Mineralogy and stable isotope geochemistry of hydrothermally altered oceanic rocks

Data for the diffusion of cations in pyroxenes are relevant to a variety of sub-solidus processes including order-disorder and exsolution. Similar data must also be available if the reliability of geobarometers and geothermometers involving pyroxenes is to be assessed. Two types of diffusion experiment have been performed to determine cation diffusion rates in pyroxenes: (1) interdiffusion between single crystals of diopside and polycrystalline sinters enriched in Al and Fe, and (2) interdiffusion between single crystals of diopside and a glass of the same composition which was isotopically enriched in²⁶Mg and⁴³Ca. Following high-temperature annealing for periods up to several hundred hours, analysis of the diffusion couples, using an electron microprobe and an ion microprobe respectively, failed to show any measurable diffusion profiles. From these “null result” experiments the diffusion coefficients (D) for Al and Fe in diopside are estimated to be less than4×10^?14cm²s^?1 at 1200°C, and values ofD for Ca and Mg in diopside are estimated to be less than7 × 10^?14cm²s^?1 at 1250°C. These rates are significantly slower than published tracer-type diffusion data for Ca and Al.A review of studies of order-disorder, microstructural coarsening, and diffusion in pyroxenes suggest that activation energies for cation exchange are typically in excess of 60 kcal mol^?1. Transport rates will be assisted, and activation energies lowered by sample non-stoichiometry, inhomogeneities, high dislocation densities and the presence of water.The collective data for Al, Mg and Ca diffusion in diopside indicate diffusion coefficients? 10^?15cm²s^?1 at 1200°C. A comparison with data for diffusion in garnet, olivine and spinel suggests that pyroxenes may have the highest blocking temperatures.     

The stable isotope geochemistry of volcanic lakes, with examples from Indonesia

Stable isotope compositions (δD, δ¹⁸O and δ³⁴S) of volcanic lake waters, gas condensates and spring waters from Indonesia, Italy, Japan, and Russia were measured. The spring fluids and gas samples plot in a broad array between meteoric waters and local high-temperature volcanic gas compositions. The δD and δ¹⁸O data from volcanic lakes in East Indonesia plot in a concave band ranging from local meteoric waters to evaporated fluids to waters heavier than local high-temperature volcanic gases. We investigated isotopic fractionation processes in volcanic lakes at elevated temperatures with simultaneous mixing of meteoric waters and volcanic gases. An elevated lake water temperature gives enhanced kinetic isotope fractionation and changes in equilibrium fractionation factors, providing relatively flat isotope evolution curves in δ¹⁸O–δD diagrams. A numerical simulation model is used to derive the timescales of isotopic evolution of crater lakes as a function of atmospheric parameters, lake water temperature and fluxes of meteoric water, volcanic gas input, evaporation, and seepage losses. The same model is used to derive the flux magnitude of the Keli Mutu lakes in Indonesia. The calculated volcanic gas fluxes are of the same order as those derived from energy budget models or direct gas flux measurements in open craters (several 100 m³ volcanic water/day) and indicate a water residence time of 1–2 decades. The δ³⁴S data from the Keli Mutu lakes show a much wider range than those from gases and springs, which is probably related to the precipitation of sulfur in these acid brine lakes. The isotopic mass balance and S/Cl values suggest that about half of the sulfur input in the hottest Keli Mutu lake is converted into native sulfur.     

Major active faults determine the location of the Tongonan geothermal field: Evidence provided by rock alteration and stable isotope geochemistry

