Use of B isotopes as a tracer of anthropogenic emissions in the atmosphere of Paris,France

In order to test the potential of B isotopes as a tracer of contamination of the atmosphere, the B isotopic composition of rainwater samples monitored over a year in the centre of Paris, France were determined. Boron concentrations range from 19 nmol/L to 500 nmol/L and δ¹¹B range from 0‰ to +38‰. Mean annual values are 148 nmol/L and +25‰, respectively. The results suggest that variability in B isotopic compositions is mainly caused by mixing of two main sources, although isotopic fractionation during the evaporation–condensation processes may also be important. One source is a marine component, which exhibits a heavy B isotopic composition. The decrease of δ¹¹B in rainwater with increasing NO₃/B and SO₄/B molar ratios suggests that a second source may be anthropogenic emissions. To constrain this end-member, B was determined in urban particulates, which were enriched in the light isotope and the lowest values were consistent with a B-rich fossil fuel composition. These results confirm the great sensitivity of B to anthropogenic sources and the ability of B isotopic ratios to decipher the origin of B in the atmosphere.     

Uranium isotopes as a tracer of sources of dissolved solutes in the Han River,South Korea

The uranium (U) content and ²³⁴U/²³⁸U activity ratio were determined for water samples collected from Korea's Han River in spring, summer, and winter 2006 to provide data that might constrain the origin of U isotope fractionation in river water and the link between U isotope systematics in river waters and the lithological nature of the corresponding bedrock. The large difference in the major dissolved loads between the two major branches of the Han River, the North Han River (NHR) and South Han River (SHR), is reflected in the contrasting U content and ²³⁴U/²³⁸U activity ratio between the tributaries: low U content (0.08–0.75 nM; average, 0.34 nM) and small ²³⁴U/²³⁸U activity ratio (1.03–1.22; average, 1.09) in the NHR; and high U content (0.65–1.98 nM; average, 1.44 nM) and large ²³⁴U/²³⁸U activity ratio (1.05–1.45; average, 1.24) in the SHR. The large spatial differences in U content and ²³⁴U/²³⁸U activity ratio are closely related to both lithological differences between the two tributaries and groundwater input. The low U content and small ²³⁴U/²³⁸U activity ratio in the NHR arise mainly from a combination of surface and meteoric weathering of the dominant silicate rocks in this branch and congruent dissolution of already weathered (secular equilibrium) materials. In contrast, the high U content and large ²³⁴U/²³⁸U activity ratio in the SHR are ascribed to the dissolution of carbonates and black shales along with significant inputs of deep groundwater.     

Boron isotopes in tourmaline as a tracer of metasomatic processes in the Bamble sector of Southern Norway

The Bamble sector of southern Norway comprises metagabbros and metasediments that were metasomatically altered to various extents during a late stage of the Sveconorwegian orogeny (~1.06 Ga). The infiltration of highly saline brines along veins led to penetrative scapolitization and albitization on a regional scale and the local deposition of Fe–Ti oxides. Typical secondary mineral assemblages include either scapolite + apatite + amphibole + phlogopite + tourmaline, or albite + epidote + calcite + chlorite + white mica, indicating that the fluids introduced large amounts of Na, Cl, Mg, Ca, K, P, and B to the system. Metasomatic tourmalines associated with different alteration stages as identified by variations in major-element composition and initial ⁸⁷Sr/⁸⁶Sr were analyzed for B isotopic compositions to constrain possible sources and the evolution of the hydrothermal fluid(s). Measured δ¹¹B values range from ?5 to +27 ‰ relative to SRM-951, suggesting marine evaporites interlayered with various amounts of continental detritus and pelagic clay as a possible B source reservoir. The influence of a seawater-derived component is clearly indicated by the heavy B isotope signature of tourmaline related to Al–Mg-rich metapelites. In contrast, negative δ¹¹B values can be explained by the influence of pneumatolytic fluids associated with granitic pegmatites. On a regional scale (i.e., several km), δ¹¹B values in tourmaline vary widely, whereas variations within a single outcrop (tens of m) are typically small and can be ascribed to different generations of tourmaline related to several fluid pulses.     

