The extent of oxygen isotope exchange between clay minerals and sea water

The extent of oxygen isotopic exchange between detrital clay minerals and sea water was investigated by analyzing $\text{O}{}^{18}\text{O}{}^{16}$ ratios of separated fine-grained size fractions of deep-sea sediments from three North Pacific ocean cores. Isotopic results were interpreted according to models based on the assumption that the extent of isotopic exchange should increase with decreasing particle size and increasing time of exchange between the sediment and sea water. The data indicate that information concerning the provenance and mode of formation of detrital clay minerals can be obtained from the $\text{O}{}^{18}\text{O}{}^{16}$ ratios of the coarser-than-0.1 μm fraction of deep-sea sediments younger than several million years and the finer-than-0.1 μm fraction of deep-sea sediments younger than several tens of thousands of years. Furthermore, if the extent of chemical reaction between detrital clays and sea water is similar to the extent of oxygen isotopic exchange, such reaction may be important in regulating the chemistry of sea water.     

Annual periodicity of the 18O16O and 13C12C ratios in the coral Montastrea annularis

The isotopic ratios ${}^{18}\text{O}{}^{16}\text{O}$ and ${}^{13}\text{C}{}^{12}\text{C}$ show an annual periodicity in the coral Montastrea annularis from Bermuda, Jamaica and Barbados. The abundances of ¹⁸O and ¹³C are positively correlated in the Jamaica and Barbados samples, but inversely related in the Bermuda sample. Annual high density growth bands are formed during the season of warmest water temperature at all 3 sites and are enriched in ¹⁶O. M. Annularis has a constant displacement from oxygen isotopic equilibrium and accurately records seasonal temperature variations via the temperature-dependent aragonite-water fractionation factor. Light intensity, through the activity of the coral's endosymbiotic algae, regulates the depth-dependent and seasonal variations in the skeletal carbon isotopic composition.     

Untersuchung von isotopenfeinvariationen des calciums in der natur an rezenten carbonaten und sulfaten

Investigations of isotopic variations of calcium were carried out. For that purpose natural calcium carbonate and calcium sulfate samples were analysed. The isotopic ratios ${}^{44}\text{Ca}{}^{40}\text{Ca}$ and ${}^{48}\text{Ca}{}^{40}\text{Ca}$ were measured with a mass spectrometer by thermal ionization. The precision of the isotopic abundance measurements was better than 1%. per mass unit. One can conclude from the results that in general chemical exchange reactions of calcium ions which imply isotopic fractionation do not take place in nature. Only in the case of one sample (‘Gipsrose’) an isotopic variation of calcium was found. This fractionation can be explained by ion exchange or different diffusion rates of the calcium isotopes.     

Atmospheric and juvenile noble gases in the Skaergaard layered igneous intrusion

Gabbro and diorite from the Skaergaard layered igneous intrusion contain noble gases which are mixtures of atmospheric and juvenile components. Atmospheric noble gases predominate in samples that have undergone extensive oxygen isotope exchange with meteoric-hydrothermal water. The source of the atmospheric noble gas component is inferred to be the hydrothermal circulation system. A juvenile component with ${}^{40}\text{Ar}{}^{36}\text{Ar}\text{≥ 6100}$ and containing fission xenon is also present This component predominates in samples showing unaltered magmatic oxygen isotope compositions. Neon of atmospheric isotopic composition is associated with the juvenile radiogenic ⁴⁰Ar and fission xenon. The source of this second noble gas component may be either the crustal country rock or the upper mantle. If the neon is juvenile primordial neon from a mantle source region, terrestrial primordial ${}^{20}\text{Ne}{}^{22}\text{Ne}$ is the same as atmospheric to within 4%. However, subduction of atmospheric noble gases into the upper mantle may provide an alternate source of neon and other noble gases in the mantle.     