Abstract The influence of major active faults on rock alteration and stable isotope geochemistry is described for the Tongonan geothermal field, Leyte, the Philippines. In the Pliocene, acid alteration with characteristic iron enrichment (3 g/100 g) and calcium depletion (2 g/100 g) occurred along a Riedel shear fault in the Malitbog sector, and initial minor acid alteration also occurred along a similar shear in the Mahiao sector. Later, sodium metasomatism (5 g/100 g) coincided with the highest aquifer chloride (10 000 mg/kg) as a result of dissociation of saline magmatic fluids discharging through the reservoir rocks in the Upper Mahiao. The incursion of magmatic fluids (possibly δD 35‰, δ¹⁸O +7‰) set up a vigorous convection cell of meteoric water, which focused around low‐angle (L) shears centered in the Sambaloran sector. Meteoric water (δD ?35 to ?40‰, δ¹⁸O ?6 ± 1‰) depleted the reservoir in silica (6 g/100 g) and potassium (1–2 g/100 g). It also completely exchanged oxygen isotopes rapidly (within months) at high temperatures (300–400°C), and now does so continuously with fractured isotopically fresh or incompletely altered rock at small scales (centimeters or less) exposed by a 2 cm/year creep around the L shears to form a new component called geothermal water. Geothermal water mixes with meteoric water at lower temperatures (<300°C) to create the characteristic shift in δ¹⁸O of 6‰ at near constant δD (?35 ± 5‰). The 10‰ variation in δD is due to groundwater recharge derived from rain falling on steep terrain (5‰) and to enrichment of deuterium in boiling saline solutions (5‰); it is not due to two‐component mixing of meteoric with magmatic water. The low (～1) isotopic water/rock (W/R) ratios calculated from oxygen isotopes in previously published reports are meaningless, because the water contains four components (predominantly geothermal and meteoric water; <10% magmatic and rock water). W/R ratios of up to 1500 calculated from spring and rock chemistry are more realistic and, with a flow rate of approximately 50 L/s through a 30 km³ reservoir, can account for the estimated 3 My age of the system.     

Major element chemistry of Galapagos Rift Zone magmas and their phenocrysts

Basalts dredged from the Galapagos Rift Zone between 85°W and 100°W were analyzed by electron microprobe to determine the chemistry of the glass exteriors and included phenocrysts, microphenocrysts and quench minerals. The basalts come from both “normal” mid-ocean ridge segments and from ridge segments that cross the Galapagos Platform. The basalts fall into two chemical and geographical groups. Group A basalts come from outside the central region of the Galapagos Platform (i.e., outside 89–92.5°W) and are chemically similar to basalts from “normal” ocean ridge segments. Group B basalts come from the center of the Galapagos Platform (89–92.5°W) and are enriched in incompatible elements like “plume-influenced” basalts from the Mid-Atlantic Ridge. The spinel, olivine, plagioclase and clinopyroxene phenocrysts in both groups of basalts are low-pressure, equilibrium phases, but the chemical difference among basalts from within each group indicates high-pressure fractional crystallization is also responsible for the chemical evolution of some of these basalts. Presently, no crystallization or partial melting model can relate the chemistry of the two groups of basalts and the compositional influence of a large-ion-lithophile elements and water-rich mantle beneath the Galapagos Platform is a viable alternate hypothesis. The eruption temperature of magmas from the “normal” ridge segments, as determined by olivine-liquid thermometry is 1217±10°C, suggesting steady-state conditions but on the Galapagos Platform the eruption temperatures are lower and more variable than on the “normal” ridge (1186°C±30°C) suggesting a more complex plumbing system and the absence of a steady-state magma chamber beneath the platform.     

Alvin-SeaBeam studies of the Sumisu Rift, Izu-Bonin arc

Bimodal volcanism, normal faulting, rapid sedimentation, and hydrothermal circulation characterize the rifting of the Izu-Bonin arc at 31°N. Analysis of the zigzag pattern, in plan view, of the normal faults that bound Sumisu Rift indicates that the extension direction (080° ± 10°) is orthogonal to the regional trend of the volcanic front. Normal faults divide the rift into an inner rift on the arc side, which is the locus for maximum subsidence and sedimentation, and an outer rift further west. Transfer zones that link opposing master faults and/or rift flank uplifts further subdivide the rift into three segments along strike. Volcanism is concentrated along the ENE-trending transfer zone which separates the northern and central rift segments. The differential motion across the zone is accommodated by interdigitating north-trending normal faults rather than by ENE-trending oblique-slip faults. Volcanism in the outer rift has built 50–700 m high edifices without summit craters whereas in the inner rift it has formed two multi-vent en echelon ridges (the largest is 600 m high and 16 km long). The volcanism is dominantly basaltic, with compositions reflecting mantle sources little influenced by arc components. An elongate rhyolite dome and low-temperature hydrothermal deposits occur at the en echelon step in the larger ridge, which is located at the intersection of the transfer zone with the inner rift. The chimneys, veins, and crusts are composed of silica, barite and iron oxide, and are of similar composition to the ferruginous chert that mantles the Kuroko deposits. A 1.2-km transect of seven alvin heat flow measurements at 30°48.5′N showed that the inner-rift-bounding faults may serve as water recharge zones, but that they are not necessarily areas of focussed hydrothermal outflow, which instead occurs through the thick basin sediments. The rift basin and arc margin sediments are probably dominated by permeable rhyolitic pumice and ash erupted from submarine arc calderas such as Sumisu and South Sumisu volcanoes.     