Natural isotopic composition of nitrogen as a tracer of origin for suspended organic matter in the Scheldt estuary

The natural isotopic composition of suspended particulate organic nitrogen was determined in the Southern Bight of the North Sea and in the Scheldt estuary. These data show that δ¹⁵N constitutes a convenient tracer of the origin of the suspended matter.In the winter, in the absence of intensive primary production, the suspended organic matter of the Scheldt estuary is a mixture of two components: a continental detrital component characterized by a low δ value of 1.5%. and a marine component with a mean δ value of 8%..During the phytoplankton flowering period, lasting from early May to October, intensive primary production occurs throughout the estuary giving rise to a third source of organic matter. This material is characterized by high δ values reflecting the isotopic composition of ammonia, the nitrogenous nutrient assimilated by phytoplankton in the estuary.The nitrification process occuring in the mixing area of the Scheldt estuary leads to higher downstream δ values of ammonia (>20%.) which permits the distinction between estuarine from fresh-water phytoplankton. Simple isotopic budget calculations show that, both in the upstream part and in the downstream part, autochthonous phytoplanktonic material contributes a major part of the total suspended matter in the Scheldt estuary during summer.     

A crustal origin for eclogites and a mantle origin for garnet peridotites: Strontium isotopic evidence from clinopyroxenes

Strontium isotopic data suggest that the classic eclogite-facies rocks of western south Norway described by Eskola (1921) formed from several parental materials in a variety of environments. Mineral separates from essentially basic, bi-minerallic (clinopyroxene and garnet) eclogites that occur as lens-shaped masses within high grade gneisses (country rock eclogites) have Sr⁸⁷/Sr⁸⁶ values that range from 0.704 for fine-grained varieties to 0.716 for coarse-grained, orthopyroxene-bearing varieties. These high, varied ratios contrast with the very low, restricted ratios (0.701 to 0.704) of similar minerals from ultrabasic, garnet-clinopyroxene-orthopyroxene-olivine assemblages (garnet peridotites) that occur as lenses within large peridotite bodies. The eclogite-facies metamorphism that generated the garnet peridotites may have occurred in the mantle. However, the metamorphism that generated at least the more radiogenic country-rock eclogites must have occurred in the crust. The high Sr⁸⁷/Sr⁸⁶ ratios of these eclogites could be generated either by forming them from crustal parental rocks or by contaminating mantle-derived parental rocks with radiogenic strontium from the country rocks. If this contamination occurred after intrusion and before eclogite-facies metamorphism, a rather contrived history must be postulated that involves intrusion, contamination accompanied by hydration, subsequent dehydration, and finally eclogite-facies metamorphism. These processes could have occurred within the long, complicated history of the enclosing country rocks. Alternatively, if the contamination occurred during eclogite-facies metamorphism, the presence of some hydrous fluid appears to be required to transport the radiogenic strontium from the enclosing country rocks. The eclogites with the highest Sr⁸⁷/Sr⁸⁶ ratios are also the most coarse-grained and it is possible that the presence of some intergranular fluid enabled these eclogites to recrystallize to a much larger grain size than would have been possible in a totally anhydrous environment. The garnet peridotites and fine-grained country rock eclogites may have formed from mantle material in the crust but escaped contamination by radiogenic strontium as a result of their position in a dry environment in the crust.Lamont-Doherty Geological Observatory Contribution No. 2443     

Establishing the potential of Ca isotopes as proxy for consumption of dairy products

A procedure has been developed which allows precise determination of Ca isotope ratios in natural and organic samples such as bones, milk and other biological materials. In this study the procedure is used to determine Ca isotope ratios in modern dietary systems and to establish the potential of Ca isotopes as a paleodiet tracer by analysis of bones. Multi-sampling across a 5 cm portion of a red deer jawbone shows invariant Ca isotope ratios and suggests negligible isotopic effect during bone remodelling. The difference between Ca isotopes in red deer diet and bones from one location was 0.65‰, in agreement with a previous study of diet/bone offsets. Similar values for modern deer-bone δ^44/42Ca from four geographically diverse populations demonstrate that geological/environmental conditions do not cause large variability and suggest that diet is the major cause for variations in bone δ^44/42Ca. δ^44/42Ca of herbivore milk is found to be ≈0.5 to 0.6 higher than the corresponding diet. Modern human milk has a δ^44/42Ca of −1.15 (n = 4) and is isotopically the lightest material reported in this study. This suggests that, for these samples, a significant portion of Ca intake was from dairy sources, and that human milk has Ca which is, again, ≈0.6‰ isotopically lighter than dietary Ca intake. Finally, Ca isotope ratios are presented from a variety of samples formed during fermentation processes (e.g., curds, whey, etc.) which indicate that these processes do not fractionate Ca isotopes significantly. Together, the data in this paper indicate that, because milk is an important dietary source of Ca with a distinctive signature, Ca isotope ratios should provide a tracer for past dairy consumption. A simplified model is outlined to demonstrate the ability to quantify dairy consumption by the analysis of Ca isotopes in bones.     