The RbSr isotope system as an index of origin and diagenetic evolution of southern Pacific red clays

Morphological, mineralogical, chemical and RbSr isotopic studies have been made on Fesmectites (nontronites) from southern Pacific red clays cored near the Marquisas Islands. These minerals have at the top of the core, an ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio of 0.70917 ± 0.00007, which indicates an authigenic origin in isotopic equilibrium with seawater. Weak leaching experiments with 1N HCl show that the nontronites also contain a volcanic component with a lower ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio which, combined with the morphology of the particles, suggests a transportation by bottom currents of clay formed elsewhere.During burial, the nontronites experience diagenetic modifications resulting in an increase in Fe, K and Rb contents, a concomitant decrease of Mg, Ca, Ti, Na and Sr, and a preferential migration of radiogenic ⁸⁷Sr from the clays into the surrounding pore waters.The ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio of the Sr adsorbed on the outermost surfaces of the nontronites does not change with depth in the core, and is, therefore, independent of diagenetic influence, which is rather characterized by the ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios of the interstitial waters. The isotopic composition of both the adsorbed Sr and that of the pore fluids may yield useful information on the crystallization environment and subsequent history of deep sea red clays.     

Hydrogen and carbon isotopic ratios of the cellulose nitrate and saponifiable lipid fractions prepared from annual growth rings of a California redwood

The $\text{D}\text{H}$ and ${}^{13}\text{C}{}^{12}$C ratios of the cellulose nitrate and saponifiable lipid fractions prepared from eleven annual growth rings of a California redwood were determined. The $\text{D}\text{H}$ ratios of the two fractions are related to one another for the annual rings in the sapwood portion of the tree, but not for those in the heartwood or in the wood undergoing the transition from sapwood to heartwood. No relationship was observed between the ${}^{13}\text{C}{}^{12}$ ratios of the two fractions. These results suggest that analysis of the hydrogen isotopic composition of the saponifiable lipid fractions in plants will provide information useful for climatic reconstruction provided the initial isotopic record has not been changed by subsequent physiological or diagenetic processes.     

A detailed Pb isotopic study of crustal contamination/assimilation: The Edgecumbe volcanic field,SE Alaska

To better understand the process of crustal contamination/assimilation, 23 Pb isotopic compositions and 12 concentrations have been measured on lavas and basement rocks from the Edgecumbe volcanic field, SE Alaska. Measured isotopic ratios have the following ranges: ${}^{206}\text{Pb}{}^{204}\text{Pb}\text{= 18.477–19.161}$; ${}^{207}\text{Pb}{}^{204}\text{Pb}\text{= 15.562–15.679}$; ${}^{208}\text{Pb}{}^{204}\text{Pb}\text{= 38.17–38.85}$. While the data form well-constrained linear arrays on Pb-Pb diagrams, no simple correlation exists with major element composition. Basaltic lavas (≤ 51 wt% SiO₂) are characterized by two isotopic groups. The olivine basalt (≤ 48% SiO₂) is more radiogenic than the plagioclase basalt (48–51%) which also shows more heterogeneity. In the silica range 52–55%, Pb isotopic ratios increase significantly but remain fairly constant in the range 55–70% SiO₂. Lead concentrations vary from 1 ppm in the basalts to 7 ppm in the rhyodacites. Analyzed basement rocks are more radiogenic than any of the lavas $\text{(}{}^{206}\text{Pb}{}^{204}\text{Pb}\text{= 19.20}$; ${}^{207}\text{Pb}{}^{204}\text{Pb}\text{= 15.65}$; ${}^{208}\text{Pb}{}^{204}\text{Pb}\text{= 38.86}$. The Pb isotopic data are qualitatively consistent with the contamination process described by Myerset al. (1984). However, because of fundamental differences in the mixing relations between the Sr system studied earlier and the Pb system, the new Pb data have revealed details of the process not apparent from the Sr data alone. In particular, it has been shown that the parent magma was more primitive than originally assumed, and that two contamination events are recorded in the lavas. The first event, involving a mafic parent and different crustal contaminants, produced the intermediate and siliceous hybrids in cupolas located above the main basaltic chamber. The types of country rock intruded as well as the degree of partial fusion achieved in individual cupolas controlled the range of hybrid compositions produced while the eruption sequence was determined by the order in which the cupolas were tapped. The second contamination event produced the plagioclase basalt, the most voluminous basaltic unit, by mixing the mafic parent with the olivine basalt, an independent, primary magma. Our results suggest crustal contamination models that assume bulk assimilation of crustal end members may be too simplistic.     