Strontium, oxygen, and hydrogen isotope geochemistry of hydrothermally altered and weathered rocks in DSDP Hole 504B, Costa Rica Rift

DSDP Hole 504B was drilled into 6 Ma crust, about 200 km south of the Costa Rica Rift, Galapagos Spreading Center, penetrating 1.35 km into a section that can be divided into four zones—Zone I: oxic submarine weathering; Zone II: anoxic alteration; Zones III and IV: hydrothermal alteration to greenschist facies. In Zone III there is intense veining of pillow basalts. Zone IV consists of altered sheeted dikes. Isotopic geochemical signatures in relation to the alteration zones are recorded in Hole 504B, as follows:

Zone	Depth(m)	Average87Sr/86Sr	Average δ18O (%o)	Average δD (%o)
I	275–550	0.7032	7.3	−63
II	550–890	0.7029	6.5	−45
III	890–1050	0.7035	5.6	−31
IV	1050–1350	0.7032	5.5	−36

Full-size table

Alteration temperatures are as low as 10°C in Zones I and II based on oxygen isotope fractionation. Strontium isotopic data indicate that a circulation of seawater is much more restricted in Zone II than in Zone I. Fluid inclusion measurements of vein quartz indicate the alteration temperature was mainly 300 ± 20°C in Zones III and IV, which is consistent with secondary mineral assemblages.The strontium, oxygen, and hydrogen isotopic compositions of hydrothermal fluids which were responsible for the greenschist facies alteration in Zones III and IV are estimated to be 0.7037, 2‰, and 3‰, respectively. Strontium and oxygen isotope data indicate that completely altered portions of greenstones and vein minerals were in equilibrium with modified seawater under low water/rock ratios (in weight) of about 1.6. This value is close to that of the end-member hydrothermal fluids issuing at 21°N EPR.Basement rocks are not completely hydrothermally altered. About 32% of the greenstones in Zones III and IV have escaped alteration. Thus 1 g of fresh basalt including the 32% unaltered portion are required in order to make 1 g of end-member solution from fresh seawater in water-rock reactions.     

Major element, trace element, and Sr, Nd and Pb isotope studies of Cenozoic basalts from the South China Sea

The whole rock K-Ar ages of basalts from the South China Sea basin vary from 3.8 to 7.9 Ma, which suggest that intra-plate volcanism after the cessation of spreading of the South China Sea (SCS) is comparable to that in adjacent regions around the SCS, i.e., Leiqiong Peninsula, northern margin of the SCS, Indochina block, and so on. Based on detailed petrographic studies, we selected many fresh ba-saltic rocks and measured their major element, trace element, and Sr-Nd-Pb isotope compositions. Geochemical characteristics of major element and trace element show that these basaltic rocks belong to alkali basalt magma series, and are similar to OIB-type basalt. The extent of partial melting of mantle rock in source region is very low, and magma may experience crystallization differentiation and cu-mulation during the ascent to or storing in the high-level magma chamber. Sr-Nd-Pb isotopic data of these basaltic rocks imply an inhomogeneous mantle below the South China Sea. The nature of magma origin has a two end-member mixing model, one is EM2 (Enriched Mantle 2) which may be originated from mantle plume, the other is DMM (Depleted MORB Mantle). Pb isotopic characteristics show the Dupal anomaly in the South China Sea, and combined with newly found Dupal anomaly at Gakkel ridge in Arctic Ocean, this implies that Dupal anomaly is not only limited to South Hemisphere. In variation diagrams among Sr, Nd and Pb, the origin nature of mantle below the SCS is similar to those below Leiqiong peninsula, northern margin of the SCS and Indochina peninsula, and is different from those below north and northeast China. This study provides geochemical constraints on Hainan mantle plume.     