87Sr/86Sr in waters from the Lincolnshire Limestone aquifer,England, and the potential of natural strontium isotopes as a tracer for a secondary recovery seawater injection process in oilfields

The Sr isotope composition of formation waters is a sensitive indicator of diagenetic processes in the host sediments, mixing processes between different bodies of water, and the connectivity of hydrological systems. The⁸⁷Sr/⁸⁶Sr ratio of present seawater is constant worldwife, while formation waters in hydrocarbon reservoirs have various values, depending on the aforementioned effects, in most cases different from modern seawater. This forms the basis of anatural tracer technique for seawater injection projects, involving characterization of the⁸⁷Sr/⁸⁶Sr ratios and Sr contents of formation waters in the reservoir before injection commences, followed by monitoring of these parameters in the produced water as injection proceeds. This method is best suited to reservoirs in which the formation waters have low Sr concentrations and⁸⁷Sr/⁸⁶Sr ratios much higher or lower than seawater. Available data for reservoir formation waters suggest that breakthrough recognition could be expected at <10% seawater in many sandstone reservoirs, while the method would be less sensitive in carbonate reservoir or situations where the formation waters had interacted with evaporites, as the associated waters tend to have high Sr contents. In heterogeneous but well-mapped reservoirs, it may be possible to obtain information about flow paths/mechanismsbefore breakthrough. Combination with other chemical and isotopic tracers creates a very powerful tool, the Sr method acting as a safeguard should the batch of water containing the conventional tracers be overtaken by subsequently injected seawater. The Sr method could also be used for injection projects that were begun without the addition of tracers. A natural analogue of a water injection process is found in the Jurassic Lincolnshire Limestone aquifer in England, where rapidly moving fresh meteoric water mixes progressively with an older saline formation water. The⁸⁷Sr/⁸⁶Sr data enable quantitative modelling of this mixing process. The infiltrating fresh water becomes progressively modified by dissolution of detrital carbonate and calcite cement in the limestone, with depth becoming increasingly dominated by Sr derived from the more soluble detrital components. The saline formation water contains water molecules of meteoric origin and an⁸⁷Sr/⁸⁶Sr ratio much higher than Jurassic seawater or marine carbonate; the solute content has been influence by interaction of the water with non-carbonate phases.     

Li isotopes and trace elements as a petrogenetic tracer in zircon: insights from Archean TTGs and sanukitoids

We report δ⁷Li, Li abundance ([Li]), and other trace elements measured by ion probe in igneous zircons from TTG (tonalite, trondhjemite, and granodiorite) and sanukitoid plutons from the Superior Province (Canada) in order to characterize Li in zircons from typical Archean continental crust. These data are compared with detrital zircons from the Jack Hills (Western Australia) with U–Pb ages greater than 3.9 Ga for which parent rock type is not known. Most of the TTG and sanukitoid zircon domains preserve typical igneous REE patterns and CL zoning. [Li] ranges from 0.5 to 79 ppm, typical of [Li] in continental zircons. Atomic ratios of (Y + REE)/(Li + P) average 1.0 ± 0.7 (2SD) for zircons with magmatic composition preserved, supporting the hypothesis that Li is interstitial and charge compensates substitution of trivalent cations. This substitution results in a relatively slow rate of Li diffusion. The δ⁷Li and trace element data constrain the genesis of TTGs and sanukitoids. [Li] in zircons from granitoids is significantly higher than from zircons in primitive magmas in oceanic crust. TTG zircons have δ⁷Li (3 ± 8‰) and δ¹⁸O in the range of primitive mantle-derived magmas. Sanukitoid zircons have average δ⁷Li (7 ± 8‰) and δ¹⁸O higher than those of TTGs supporting genesis by melting of fluid-metasomatized mantle wedge. The Li systematics in sanukitoid and TTG zircons indicate that high [Li] in pre-3.9-Ga Jack Hills detrital zircons is a primary igneous composition and suggests the growth in proto-continental crust in magmas similar to Archean granitoids.     