The geochemical evolution of the Pleistocene Lake Lisan-Dead Sea system

The geochemical history of Lake Lisan, the Pleistocene precursor of the Dead Sea, has been studied by geological, chemical and isotopic methods.Aragonite laminae from the Lisan Formation yielded (equivalent) Sr/Ca ratios in the range 0.5 × 10^?2?1 × 10^?2, Na/Ca ratios from 3.6 × 10^?3 to 9.2 × 10^?3, $\text{δ}{}^{18}\text{O}{}_{\mathrm{PDB}}$ values between 1.5 and 7%. and $\text{δ}{}^{13}\text{C}{}_{\mathrm{PDB}}$ from ?7.7 to 3.4%..The distribution coefficient of Na⁺ between aragonite and aqueous solutions, $\text{λ}{}^{\mathrm{A}}{}_{\mathrm{Na}}$, is experimentally shown to be very sensitive to salinity and nearly temperature independent. Thus, Na/Ca in aragonite serves as a paleosalinity indicator.Sr/Ca ratios and $\text{δ}{}^{18}\text{O}$ values in aragonite provide good long-term monitors of a lake's evolution. They show Lake Lisan to be well mixed, highly evaporated and saline. Except for a diluted surface layer, the salinity of the lake was half that of the present Dead Sea (15 vs 31%).Lake Lisan evolved from a small, yet deep, hypersaline Dead Sea-like, water body. This initial lake was rapidly filled-up to its highest stand by fresh waters and existed for about 40,000 yr before shrinking back to the present Dead Sea. The chemistry of Lake Lisan at its stable stand represented a material balance between a Jordan-like input, an original large mass of salts and a chemical removal of aragonite. The weighted average depth of Lake Lisan is calculated, on a geochemical basis, to have been at least 400, preferably 600 m.The oxygen isotopic composition of Lake Lisan water, which was higher by at least 3%. than that of the Dead Sea, was probably dictated by a higher rate of evaporation.Na/Ca ratios in aragonite, which correlate well with $\text{δ}{}^{13}\text{C}$ values, but change frequently in time, reflect the existence of a short lived upper water layer of varying salinity in Lake Lisan.     

Strontium isotopic studies of the volcanic rocks of the Saunda arc,Indonesia, and their petrogenetic implications

Pleistocene and Recent lavas from the Sunda arc range from those showing affinities with the island arc tholeiitic series, through a spectrum of calc-alkaline to high-K alkaline rocks. The tholeiitic rocks have relatively low ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios averaging 0–7043; the calc-alkaline rocks show a wide range (from 0.7038 to 0.7059, averaging 0.7048); the high-K alkaline rocks average 0.7045. A rhyolitic ignimbrite from Sumatra has an ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio of 0.7139.The relationship between ${}^{87}\text{Sr}{}^{86}\text{Sr}$ and major and trace element geochemistry is variable and complex. Lavas from the same volcano sometimes show significant differences in ${}^{87}\text{Sr}{}^{86}\text{Sr}$ despite close geochemical relationships. Rocks of the calc-alkaline suite show a regular decrease in ${}^{87}\text{Sr}{}^{86}\text{Sr}$ from West Java to Bali and there is some evidence for increasing ${}^{87}\text{Sr}{}^{86}\text{Sr}$ with increasing depth to the Benioff zone. Calc-alkaline and tholeiitic rocks from the Sunda arc have significantly higher ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios than those from other island arcs, except from those arcs where continental crustal involvement has been inferred (e.g. New Zealand).A model of ⁸⁷Sr enrichment due to isotopic equilibration of oceanic crust with sea water and disequilibrium melting in the slab and/or mantle is favoured to explain the Sr isotopic composition of the tholeiitic and normal calc-alkaline lavas. Calc-alkaline lavas with high ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios are best explained by either sialic contamination, or the presence of alkali basalt as a component of the downgoing slab. The Sr isotopic data for the high-K alkaline lavas suggest a mantle origin. The high ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio in the Lake Toba rhyolite implies a crustal origin.     

FUN with PANURGE: High mass resolution ion microprobe measurements of Mg in Allende inclusions