Osmium isotope geochemistry in the Mackenzie River basin

The Cenozoic marine osmium isotope record is largely driven by changes in the continental input. We aid its interpretation by supplying direct measurements of present day riverine Os in known geological and environmental settings. We analyzed Os concentrations and isotopic ratios in the dissolved, suspended, and bed materials of the Mackenzie River in Canada and smaller rivers draining the Western Cordillera into the Pacific Ocean. Rhenium content was measured for suspended and bed materials to provide further constraint. Dissolved ¹⁸⁷Os/¹⁸⁸Os ratios range from 0.74 to 4.5 and are controlled to first order by age and lithology of the bedrock. The rivers draining Jurassic volcanic rocks are unradiogenic, as low as 0.74, and those draining the Precambrian Canadian Shield are radiogenic, as high as 3.5. The headwaters of the Mackenzie left bank tributaries draining metamorphic carbonates in the Eastern Cordillera and Paleozoic black and gray shales in the Transition zone and the Interior Platform are especially radiogenic (3.0-4.5) with relatively high concentrations of Os. These latter rivers are responsible for the Mackenzie being above world average in Os concentration and yield (mol Os/km²/year) as well as in ¹⁸⁷Os/¹⁸⁸Os. The dissolved load is more radiogenic than the suspended or bed loads and constitutes a significant fraction of total fluvial Os.     

Groundwater mixing between different aquifer types in a complex structural setting discerned by elemental and stable isotope geochemistry

Karst aquifers are well known for their intricate stratigraphy and geologic structures, which make groundwater characterization challenging because flowpaths and recharge sources are complex and difficult to evaluate. Geochemical data, collected from ten closely spaced production wells constructed in two karst aquifers (Bangor Limestone (Mb) and Tuscumbia Limestone/Fort Payne Chert (Mftp)) in Trussville, north‐central Alabama, illustrate two distinctive groundwater end‐members: (1) higher major ion, dissolved inorganic carbon, conductivity, alkalinity concentrations, heavier δ¹³C ratios (max: −10.2 ± 0.2‰ Vienna Pee Dee Belemnite (PDB)) and lower residence times (mean: 19.5 ± 2 years, n = 2) of groundwater in the Mb aquifer and (2) lower constituent concentrations, lighter δ¹³C ratios (min: −13.4 ± 0.2‰ PDB) and longer residence times of groundwater (mean: 23.6 ± 2 years, n = 4) in the Mftp aquifer. Summer and fall data and the binary mixing model show aquifer inter‐flow mixing along solution fractures and confirms the distinctive groundwater geochemistry of the two aquifers. Lowering of static water levels over the summer (drawdown from 2 to 5.2 m) leads to more reducing groundwater conditions (lower Eh values) and slightly enriched δ¹⁸O and δD ratios during the fall [δ¹⁸O: −4.8 ± 0.1 to −5.4 ± 0.1‰ Vienna Standard Mean Oceanic Water (VSMOW), n = 9; δD: −25.4 ± 1 to −27.4 ± 1‰ VSMOW, n = 9] when compared with summer season samples (δ¹⁸O: −5.1 ± 0.1 to −5.7 ± 0.1‰ VSMOW, n = 11; δD: −25.0 ± 1 to −30.6 ± 1‰ VSMOW, n = 11). GIS analyses confirm the localized origin of recharge to the investigated aquifers. The combination of GIS, field parameters and geochemistry analyses can be successfully used to identify recharge sources, evaluate groundwater flow and transport pathways and to improve understanding of how groundwater withdrawals impact the sustainability and susceptibility to contamination of karst aquifers. Copyright © 2015 John Wiley & Sons, Ltd.     

腾格里沙漠盐湖氯同位素地球化学特征

δ~(37)Cl值可以用来指示盐湖演化过程中卤水的蒸发浓缩程度、可能的补给来源和控制因素,本文对腾格里沙漠地区12个代表性盐湖卤水样品开展了氯同位素组成研究.结果表明,研究区内沙漠盐湖卤水的δ~(37)Cl值变化范围为-0.10‰~1.36‰,平均值为0.55‰;其中,硫酸钠亚型卤水的δ~(37)Cl值范围为-0.10‰~1.36‰(平均值为0.56‰),硫酸镁亚型卤水的δ~(37)Cl值范围为0.14‰~0.82‰(平均值为0.48‰).对比柴达木盆地现代盐湖分析数据,发现区内沙漠盐湖的δ~(37)Cl平均值明显大于柴达木盆地盐湖的δ~(37)Cl平均值,并且,硫酸钠亚型卤水δ~(37)Cl最高,硫酸镁亚型卤水次之,氯化物型卤水最小.基于不同盐湖地下水咸化程度以及盐湖卤水中δ~(37)Cl值与Br/Cl系数关系的研究,揭示了研究区东部和东北部盐湖可能受到第三系地层咸水的补给,而其他盐湖主要受蒸发浓缩作用影响.δ~(37)Cl值分布特征则显示,腾格里沙漠地区部分盐湖在形成过程中可能受到区域构造活动诱发的第三系深部水补给及水-岩作用等多重因素的影响.     

