxene elemental partitioning in most peridotite xenoliths from all three Tanzanian localities probably reflects incipient Li addition during interaction with the host magma. Low δ⁷Li (< ? 3‰), combined with high Li concentrations (> 3 ppm) in some clinopyroxene may require very recent (minutes) Li ingress from a Li-rich melt (100s of ppm) having mantle-like δ⁷Li. This might happen during late fragmentation of some mantle xenoliths caused by a volatile- (and Li-) rich component exsolved from the host basalt. In contrast, high Li concentrations (> 2 ppm) and δ⁷Li (> 4‰) in olivine from many Labait and Olmani samples are attributed to an older, pre-entrainment enrichment event during which isotopic equilibrium was attained and whose signature was not corrupted during xenolith entrainment. Low Li concentrations and mantle-like isotopic composition of olivine from most Lashaine xenoliths indicate limited metasomatic Li addition.Thus, Li concentrations and isotope compositions of mantle peridotites worldwide may reflect two processes, with olivine mainly preserving a signature of depletion in refractory samples (low Li contents and δ⁷Li) or of older (precursory) melt addition in metasomatised samples (high Li contents and δ⁷Li), while non mantle-like, low δ⁷Li in almost all clinopyroxene can be due to Li ingress during transport in the host magma and/or slow cooling, if the samples were erupted in lavas. In Tanzania, the peridotites experienced rift-related heating prior to entrainment and were quenched upon eruption, so Li ingress is the most likely process responsible for the isotopically light clinopyroxene here.     

Carbon and hydrogen isotopic compositions of algae and bacteria from hydrothermal environments,Yellowstone National Park

Stromatolites forming today on a small scale in hydrothermal environments are chemical and biological analogues of much larger Precambrian formations. Carbon isotopic composition varied as a function of CO₂ concentration, pH, and species composition. Stratiform, layered stromatolites grew in silica-depositing springs at 55° to 70°C; they consisted mainly of a unicellular alga, Synechococcus, and a filamentous, photosynthetic bacterium, Chloroflexus. These thermophiles become enriched in ¹²C as the concentration of carbon dioxide in the effluent waters increases. At a concentration of 40 ppm total inorganic C, and δ¹³C of organic carbon was ～ ?12%., whereas at 900 ppm total inorganic C, the δ¹³C of similar species was ～ ?25%.. Conical stromatolites or conophytons (principally a filamentous, blue-green alga Phormidium and Chloroflexus) grew at 40°-55°C. In older, broader conophytons, Chloroflexus was the dominant organism. Their δ¹³C values were ～ ?18%. in a variety of hot springs. In carbonate-depositing springs, i.e., carbon dioxide saturated, conophytons and stromatolites consisting of a variety of blue-green algae and photosynthetic bacteria had the most negative δ¹³C values (to ?30%.). These carbon isotope ratios are directly comparable to carbon isotope ratios of kerogen from Precambrian stromatolites. The presence and activity of methanogenic bacteria or heterotrophic, aerobic and anaerobic bacteria did not alter significantly the δ¹³C of the original organic matter.The hydrogen isotopic fractionation between thermophilic organisms and water is 0 to ?74 for temperatures of 85° to 46°C, respectively. Acidophilic algae fractionated hydrogen isotopes to a lesser extent than did the photosynthetic organisms inhabiting neutral pH springs. Because organic matter retains some of its original isotopic signature, relationships of CO₂ levels, pH, temperature, and species composition between modern stromatolites and their environment and those of the Precambrian can be inferred.     