The performance characteristics of PANURGE, a modified CAMECA IMS3F ion microprobe, have been studied at a mass resolving power of 5000 for the purpose of determining isotopic ratios at a precision level approaching that of counting statistics using beam switching. The techniques used for this type of measurement are described. Using this approach, the isotopic composition of Mg and Si and the atomic ratio of $\text{Al}\text{Mg}$ in minerals from the Allende inclusion WA and the Allende FUN inclusion Cl have been measured with the ion microprobe at high mass resolving power. Enrichments in ²⁶Mg of up to 260%. have been found. Mg and $\text{Al}\text{Mg}$ measurements on cogenetic spinel inclusions and host plagioclase crystals yield Mg-Al isochrons in excellent agreement with precise mineral isochrons determined by thermal emission mass spectrometry. The measurements confirm the presence of substantial excess ²⁶Mg in WA (${}^{26}\text{Mg}{}^1{}^{27}\text{Al = 5 × 10}{}^{\mathrm{?5}}$) and its near absence in Cl (${}^{26}\text{Mg}{}^1{}^{27}\text{Al}\text{< 4 × 10}{}^{\mathrm{?6}}$). In WA plagioclase, data for which ${}^{27}\text{Al}{}^{24}\text{Mg}\text{= 300 to 1000}$ define a linear array with ${}^{26}\text{Mg}{}^1{}^{27}\text{Al}\text{= 3 × 10}{}^5$ and with initial ${}^{26}\text{Mg}{}^{24}\text{Mg}$ composition 30%. greater than in high Mg phases. This suggests a metamorphic reequilibration of Mg in Allende plagioclase at least 0.6 my after WA formation. There were no variations in detected ${}^{26}\text{Mg}{}^1{}^{27}\text{Al}$ in WA plagioclase associated with concentration of ²⁶Mg¹ into isolated clusters. We have confirmed by ion probe measurements that the Mg composition in Allende Cl is highly fractionated and is uniform among pyroxene, melilite, plagioclase, spinel crystals and spinel included in melilite and plagioclase crystals. Likewise, the Si composition is mass fractionated and is the same in pyroxene, melilite and plagioclase.     

Sulphur isotope effects in the dissociation and evaporation of troilite: A possible mechanism for 34S enrichment in lunar soils

Both the dissociation and evaporation of troilite. heated to its melting point in vacuo, are isotopically selective. The elemental sulphur from the dissociation of troilite has a ${}^{34}\text{S}{}^{32}\text{S}$ ratio which is 13.0‰ less than that of the undissociated material while the ${}^{34}\text{S}{}^{32}\text{S}$ ratio in evaporated troilite is 5.4‰ less than that of the residual material. The two processes occur simultaneously and the isotopic variations during the course of the reaction are in accord with those for a branched reaction where the unreacted material remains isotopically well-mixed, as in a Rayleigh distillation process. This isotopic selectivity must be taken into account, along with that in other lunar surface processes, when considering the heavy isotope enrichment of sulphur in lunar soils.     

A study of strontium in core 119K,Discovery deep,Red Sea

The isotopic composition of strontium of pore water and of authigenic minerals leached from the sediment of core 119K with hot aqua regia is similar to that of the brine in the Discovery deep and differs from that of normal seawater. The average ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratio of strontium removed by acid leaching is 0.7077 ± 0.0007 (1σ) compared to a value of 0.70904 for the Red Sea. The detrital silicate fraction exhibits an approximate inverse correlation between ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios and strontium concentrations which provides tentative support for a model in which the detrital silicate fraction of deep-sea sediment is considered to be a mixture of terrigenous dust of sialic composition enriched in radiogenic ⁸⁷Sr and of volcanogenic material of basaltic composition and low ⁸⁷Sr abundance. The ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios of the shells of foraminifers and pteropods, expressed as δ ⁸⁷Sr‰ relative to 0.70904 for seawater, decrease from $\text{?0.23 ± 0.17‰}$ at 90 cm to $\text{?0.82 ± 0.17‰}$ at 273 cm and remain constant at this value to a depth of 450 cm. The lowering of the δ ⁸⁷Sr values is attributed both to the presence of aragonite overgrowths on pteropod shells and to possible isotope exchange with strontium in the connate fluid.     

Source rock-crude oil correlation by isotopic type-curves

An isotopic type-curve has been defined based on the ${}^{13}\text{C}{}^{12}\text{C}$ ratios of the saturated, aromatic, heterocomponent (NOSs), and asphaltene fractions of crude oils. These fractions show ¹³C enrichments with increasing polarity or polarizability. This systematic pattern can be used to estimate the ${}^{13}\text{C}{}^{12}\text{C}$ ratio of the kerogen from which the oil had been generated. Genetically associated source rock oil pairs have been used to show that the difference between the measured and the estimated δ-values of kerogen is about ?0.5%., and between the δ-values of the kerogen and the asphaltene fraction is approximately +0.6%.     