Effect of mining and related activities on the sediment trace element geochemistry of lake coeur D'Alene,idaho, USA. Part I: Surface sediments

During the summer of 1989 surface sediment samples were collected in Lake Coeur d'Alene, the Coeur d'Alene River and the St Joe River, Idaho, at a density of approximately one sample per square kilometre. Additional samples were collected from the banks of the South Fork of the Coeur d'Alene and the Coeur d'Alene Rivers in 1991. All the samples were collected to determine trace element concentrations, partitioning and distribution patterns, and to relate them to mining, mining related and discharge operations that have occurred in the Coeur d'Alene district since the 1880s, some of which are ongoing. Most of the surface sediments in Lake Coeur d'Alene north of Conkling Point and Carey Bay are substantially enriched in Ag, As, Cu, Cd, Hg, Pb, Sb and Zn relative to unaffected sediments in the southern portion of the lake near the St Joe River. All the trace element enriched sediments are extremely fine grained (mean grain sizes « 63 μm). Most of the enriched trace elements, based on both the chemical analyses of separated heavy and light mineral fractions and a two step sequential extraction procedure, are associated with an operationally defined Fe oxide phase; much smaller percentages are associated either with operationally defined organics/sulphides or refractory phases. The presence, concentration and distribution of the Fe oxides and heavy minerals indicates that a substantial portion of the enriched trace elements are probably coming from the Coeur d'Alene River, which is serving as a point source. Within the lake, this relatively simple point source pattern is complicated by a combination of (1) the formation of trace element rich authigenic Fe oxides that appear to have reprecipitated from material solubilized from anoxic bed sediments and (2) physical remobilization by currents and wind driven waves. The processes that have caused the trace element enrichment in the surface sediments of Lake Coeur d'Alene are likely to continue for the foreseeable future.     

Helium and argon isotope geochemistry of the Tibetan Qulong porphyry Cu-Mo deposit,China

The Qulong porphyry Cu-Mo deposit,generated in the Miocene post-collisional extension environment of the Gangdese Copper(Molybdenum) Metallogenic Belt,is one of the largest porphyry Cu deposits in China.This study reports the noble gas isotopic compositions of volatiles released from fluid inclusion reserved in pyrite from the Qulong deposit.~3He/~4 He and ~(40)Ar/~(36)Ar ratios range from 0.54 to 1.015 Ra and 300-359,respectively.Concentrations of ~4 He and ~(40)Ar range from 1.77 to 2.62 × 10~(-8) cm~3 STP and 1.7-34 × 10~(-8) cm~3 STP,respectively.The isotopic composition of noble gases indicates that the ore-forming fluids of the Qulong Cu-Mo deposit were a mixture of fluid containing mantle component,which is exsolved from the porphyry magma,and crustal fluid characterized by atmospheric Ar and crustal radiogenic He.The δ~(34)S values of pyrite and molybdenite range from-0.52‰ to 0.31‰,with an average of-0.12‰,indicating a magmatic origin.More mantle components were involved in the Cu-Mo deposit than in the Mo-Cu deposit in the Qulong-Jiama ore-district.     

Mineralogy and hydrogen isotope geochemistry of clay minerals in the Ohnuma geothermal area,Northeastern Japan

Mineralogical and hydrogen isotopic studies have been made on clay minerals occurring in the Ohnuma geothermal area, northeastern Japan. Here, clay minerals such as smectite, kaolinite, dickite, sericite, and chlorite were formed by hydrothermal alteration of Miocene rocks. A chemical equilibrium can be assumed to be attained from the fact that the amount of expandable layer in the interstratified chlorite/smectite decreases and the polytype of sericite changes from 1M to 2M₁ with increasing depth and temperature. The hydrogen isotopic composition (D/H) of the clay minerals is lighter than that of the geothermal and local meteoric waters by about 20–40‰. The hydrogen isotopic fractionation factors α_{mineral-water} are as follows: 0.972–0.985 for kaolinite and dickite, 0.973–0.977 for sericite, and 0.954–0.987 for chlorite. In the temperature range from 100 to 250°C, the hydrogen isotopic fractionation factors between these minerals and water are not sensitive to the temperature. α_{chlorite-water} depends on the kind of octahedrally coordinated cations which lie close to the hydroxyl groups; it becomes large with an increase of Mg content of chlorite.     