On the origin of oriented rutile needles in garnet from UHP eclogites

Although oriented rutile needles in garnet have been reported from several ultrahigh‐pressure (UHP) rocks and considered to be important UHP indicators, their crystallographic features including growth habit and lattice correspondences with garnet host have never been properly characterized. This paper presents a detailed analytical electron microscopic (AEM) study on evenly distributed oriented rutile needles in garnet of two eclogitic rocks from Sulu. Some garnet in one UHP diamondiferous quartzofeldspathic rock from the Saxonian Erzgebirge, and in one high‐pressure (HP) felsic granulite from Bohemia also contain a few unevenly distributed oriented rutile needles. They have also been studied for the purpose of comparison. Despite different distribution patterns, AEM revealed that all rutile needles are oriented along the 〈111〉 directions of garnet with their lateral sides surrounded by the {110} planes of garnet, and that the growth directions of most needles are close to the normal of the {101} planes of rutile. No other specific crystallographic orientation relationships between rutile and garnet host were observed, and there is no pyroxene associated with rutile, as necessitated by the precipitation reaction of rutile in garnet as previously proposed. A simple solid‐state precipitation scenario for the formation of the rutile needles in garnet in these two eclogitic rocks is not justified. Three alternative mechanisms are considered for the formation of oriented rutile needles: (i) the rutile needles may be inherited from precursor minerals; (ii) the rutile needles may be formed by a dissolution–reprecipitation mechanism; and (iii) the rutile needles may be formed by cleaving and healing of garnet with rutile deposition. None of these mechanisms can fully explain the observations, although the first one is less likely and the third one is preferred. This study presents an example where the presence of oriented/aligned inclusions in minerals does not necessarily imply a precipitation origin.     

Radon as a tracer of tectonic movements

We suggest a model of radon emanation under compression or extension strain from a medium equivalent to rocks containing pores and cracks. The model is shown in several examples to be suitable for simulating the nucleation of rock bursts in deep mines and earthquakes. According to correlation of strain and radon measurements at the same sites, a relative strain change of n×10^?7 corresponds to a 200% change of radon activity concentration. This high sensitivity means that radon data can be good tracers of tectonic movements.     

Sr isotopes as a tracer of weathering processes and dust inputs in a tropical granitoid watershed, Luquillo Mountains, Puerto Rico

Sr isotope data from soils, water, and atmospheric inputs in a small tropical granitoid watershed in the Luquillo Mountains of Puerto Rico constrain soil mineral development, weathering fluxes, and atmospheric deposition. This study provides new information on pedogenic processes and geochemical fluxes that is not apparent in watershed mass balances based on major elements alone. ⁸⁷Sr/⁸⁶Sr data reveal that Saharan mineral aerosol dust contributes significantly to atmospheric inputs. Watershed-scale Sr isotope mass balance calculations indicate that the dust deposition flux for the watershed is 2100 ± 700 mg cm⁻² ka⁻¹. Nd isotope analyses of soil and saprolite samples provide independent evidence for the presence of Saharan dust in the regolith. Watershed-scale Sr isotope mass balance calculations are used to calculate the overall short-term chemical denudation velocity for the watershed, which agrees well with previous denudation rate estimates based on major element chemistry and cosmogenic nuclides. The dissolved streamwater Sr flux is dominated by weathering of plagioclase and hornblende and partial weathering of biotite in the saprock zone. A steep gradient in regolith porewater ⁸⁷Sr/⁸⁶Sr ratio with depth, from 0.70635 to as high as 0.71395, reflects the transition from primary mineral-derived Sr to a combination of residual biotite-derived Sr and atmospherically-derived Sr near the surface, and allows multiple origins of kaolinite to be identified.     