桂东南大容山-十万大山S型花岗岩带的成因：地球化学及Sr-Nd-Hf同位素制约

本文报道桂东南大容山-十万大山花岗岩带浦北岩体（东北带）、旧州岩体（中部带）和台马岩体（西南带）全岩的主、微量元素、Sr-Nd同位素和锆石的LAM-MC-ICPMS原位Hf同位素分析结果.岩石学及元素地球化学结果显示：上述三个岩体为典型S型花岗岩;高ISr（＞0.721）和低εNd（t）（-13.0～-9.9）意味着它们可能来自古老地壳的重熔.岩浆结晶（～230Ma）锆石的εHf（t）值主要集中在-11～-9,相应的TDM2模式年龄为1.9～1.8 Ga;少数结晶锆石的εHf（t）值逐渐升高到-4.5,TDM2降低为～1.5 Ga.捕获锆石（1681～384 Ma）的的εHf（t）值分布在-17.1～＋3.4,TDM2主要集中在2.4 Ga、1.9 Ga和1.5 Ga.大部分岩浆结晶锆石εHf（t）值与根据＂全岩εNd（t）值和‘地壳Hf-Nd相关＇预测值＂基本一致,表明平均地壳存留年龄为1.9 Ga的地壳是最重要的物源区.部分岩浆锆石与捕获锆石具有相同的TDM2～1.5 Ga,表明平均地壳存留年龄为1.5 Ga的物源区参与了该花岗岩带的形成;由于缺少TDM2＞2.0 Ga的岩浆锆石,少量平均地壳存留年龄为2.4 Ga的再循环地壳物质参与了该花岗岩带的形成.因为缺少显著幔源特征的高εHf（t）值锆石,本文认为地幔物质基本没有参与该S型花岗岩带的形成.     

Equilibrium isotopic fractionation in the kaolinite, quartz, water system: Prediction from first-principles density-functional theory

Isotopic fractionation factors for oxygen, hydrogen and silicon have been calculated using first-principles methods for the kaolinite, quartz, water (ice and gas water) system. Good agreement between theory and experiment is obtained for mineral-water oxygen isotope fractionation. This approach gives reliable results on isotopic fractionation factors as a function of temperature, within a relative precision of typically 5%. These calculations provide independent quantitative constraints on the internal fractionation of oxygen in kaolinite, the fractionation of silicon isotopes at equilibrium, or hydrogen fractionation between kaolinite and water. Calculated fractionation factors at 300 K are 12.5‰ for the kaolinite internal-fractionation of oxygen, and 1.6‰ for silicon fractionation between quartz and kaolinite.     

Carbon isotopic composition of diamonds from the Archangelsk diamond province

The first data are reported on the carbon isotopic composition of diamond crystals from the Grib pipe kimberlite deposit of the Archangelsk diamond province (ADP). The δ¹³C value of the crystals ranges from ?2.79 to ?9.61‰. The isotopic composition of carbon was determined in three zoned crystals (δ¹³C of ?5.8 ?6.96 ‰, ?5.64/ ?5.85 ‰, and ?5.94/ ?5.69 ‰), two “diamond in diamond” samples (diamond inclusion with δ¹³C of ?4.05 and ?6.34 ‰ in host diamond crystals with δ¹³C of ?8.05 and ?7.54 ‰, respectively), and two samples of coated diamonds (cores with δ¹³C of ?6.98 and ?6.78‰ and coats with δ¹³C of ?7.51 and ?8.01 ‰, respectively). δ¹³C values were obtained for individual diamond crystals from bort-type aggregates (δ¹³C of ?4.24/ ?4.05 ‰, ?6.58/ ?7.48 ‰, and ?5.48/ ?6.08 ‰). Correlations were examined between the carbon isotopic composition of diamonds and their crystal morphology; the color; the concentration of nitrogen, hydrogen, and platelet defects; and mineral inclusions content. It was supposed that the observed δ¹³C variations in the crystals are most likely related to the fractionation of carbon isotopes rather than to the heterogeneity of carbon sources involved in diamond formation. The isotopic characteristics of diamonds from the Grib pipe were compared with those of previously investigated diamonds from the Lomonosov deposit. It was found that diamonds from these relatively closely spaced kimberlite fields are different; this also indicates the existence of spatially localized peculiarities of isotope fractionation in processes accompanying diamond formation.     