Strontium isotope geochemistry of late cretaceous granodiorites,Jamaica and Haiti,greater Antilles

Initial⁸⁷Sr/⁸⁶Sr ratios have been determined for a representative suite of Upper Cretaceous granodiorites and associated rocks from the Above Rocks composite stock in central Jamaica and the Terre-Neuve pluton in northwestern Haiti. The average initial⁸⁷Sr/⁸⁶Sr ratio for severn samples of the Terre-Neuve intrusion is 0.7036, with a range of 0.7026–0.7047. For two samples of the Above Rocks the initial ratios are 0.7033 and 0.7034. A third sample from this intrusive has an initial ratio of 0.7084, which is tenatively attributed to contamination. The initial⁸⁷Sr/⁸⁶Sr ratios indicate that neither ancient sialic crust nor sediments carried down a Benioff zone can be the primary source of the granodioritic magma. K/Rb ratios for these rocks range from 178 to 247, which are much lower than the average values (≥1000) for tholeiitic basalts. It is concluded that the magmas originated primarily by melting of downthrust oceanic crust or adjacent mantle material.     

Strontium isotope geochemistry of the Lemachang independent silver ore deposit, northeastern Yunnan, China

Sr isotope geochemical studies (the 87Sr/86Sr and ?18O-87Sr/86Sr systems) on the wall rocks and ores from the Lemachang independent Ag deposit in northeastern Yunnan provide strong evidence that the ore-forming fluids had flown through radiogenetically Sr-enriched rocks or strata prior to their entry into the locus of ore precipitation, and water-rock interaction is the main mechanism of Ag ore precipitation. The radiogenetically Sr-enriched source region may be the Proterozoic basement (the Kunyang and Hekou groups). Moreover, the theoretical modeling of the Sr isotopic system indicates that the ore-forming fluids contain as much as 3×10?6 Sr with isotopic composition of Sr being 0.750 and that of oxygen 7.0‰. The ore-forming temperatures were estimated at 150-250℃ for the carbonate rock-type ores and at 200-260℃ for the clastic rock-type.     

Rb-Sr isotope geochemistry of lherzolites and their constituent minerals from Victoria,Australia

Major element data and Rb, Sr and⁸⁷Sr/⁸⁶Sr analyses for seven spinel lherzolite xenoliths and their Recent host basalt from Victoria, Australia, are presented. The exotic nature of the xenoliths is indicated by a wide spread in⁸⁷Sr/⁸⁶Sr values (0.7035–0.7076) compared with the basalt (0.7041). Five of the lherzolites provide evidence of a thermal event in the mantle 650 m.y. ago. Equilibration temperatures calculated from the compositions of the lherzolite phases (ca. 1050°C) apparently relate to this event. Estimates of the local geothermal gradient suggest temperatures of less than 700°C in the source region before eruption of the lherzolites.Isotopic analyses of the lherzolite minerals show that orthopyroxene contains more radiogenic Sr than coexisting olivine and clinopyroxene in three of the xenoliths. The⁸⁷Sr/⁸⁶Sr relationships between clinopyroxene and orthopyroxene suggest that internal isotopic disequilibrium has existed in the source region for up to 550 m.y.     

Evaluation and application of the ion microprobe in the strontium isotope geochemistry of carbonates