环境同位素及其示踪技术在地震预测研究中的应用前景

随着新的观测技术和理论的快速发展,环境同位素示踪技术在分析与地震孕育、发生有关的地下水动态信息中有可能发挥重要作用。简单介绍了稳定同位素2H、18O以及放射性同位素3H、14C的特征与示踪技术,详细阐述前人应用环境同位素在地下水活动规律中所开展的研究,包括地下水的补给来源、地下热水的循环深度、水岩相互作用、地下水的年龄等,并重点分析了这种示踪技术在研究地下水对构造活动发生和对应力应变响应等方面的应用。积极推进环境同位素示踪技术的应用,对地下流体地震前兆信息的评估、地震活动性强度的判定、流体在孕震过程中作用的探讨,以及井孔映震效能的评价等方面的研究具有重要的意义。     

Intra-oceanic island arc origin for Iratsu eclogites of the Sanbagawa belt,central Shikoku,southwest Japan

New geochemical and Sr–Nd isotopic data for the Iratsu eclogite and surrounding metamorphic rocks of the Sanbagawa belt, Japan, show that, while the protoliths of the metamorphic rocks formed in a variety of tectonic settings, the Iratsu body represents a deeply subducted and accreted island arc. The igneous protoliths of eclogites and garnet amphibolites were probably generated from a mantle source that had components of both a depleted mantle modified by slab-released fluid (as seen in a negative Nb anomaly) and an enriched mantle, similar to that of ocean island basalts (OIB). Fractional crystallization modeling indicates that the protoliths of some garnet clinopyroxenites from the Iratsu body are cumulates from a basaltic magma that crystallized under high O₂ and H₂O fugacities in the middle to lower crust. The source characteristics and crystallization conditions suggest that the protoliths of the Iratsu rocks formed in an oceanic island arc. Quartz eclogites from the marginal zone of the Iratsu body have geochemical signatures similar to turbidites from the Izu–Bonin island arc (as seen in a negative Nb anomaly and a concave REE pattern). The protoliths might be volcaniclastic turbidites that formed in a setting proximal to the oceanic island arc. Geochemical and isotopic signatures of the surrounding mafic schists are similar to normal (N-) and enriched (E-) mid-ocean-ridge basalt (MORB), and distinct from the rocks from the Iratsu body. The protoliths of the mafic schists likely formed in a plume-influenced mid-ocean ridge or back-arc basin. Pelitic schists from the surrounding rocks and pelitic gneisses from the marginal zone of the Iratsu body have evolved, continental geochemical signatures (as seen in a negative ε_Nd(t) value (~?5)), consistent with their origin as continent-derived trench-fill turbidites.     

Estimating contamination potential at waste-disposal sites using a natural tracer

Chloride is a conservative, natural tracer found in precipitation, soil water, and groundwater. The chloride mass-balance approach, long used to estimate groundwater recharge, also provides a downward flux of moisture and solute at sites where there is a potential for groundwater contamination. The flux is obtained by dividing the product of the mean annual precipitation and total annual chloride input (via precipitation and dust) by the mean soil-water chloride content. Chlorideversusdepth profiles can also be used to determine optimum depth of waste burial to minimize deterioration of waste containers. The method has been applied to three sites in arid alluvial-basin settings in New Mexico, U.S.A.: a proposed landfill, a battery recycling plant, and a hazardous-waste disposal facility. It is concluded that the method is reliable, economical, and practical. Furthermore, it can be applied at any stage in the development of a site. The chloride method should apply in any recharge area where the base of the root zone is separated from the water table by at least 3 m or so and chloride in soil water comes only from precipitation and dust.     