Improved reliability in the interpretation of geochemical measurements by the quantification of uncertainty from sampling

All geochemical measurements require the taking of field samples, but the uncertainty that this process causes is often ignored when assessing the reliability of the interpretation, of the geochemistry or the health implications. Recently devised methods for the estimation, optimisation and reduction of this uncertainty have been evaluated by their application to the investigation of contaminated land. Uncertainty of measurement caused by primary sampling has been estimated for a range of six different contaminated land site investigations, using an increasingly recognized procedure. These site investigations were selected to reflect a wide range of different sizes, contaminants （organic and metals）, previous land uses （e.g. tin mining, railway sidings and gas works）, intended future use （housing to nature reserves） and routinely applied sampling methods. The results showed that the uncertainty on measurements was substantial, ranging from 25% to 186% of the concentration values at the different sites. Sampling was identified as the dominant source of the uncertainty （〉70% of measurement uncertainty） in most cases. The fitness-for-purpose of the measurements was judged using the optimized contaminated land investigation （OCLI） method. This identifies the optimal level of uncertainty that reduces to overall financial loss caused by the measurement procedures and the misclassification of the contamination, caused by the uncertainty. Generally the uncertainty of the actual measurements made in these different site investigations was found to be sub-optimal, and too large by a factor of approximately two. The uncertainty is usually limited by the sampling, but this can be reduced by increasing the sample mass by a factor of 4 （predicted by sampling theory）. It is concluded that knowing the value of the uncertainty enables the interpretation to be made more reliable, and that sampling is the main factor limiting most investigations. This new approach quantifies this problem for the first time, and allows sampling procedures to be critically evaluated, and modified, to improve the reliability of the geochemical assessment.     

The isotopic effects of electron transfer: An explanation for Fe isotope fractionation in nature

Isotope fractionation of electroplated Fe was measured as a function of applied electrochemical potential. As plating voltage was varied from −0.9 V to 2.0 V, the isotopic signature of the electroplated iron became depleted in heavy Fe, with δ⁵⁶Fe values (relative to IRMM-14) ranging from −0.18(±0.02) to −2.290(±0.006) ‰, and corresponding δ⁵⁷Fe values of −0.247(±0.014) and −3.354(±0.019) ‰. This study demonstrates that there is a voltage-dependent isotope fractionation associated with the reduction of iron. We show that Marcus’s theory for the kinetics of electron transfer can be extended to include the isotope effects of electron transfer, and that the extended theory accounts for the voltage dependence of Fe isotope fractionation. The magnitude of the electrochemically-induced fractionation is similar to that of Fe reduction by certain bacteria, suggesting that similar electrochemical processes may be responsible for biogeochemical Fe isotope effects. Charge transfer is a fundamental physicochemical process involving Fe as well as other transition metals with multiple isotopes. Partitioning of isotopes among elements with varying redox states holds promise as a tool in a wide range of the Earth and environmental sciences, biology, and industry.     

A record of Holocene climate change from lake geochemical analyses in southeastern Arabia

Lacustrine sediments from southeastern Arabia reveal variations in lake level corresponding to changes in the strength and duration of Indian Ocean Monsoon (IOM) summer rainfall and winter cyclonic rainfall. The late glacial/Holocene transition of the region was characterised by the development of mega-linear dunes. These dunes became stabilised and vegetated during the early Holocene and interdunal lakes formed in response to the incursion of the IOM at approximately 8500 cal yr BP with the development of C3 dominated savanna grasslands. The IOM weakened ca. 6000 cal yr BP with the onset of regional aridity, aeolian sedimentation and dune reactivation and accretion. Despite this reduction in precipitation, the lake was maintained by winter dominated rainfall. There was a shift to drier adapted C4 grasslands across the dune field. Lake sediment geochemical analyses record precipitation minima at 8200, 5000 and 4200 cal yr BP that coincide with Bond events in the North Atlantic. A number of these events correspond with changes in cultural periods, suggesting that climate was a key mechanism affecting human occupation and exploitation of this region.     