Strontium isotopic contamination and oxidation during ocean floor hydrothermal metamorphism of the ophiolitic rocks of the Troodos Massif,Cyprus

Twenty-six new high precision ${}^{87}\text{Sr}{}^{86}\text{Sr}$ratio determinations and existing analyses are used to discuss the strontium isotopic composition of the Upper Cretaceous ophiolitic rocks of the Troodos Massif, Cyprus. Relative to initial magmatic ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios (0.70338 ± 0.00010 to 0.70365 ± 0.00005), the hydrothermally metamorphosed pillow lavas and dyke complex have been contaminated by isotopically heavier strontium.This observation confirms the hypothesis that hydrothermal metamorphism was a consequence of sea water-rock interaction, since sea water was the only readily accessible reservoir of isotopically heavier strontium. The fact that metagabbros and altered trondhjemites were also Sr isotopically contaminated shows that sea water penetrated approximately 2 km into the oceanic crust represented by the ophiolitic sequence.The amount of Sr isotopic contamination requires that the bulk sea water: rock ratio was at least ~15:1 and shows that water-rock interaction occurred in a flow system. The degree of oxidation decreases with increasing depth. This shows that the vertical component of fluid flow was downward. The absolute bulk water/rock ratio (for water at S.T.P.), as estimated from the oxidation profile, may have been as large as ~3 × 10³:1 —a large figure which independently confirms that rocks showing strong δ¹⁸O shifts have interacted with large volumes of water.The sites of discharge of the hot fluid, which must have come out of the system, are identified as the cupriferous pyrite ore deposits. This process of mass transfer corresponds to hydrothermal convection in a permeable medium with an open upper boundary surface.     

Strontium isotope geochemistry of Icelandic geothermal systems and implications for sea water chemistry

Chemical and Sr isotopic analyses have been made of waters from 16 geothermal sites in Iceland with particular reference to the systems at Reykjanes and Svartsengi for which compositions of geothermal sea water and fresh and hydrothermally-altered rocks have been compared. The alkalies display mixing relationships indicating a hydrothermal input of Rb and K to local meteoric and sea waters as do results for Sr and Ca involving high-temperature fluids. ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios of the geothermal waters of meteoric origin parallel those of associated rocks but are higher. Ratios for geothermal sea waters are 0.7042 (Reykjanes) and 0.7040 (Svartsengi), lower than for normal sea water (0.7092) because of leaching of Sr from rocks followed by partial removal into alteration minerals, of which epidote and chlorite may be most important. Consequently, associated hydrothermally-altered rocks have been subject to significant Sr isotopic contamination by sea water Sr raising ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios from 0.7032 for fresh rock to 0.7038–0.7042 (Reykjanes) and to 0.7039–0.7041 (Svartsengi). Altered basalt is only ~50% equilibrated isotopically with geothermal sea water, at a water/rock ratio of ~2, but is internally equilibrated whereas palagonitized rocks (water/rock ratio of 3 to 4) are close to Sr isotopic equilibrium with associated sea water but show significant internal Sr disequilibrium. Hydrothermal input is unlikely to be important in the oceanic mass balance of Sr but is likely to be highly significant in controlling the strontium isotopic composition of sea water.     

Isotopic composition of strontium in Indian kimberlites

Strontium isotopic studies on twenty three whole rock kimberlites from two petrographic provinces in India show variation of initial ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios from 0.7027 to 0.7102. The variation is unrelated to the degree of alteration. Between the micaceous and basaltic varieties there is some overlap in the Sr isotopic ratios. Leaching experiments on whole rock samples showed more highly radiogenic Sr in leaches compared to the bulk samples.In two diatremes, the initial ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios show a positive correlation with $\text{Rb}\text{Sr}$ which is believed to reflect a source event earlier than the formation of the kimberlites. The observed Sr isotopic data can be caused by (i) melting of a heterogeneous source or (ii) disequilibrium partial melting in the source region. In the former case, variable isotopic composition would be a necessary consequence of melting in small subsystems.     