The secondary origin of diamonds: multi-modal radiation tomography of diamondiferous mantle eclogites

Three-dimensional neutron and X-ray tomography reveals the textural and spatial relationship of diamonds and associated minerals in situ, in a unique suite of 17 diamondiferous eclogites. We emphasize the reporting of X-ray imaging on mantle xenoliths, which in combination with neutron imaging enables the clear identification of diamonds and interstitial metasomatic secondary minerals. In particular, neutrons are highly sensitive to hydrogen (H), allowing for the identification of OH- and H₂O-bearing metasomatic minerals. The identification of metasomatic minerals allows for the delineation of distinct metasomatic pathways through the eclogite xenoliths. Diamonds are readily identified as the darkest greyscales due to their low attenuation, and are typically surrounded by secondary minerals, never in contact with primary minerals, and always confined within metasomatic pathways. The ubiquitous occurrence of diamonds in association with pathways suggests a potential genetic link. Both octahedral and dodecahedral diamonds are observed within individual xenoliths, suggesting multiple heterogeneous growth and dissolution processes at small scales. The distinct age dichotomy between eclogite xenoliths and metasomatic mineral assemblages implies that the observed textural relationship of diamonds and late-stage metasomatic pathways for this suite of 17 eclogites casts doubt on the theory that eclogitic diamonds formed billions of years ago. Diamonds are interpreted to have formed from multiple growth episodes, with the last of these episodes represented by the metasomatic assemblages observed in this study. This further indicates that eclogitic diamond inclusions may span large time scales from ancient ages (>2 Ga) all the way to the last growth event, perhaps even close to the time of kimberlite emplacement (~360 Ma), which has significant implications for age-dating of diamonds and the study of diamonds as a whole.     

The characterisation and origin of graphite in cratonic lithospheric mantle: a petrological carbon isotope and Raman spectroscopic study

Graphite-bearing peridotites, pyroxenites and eclogite xenoliths from the Kaapvaal craton of southern Africa and the Siberian craton, Russia, have been studied with the aim of: 1) better characterising the abundance and distribution of elemental carbon in the shallow continental lithospheric mantle; (2) determining the isotopic composition of the graphite; (3) testing for significant metastability of graphite in mantle rocks using mineral thermobarometry. Graphite crystals in peridotie, pyroxenite and eclogite xenoliths have X-ray diffraction patterns and Raman spectra characteristic of highly crystalline graphite of high-temperature origin and are interpreted to have crystallised within the mantle. Thermobarometry on the graphite-peridotite assemblages using a variety of element partitions and formulations yield estimated equilibration conditions that plot at lower temperatures and pressures than diamondiferous assemblages. Moreover, estimated pressures and temperatures for the graphite-peridotites fall almost exclusively within the experimentally determined graphite stability field and thus we find no evidence for substantial graphite metastability. The carbon isotopic composition of graphite in peridotites from this and other studies varies from δ¹³ C_PDB = ? 12.3 to ? ?3.8%o with a mean of-6.7‰, σ=2.1 (n=22) and a mode between-7 and-6‰. This mean is within one standard deviation of the-4‰ mean displayed by diamonds from peridotite xenoliths, and is identical to that of diamonds containing peridotite-suite inclusions. The carbon isotope range of graphite and diamonds in peridotites is more restricted than that observed for either phase in eclogites or pyroxenites. The isotopic range displayed by peridotite-suite graphite and diamond encompasses the carbon isotope range observed in mid-ocean-ridge-basalt (MORB) glasses and ocean-island basalts (OIB). Similarity between the isotopic compositions of carbon associated with cratonic peridotites and the carbon (as CO₂) in oceanic magmas (MORB/OIB) indicates that the source of the fluids that deposited carbon, as graphite or diamond, in catonic peridotites lies within the convecting mantle, below the lithosphere. Textural observations provide evidence that some of graphite in cratonic peridotites is of sub-solidus metasomatic origin, probably deposited from a cooling C-H-O fluid phase permeating the lithosphere along fractures. Macrocrystalline graphite of primary appearance has not been found in mantle xenoliths from kimberlitic or basaltic rocks erupted away from cratonic areas. Hence, graphite in mantle-derived xenoliths appears to be restricted to Archaean cratons and occurs exclusively in low-temperature, coarse peridotites thought to be characteristic of the lithospheric mantle. The tectonic association of graphite within the mantle is very similar to that of diamond. It is unlikely that this restricted occurrence is due solely to unique conditions of oxygen fugacity in the cratonic lithospheric mantle because some peridotite xenoliths from off-craton localities are as reduced as those from within cratons. Radiogenic isotope systematics of peridotite-suite diamond inclusions suggest that diamond crystallisation was not directly related to the melting events that formed lithospheric peridotites. However, some diamond (and graphite?) crystallisation in southern Africa occurred within the time span associated with the stabilisation of the lithospheric mantle (Pearson et al. 1993). The nature of the process causing localisation of carbon in cratonic mantle roots is not yet clearly understood.     