Evidence for mass-dependent isotopic fractionation of strontium in a glaciated granitic watershed

The stable isotope composition of strontium (expressed as δ^88/86Sr) may provide important constraints on the global exogenic strontium cycle. Here, we present δ^88/86Sr values and ⁸⁷Sr/⁸⁶Sr ratios for granitoid rocks, a 150 yr soil chronosequence formed from these rocks, surface waters and plants in a small glaciated watershed in the central Swiss Alps. Incipient chemical weathering in this young system, whether of inorganic or biological origin, has no resolvable effect on the ⁸⁷Sr/⁸⁶Sr ratios and δ^88/86Sr values of bulk soils, which remain indistinguishable from bedrock in terms of Sr isotopic composition. Although due in part to the chemical heterogeneity of the forefield, the lack of a resolvable difference between soil and bedrock isotopic composition indicates that these soils have thus far witnessed minimal net loss of Sr; a low degree of chemical weathering is also implied by bulk soil chemistry. The isotopic composition of Sr in streamwater is more radiogenic than median soil, reflecting the preferential weathering of biotite in the catchment; streamwater δ^88/86Sr values, however, are indistinguishable from bulk soil δ^88/86Sr values, implying that no resolvable fractionation of Sr isotopes takes place during release to the weathering flux in the Damma forefield. Analyses of plant tissue reveal that plants (Rhododendron and Vaccinium) preferentially assimilate the lighter isotopes of Sr such that their δ^88/86Sr values are significantly lower than those of the soils in which they grow. Additionally, δ^88/86Sr values of foliar and floral tissues are lower than those of roots, contrary to observations for Ca, for which Sr is often used as an analogue in weathering studies. We suggest that processes that discriminate against Sr in favour of Ca, due to the different nutritional requirement of plants for these two elements, are responsible for the observed contrast.     

Surface kinetic model for isotopic and trace element fractionation during precipitation of calcite from aqueous solutions

A surface reaction kinetic model is developed for predicting Ca isotope fractionation and metal/Ca ratios of calcite as a function of rate of precipitation from aqueous solution. The model is based on the requirements for dynamic equilibrium; i.e. proximity to equilibrium conditions is determined by the ratio of the net precipitation rate (R_p) to the gross forward precipitation rate (R_f), for conditions where ionic transport to the growing crystal surface is not rate-limiting. The value of R_p has been experimentally measured under varying conditions, but the magnitude of R_f is not generally known, and may depend on several factors. It is posited that, for systems with no trace constituents that alter the surface chemistry, R_f can be estimated from the bulk far-from-equilibrium dissolution rate of calcite (R_b or k_b), since at equilibrium R_f = R_b, and R_p = 0. Hence it can be inferred that R_f ≈ R_p + R_b. The dissolution rate of pure calcite is measureable and is known to be a function of temperature and pH. At given temperature and pH, equilibrium precipitation is approached when R_p (=R_f − R_b) ? R_b. For precipitation rates high enough that R_p ? R_b, both isotopic and trace element partitioning are controlled by the kinetics of ion attachment to the mineral surface, which tend to favor more rapid incorporation of the light isotopes of Ca and discriminate weakly between trace metals and Ca. With varying precipitation rate, a transition region between equilibrium and kinetic control occurs near R_p ≈ R_b for Ca isotopic fractionation. According to this model, Ca isotopic data can be used to estimate R_f for calcite precipitation. Mechanistic models for calcite precipitation indicate that the molecular exchange rate is not constant at constant T and pH, but rather is dependent also on solution saturation state and hence R_p. Allowing R_b to vary as , consistent with available precipitation rate studies, produces a better fit to some trace element and isotopic data than a model where R_b is constant. This model can account for most of the experimental data in the literature on the dependence of ⁴⁴Ca/⁴⁰Ca and metal/Ca fractionation in calcite as a function of precipitation rate and temperature, and also accounts for ¹⁸O/¹⁶O variations with some assumptions. The apparent temperature dependence of Ca isotope fractionation in calcite may stem from the dependence of R_b on temperature; there should be analogous pH dependence at pH < 6. The proposed model may be valuable for predicting the behavior of isotopic and trace element fractionation for a range of elements of interest in low-temperature aqueous geochemistry. The theory presented is based on measureable thermo-kinetic parameters in contrast to models that require hyper-fast diffusivity in near-surface layers of the solid.     