A modified AEI-IM20 ion microprobe has been used to measure⁸⁷Sr/⁸⁶Sr ratios in carbonates. A suite of carbonates with varying major elements (Ca, Mg, Fe, Mn) was studied at low and high (M/ΔM ? 3000) mass resolution to determine the types and intensities of molecular species isobaric with Sr peaks; Sr data collected at low mass resolution must be corrected for Ca₂ and CaMgO species. Rb/Sr ratios are extremely low, and correction for⁸⁷Rb is not required (< 0.1‰ of⁸⁷Sr).Usable Sr isotopic data may be obtained from calcite givenSr≥ 400ppm, and for Sr > 5000 ppm a precision of ～ ± 1‰ (± 0.0007) in⁸⁷Sr/⁸⁶Sr (2σ mean) can be achieved under optimum conditions. The corrections for Ca₂ and CaMgO are smaller than the within-run precision in calcite, but in dolomite the correction for CaMgO is + 1.5%. Mass fractionation corrections to⁸⁷Sr/⁸⁶Sr (based on⁸⁶Sr/⁸⁸Sr= 0.1194) are typically +8 to +10‰. Good agreement between ion probe and solid source mass spectrometer results was found for calcites of known Sr isotopic composition: ST4a (～ 400ppm Sr), average ion probe⁸⁷Sr/⁸⁶Sr= 0.7267 ± 0.0015, solid source⁸⁷Sr/⁸⁶Sr= 0.72680 ± 0.00008 [14]; JCG36 (～ 6000ppm Sr), average ion probe⁸⁷Sr/⁸⁶Sr= 0.7056 ± 0.0009, solid source⁸⁷Sr/⁸⁶Sr= 0.70588 ± 0.00009 [16]; JCG44 (～ 6000ppm Sr), average ion probe⁸⁷Sr/⁸⁶Sr= 0.7057 ± 0.0006, solid source⁸⁷Sr/⁸⁶Sr= 0.70540 ± 0.00008 [16]. The ability of the ion microprobe to measure⁸⁷Sr/⁸⁶Sr for 10-μm spots in calcite was used: (1) to measure variation in⁸⁷Sr/⁸⁶Sr of ～ 0.01 on a centimetre scale in a hydrothermally altered basalt from the Isle of Skye, northwestern Scotland; and (2) to determine the Sr isotopic composition of tiny (< 35 μm) calcite grains in a veined mantle lherzolite from Bultfontein, South Africa. Because of calcite's ubiquitous occurrence in many parageneses this technique may offer many opportunities for the measurement of fine scale heterogeneities in⁸⁷Sr/⁸⁶Sr.     

Organic carbon isotope geochemistry of clayey deposits and their associated porewaters, southern Alberta

The organic carbon cycle of slowly permeable, clayey glacial till deposits in the Western Interior Great Plains, southern Alberta, was investigated by examining the relationship between solid organic matter (SOM) in the till sediments and dissolved organic carbon (DOC) in the till porewaters. Geochemically, the tills can be divided into two distinct zones: an upper oxidized (low SOM) till zone, and a lower unoxidized (high SOM) till zone. Till porewaters in both zones are characterized by high DOC contents. Radiocarbon dating and comparison of SOM and DOC fractions suggest DOC in the deep unoxidized zone originated during deglaciation, and is probably representative of groundwater ages in this till zone. In the oxidized zone, DOC originates from variable mixtures of soluble organic matter emplaced during deglaciation, and Cretaceous age coal fragments in this till zone. SOM in the upper till zone was mainly oxidized to CO₂ gas during lowered water table conditions of the Altithermal climatic period. The subsurface production of fossil CO₂ gas has serious implications for using the conventional dissolved inorganic carbon (DIC) ¹⁴C groundwater dating method in these clayey till porewaters.     

Oxygen isotope activities and concentrations in aqueous salt solutions at elevated temperatures: Consequences for isotope geochemistry

Studies of the effect of dissolved salts on the oxygen isotope activity ratio of water have been extended to 275°C. Dehydrated salts were added to water of known isotope composition and the solutions were equilibrated with CO₂ which was sampled for analysis. For comparison similar studies were made using pure water. Results on water nearly coincide with earlier calculations. Salt effects diminish with increasing temperature only for solutions of MgCl₂ and LiCl. Other salt solutions show complex behavior due to the temperature-dependent formation of ion pairs of changing character. Equilibrium fractionations (10³ ln α) between 1 molal solutions and pure water at 25, 100, and 275°C are: NaCl 0.0, ?1.5, +1.0; KCl 0.0, ?1.0, +2.0; LiCl ?1.0, ?0.6, ?0.5; CaCl₂ ?0.4, ?1.8, +0.8; MgCl₂ ?1.1, ?0.7, ?0.3; MgSO₄ ?1.1, +0.1, ?; NaF (0.8 m) 0.0, ?1.5, ?0.3; and NH₄Cl (0.55 m) 0.0, ?1.2, ?1.3. These effects are significant in the isotope study of hot saline fluids responsible for ore deposition and of fluids found in certain geothermal systems. Minor modification of published isotope geothermometers may be required.