The origin of epigenetic graphite: evidence from isotopes

Stable carbon isotope ratios measured in syngenetic graphite, epigenetic graphite, and graphitic marble suggests that syngenetic graphite forms only by the metamorphism of carbonaceous detritus. Metamorphism of calcareous rocks with carbonaceous detritus is accompanied by an exchange of carbon between the two, which may result in large changes in isotopic composition of the non-carbonate phase but does not affect the relative proportions of the two reactants in the rock. Epigenetic graphite forms only from carbonaceous material or preexisting graphite. The reactions involved are the water gas reaction (C + H₂O → CO + H₂) at 800–900°C, and the Boudouard reaction (2CO → C + CO₂), which probably takes place at temperatures about 50–100°C lower.     

Use of deuterated water as a conservative artificial groundwater tracer

Conservative tracers are necessary to obtain groundwater transport velocities at the field scale. Deuterated water is an effective tracer for this purpose due to its similarity to water, chemical stability, non-reactivity, ease of handling and sampling, relatively neutral buoyancy, and reasonable price. Reliable detection limits of 0.1 mg deuterium/L may be obtained in field tests. A field example is presented in which deuterated water, bromide, and pentafluorobenzoic acid are used as groundwater tracers. Deuterated water appeared to be transported conservatively, producing almost identical breakthrough curves as that of other soluble tracers. Electronic Publication     

Thallium,a biogeochemical prospecting tool for gold

The role of thallium as a biogeochemical pathfinder for gold is investigated. Several hundred plants of various species were analyzed for gold and thallium. A striking resemblance of absorption potential of plants for gold and thallium was observed, thallium having about tenfold higher concentrations than gold. This fact makes it analytically easier to detect and qualifies thallium as a good pathfinder for gold.     

Sulphur and sulphate-oxygen isotopes and the origin of the silvermines deposits,Ireland

New sulphur and sulphate-oxygen isotope measurements for the main discordant and stratiform lead-zinc-barite orebodies at Silvermines Co. Tipperary, allow reappraisal of previously offered differing interpretations (Graham, 1970; Greig et al., 1971) of the bearing of sulphur isotopes on the genesis of this important Irish deposit. The following aspects of the data are confirmed: barite ³⁴ S-values range from 17–21, similar to lower Carboniferous seawater sulphate: stratiform sulphide lens pyrites have ³⁴ S-values ranging from –13 to –36; vein sulphide ³⁴ S-values range from –8 to 4; sulphide ³⁴ S-values increase upwards and outwards respectively in the related discordant and stratiform G orebodies; galena-sphalerite isotope palaeotemperatures are not too consistent, ranging from 40 to 430°C (using the calibration of Czamanske and Rye (1974). New facts are as follows: barite ¹⁸O-values range from –13 to –17, stratiform barites ranging from 13 to 14.5; sulphides separated from a single stratiform ore lens hand specimen usually have ³⁴ S_sl > ³⁴ S_ga > ³⁴ S_py; the outward decrease in ³⁴ S-values in the stratiform G orebody is confined to the first few hundred feet only; pyrite ³⁴ S-values progressively increase downwards through one stratiform sulphide orebody; yet variations of 13 occur within a single colloform pyrite structure from another stratiform orebody. It is concluded that there were at least two sources of sulphur, seawater sulphate and deep-seated sulphur. The former was the dominant source of all sulphate and, via biogenic reduction, of the sulphur in the bulk of the stratiform sulphide. The latter was the source of the sulphur in the vein sulphides. There was minimal isotopic interaction between the cool seawater sulphate and the warm unwelling ore fluid sulphur species, even though the latter precipitated under near isotopic equilibrium conditions when the temperature dropped and/or the pH and Eh increased. The lack of isotopic equilibrium between pyrite and ore sulphides in the stratiform ore lenses may result from the latter having precipitated slightly later than the former because of solubility relationships. Overall the present isotopic evidence supports considerable geological evidence favoring a syngenetic origin for the stratiform Silvermines orebodies.