Ga isotopic fractionation in sulfides from the Yuhuang and Duanqiao hydrothermal fields on the Southwest Indian Ridge

This study examines the Ga isotopic compositions of sulfides in the Yuhuang and Duanqiao hydrothermal fields on the Southwest Indian Ridge,mid-ocean ridge basalts(MORB),and calcareous sediments around the hydrothermal fields.The δ~(71/69)Ga_(NIST-994) values of the MORB samples vary little(+1.20‰ to +1.23‰,with an average of +1.22‰) and are consistent with the δ~(71/69)Ga_(NIST-994) values of two standard basalt samples(BCR-2 and BHVO-2),indicating that Ga isotopes may either not fractionate or fractionate only slightly under high-temperature geological processes;therefore,the δ~(71/69)Ga_(NIST-994) value of oceanic crust may be +1.22‰.The sediments(+1.28‰to +1.47‰,with an average of +1.38‰) are rich in heavier Ga isotopes than the basalts,and the Ga present in the sediments may have originated from soluble Ga present in the seawater that was adsorbed by(Mn,Fe) oxides/hydroxides.The Ga contribution of basaltic debris to the sediments was almost negligible.Thus,we speculate that the δ~(71/69)Ga_(NIST-994) value of seawater in the study area fell within a range from +1.92‰ to +2.36‰.The δ~(71/69)Ga_(NIST-994) values of the sulfides in the Yuhuang hydrothermal field range from +0.99‰ to +1.57‰,with an average of +1.25‰,and the δ~(71/69)Ga_(NIST-994) values of the sulfides in the Duanqiao hydrothermal field range from+0.93‰ to +1.55‰,with an average of +1.19‰.The δ~(71/69)Ga_(NIST-994) ranges of the sulfides in the Yuhuang and Duanqiao hydrothermal fields are similar,with the Ga isotopic fractionation reaching 0.58‰ and 0.62‰,respectively.The average δ~(71/69)Ga_(NIST-994) values in the sulfides are close to those in the MORBs.This suggests that Ga within the sulfides in the Yuhuang and Duanqiao hydrothermal fields mainly originated from MORBs,with seawater and sediments making only small contributions.The Ga isotopic fractionation in the sulfides may be related to processes associated with the formation of sulfides,such as rapid precipitation or the admixture of different stages of sulfide.This study is of great significance for understanding the global distribution of Ga isotopes and the Ga cycle in submarine hydrothermal systems.     

Q'gas: a minicomputer-based system to aid in the interpretation of exploration-oriented geochemical data

The past few years have seen an increasing application of computer-based procedures in the processing and interpretation of geochemical data. In many cases this has been carried out by non-geologists using large, general purpose computers remote from the exploration effort. In such situations, appreciation of the geological nature of the problems is often inadequate and in a number of cases misapplication of procedures has resulted. The present paper describes the Q'GAS system which consists of a minicomputer and a series of compatible interactive programs. These programs can be used independently by geologists who have a minimum of experience with computers allowing them the opportunity to carry out personally the processing and interpretation of geochemical data and to ensure that the methodology is based on a firm geological framework. The expense of such a system is relatively low: approximately $25,000 capital costs, and $3500 per year running costs including a maintenance contract. In addition approximately one man-month per year is required for supervision and up-keep.The system has the capability of: (a) selecting subgroups of samples that meet specified criteria (e.g. specific rock type or value ranges); (b) transforming data (addition, subtraction, multiplication, division, logarithms, exponentiation and random number generation); (c) making statistical computations; and (d) producing graphical displays (e.g. histograms, X-Y plots, symbol maps etc.). Flexible diskettes are used for data storage and communication with the system is achieved through a video terminal. Hard-copy output is produced on a small printer. The system presently includes programs for data management, univariate statistics with histograms, correlation analysis, X-Y plots, line printer symbol maps, line printer geochemical profiles, multiple linear regression, discriminant analysis, and R-mode factor analysis. Attention is presently being given to developing programs that use a pen plotter for producing better quality maps and diagrams at any scale.Experience has shown that the simpler programs for construction of maps, graphs, and diagrams can provide an immediate improvement in the quality, thoroughness, and speed of data interpretation as well as significantly reducing the tedium associated with manual methods. The multivariate statistical techniques, as always, require a higher level of expertise and many more man hours if they are to be used successfully.