The isotopic composition and concentration of Ag in iron meteorites and the origin of exotic silver

The isotopic composition of Ag and the concentration of Ag and Pd have been determined in Canyon Diablo (IA), Grant (IIIB), Hoba, Santa Clara, Tlacotepec and Warburton Range (IVB), Piñon and Deep Springs (anom.). Troilite from Grant and Santa Clara have also been analyzed. All of these meteorites, with the exception of Canyon Diablo, give ${}^{107}\text{Ag}{}^{109}\text{Ag}$ in the metal phase that is greater than the terrestrial value with the enrichments of ¹⁰⁷Ag ranging from ~2% to 212%. These data show that Ag of anomalous isotopic composition is common to all IVB and anomalous meteorites. The results on Grant suggest that the anomalies may be widespread including more common meteorite groups. There is a general correlation of ${}^{107}\text{Ag}{}^{109}\text{Ag}$ with $\text{Pd}\text{Ag}$ except for the data from FeS of Santa Clara. It is concluded that the excess ¹⁰⁷Ag is the result of decay of ¹⁰⁷Pd, a nuclide that is extinct at present with an abundance of ${}^{107}\text{Pd}{}^{108}\text{Pd}$ of about 3 × 10^?5. The troilite in Grant exhibits normal ${}^{107}\text{Ag}{}^{109}\text{Ag}$ to within errors, a high Ag concentration and a low ratio of ${}^{108}\text{Pd}{}^{109}\text{Ag}$ ~0.17. Grant metal has ${}^{107}\text{Ag}{}^{109}\text{Ag}$ that is ~2% greater than normal and a high ratio of ${}^{108}\text{Pd}{}^{109}\text{Ag}$ ~ 10³. The data from Grant appear to represent a ¹⁰⁷Pd-¹⁰⁷Ag isochron and indicate that the cooling rate at elevated temperatures was sufficiently rapid to preserve substantial isotopic differences between metal and troilite. Troilite in Santa Clara was found to contain Ag with a very high ${}^{107}\text{Ag}{}^{109}\text{Ag}$ ratio (108% above normal), an Ag concentration only a factor of three above the metal and a high value of ${}^{108}\text{Pd}{}^{109}\text{Ag}$ ~1.3 × 10⁴. The troilite has a higher ${}^{107}\text{Ag}{}^{109}\text{Ag}$ than the metal. These data are not compatible with a simple model of in situ decay and subsequent local Ag redistribution between metal and troilite during cooling. These data suggest that Ag in Santa Clara and possibly other IVB meteorites is made up of almost pure ¹⁰⁷Ag produced from ¹⁰⁷Pd decay and ¹⁰⁹Ag produced by nuclear reactions with only a small amount of “normal” Ag. This indicates an intense energetic particle bombardment history in the early solar system (~10²⁰ p/m²) which occurred after the formation of small planetary bodies. We infer that a T-Tauri activity by the early sun contributed to some late stage “nucleosynthesis” and the heating of a dust cloud. In addition, implications on the early thermal evolution of iron meteorites are presented based on ¹⁰⁷Pd decay and models of the cooling history.     

Oxygen-isotope variations in sulfate ions in the water of some Italian lakes

The results obtained by measuring the sulfate content and its $\text{O}{}^{18}\text{O}{}^{16}$ ratios through time in some volcanic, tectonic and dam Italian lakes are reported here. The variations with time of the oxygen isotopic composition of the lake waters are also reported. The measurements refer mainly to surface water; however, a few deep samples were also studied.In the case of all the lakes examined, the variations with time of the oxygen isotopic composition and of the concentration of the dissolved sulfate cannot be explained in terms of the addition and of seasonal variations of the O¹⁸ content of rainwater sulfate. Biological redox processes involving bacterial reduction of sulfate and sulfide oxidation can reasonably account for the results obtained.According to Lloyd (1967), when sulfate is formed by bacterial sulfide oxidation, 68 per cent of the sulfate oxygen is water oxygen, while 32 per cent is dissolved molecular oxygen. The isotopic enrichment of the dissolved molecular oxygen in the lake waters relative to the isotope content of the atmospheric oxygen is mainly related to the biological activity in the waters.Assuming that a stagnation period takes place during summer and fall while a period of strong bio-respiratory activity takes place during winter and spring, it follows that a small isotope fractionation effect on molecular dissolved oxygen can be expected during stagnation while a high isotope fractionation can be expected during winter and spring. The O¹⁸ content of the sulfate dissolved in volcanic and tectonic lakes varies according to this hypothesis. The fact that similar O¹⁸ contents of the dissolved sulfate are or are not found in the same period of different years is probably related to similarities or differences in the climatic conditions.The bio-physical behaviour of the Corbara dam lake is different from that of other lakes. However, because of the continuous feeding by the Tiber River, variations of the sulfate concentration and its oxygen isotopic composition can be caused by the contribution of polluted water.