S, O and Sr isotope systematics of active vent materials from the Mariana backarc basin spreading axis at 18°N

Stable isotope ratios of S, O and Sr have been measured for active vent materials which were first found and sampled in April 1987 from the Mariana backarc spreading axis at 18°N. Chimneys consisted mostly of barite with a lesser proportion of sulfide minerals such as sphalerite, galena, chalcopyrite and pyrite. Theδ³⁴S values of sphalerite and galena taken from several chimneys and various parts of a chimney showed a narrow range from 2.1 to 3.1‰, suggesting uniform conditions of fluid chemistry during chimney growth. The sulfur isotopic results imply a contribution of hydrogen sulfide reduced from seawater sulfate in the deep hydrothermal reaction zone, considering that fresh glasses of the Mariana Trough basalts haveδ³⁴S= −0.6 ± 0.3‰. Sulfur isotopic compositions of hydrogen sulfide in the high temperature vent fluids (δ³⁴S= 3.6–4.8‰) which are higher than those of the sulfide minerals suggest the secondary addition of hydrogen sulfide partially reduced from entrained seawater SO₄²⁻ at a basal part of the chimneys. This interpretation is consistent with theδ³⁴S values of barite (21–22‰) that are higher than those of seawater sulfate. The residence time of the entrained SO₄²⁻ was an order of an hour on a basis of oxygen isotopic disequilibrium of barite. Strontium isotopic variations of barite and vent waters indicated that Sr in barite was mostly derived from the Mariana Trough basalts with a slight contribution from Sr in circulating sea-water, and that 10–20% mixing of seawater with ascending hydrothermal fluids induced precipitation of barite at the sea-floor.     

East Pacific Rise at latitude 21°N: isotopic composition and origin of the hydrothermal sulphur

The sulphur isotope composition of 16 pyrite and chalcopyrite samples from recent sulphide deposits (“Cyana”—project RITA) and active sulphide mineralisation (“Alvin”—project RISE) associated with hydrothermal sources at 380±30°C on the East Pacific Rise at latitude 21°N have been measured. The³⁴S/³²S ratios are relatively uniform and essentially identical for both sites: δ³⁴S=+1.4to3.0%. (CDT), mean +2.1‰. The sulphides were analysed after the majority of the very numerous micro-inclusions of anhydrite had been removed.Two independent physico-chemical analyses of the data demonstrate that about 90% of the sulphur was leached from the basaltic host rocks by the circulating seawater-hydrothermal fluids.     

Sulphur isotope equilibrium during sulphur hydrolysis at high temperatures

Studies of the sulphur hydrolysis reaction, 4S + 4H₂O /ag 3H₂S + HSO₄^? + H⁺, were conducted between 200 and 320°C in sealed silica glass tubes. The isotope exchange reaction: H₂¹⁸O + HS¹⁶O₄^? /ag H₂¹⁶O + HS¹⁸O₄^? is so rapid at the low pH (1.5–3) as to be unquenchable. However, the sulphur isotope exchange reaction: H₂³⁴S+ H³²SO₄^? /ag H₂³²S + H³⁴SO₄^? gave t12 values of 0.1, 0.3 and 1.7 days at 320, 260 and 200°C respectively and equilibrium H₂S - HSO₄^? sulphur isotope fractionation values of 20.9, 22.4, 24.8, 26.7 and 29.3‰ at 320, 290, 260, 230 and 200°C respectively. This latter data is represented by: 1000lnα_(HSO4^??H2S) = 5.07 (10⁶T^?2) + 6.33, and has valuable applications in geothermal and ore deposit studies.     

Experimental determination of the rate and equilibrium fractionation factors of sulfur isotope exchange between sulfate and sulfide in slightly acid solutions at 300°C and 1000 bars

A sulfur isotope fractionation of 20.0 ± 0.2‰ was measured between aqueous sulfide and sulfate at 300°C and 1000 bars using gold-cell hydrothermal solution equipment. The value is 2‰ smaller than previously published values. Rates of exchange were determined as a function of pH and total sulfur content. Initial mean ³⁴S concentration was changed to approach equilibrium from two directions. Half-times ranged from 3.4 to 8.2 days, with shorter times obtained for more acid and more concentrated solutions.The sulfate-sulfide isotope temperature scale based on theory should be revised according to this new fractionation factor. The rate data permit assessment of the extent to which equilibrium may be attained in some natural systems. For example, the lack of agreement between temperatures based on sulfide mineral pairs and sulfide-sulfate mineral pairs from Kuroko ore deposits of Japan might imply that the residence time of sulfate and sulfide in Kuroko solutions was not longer than 1000 years, if the present kinetic data are correct. Geothermal systems such as the Wairakei system of New Zealand may reach sulfur isotope equilibrium between sulfate and sulfide in 300 years at 300°C, but would be increasingly removed from equilibrium at lower temperatures if residence times were 300 years or less.     

Water recovery rate and isotopic signature of cryogenic vacuum extracted spiked soil water following oven-drying at different temperatures

Extracting water from soils is often a critical step for obtaining soil water isotope information. Cryogenic vacuum extraction (CVE), the most widely used laboratory-based removal technique, produces biased isotope composition and the mechanisms causing the biases remain uncertain. Here, we conducted spiking tests on soil samples oven-dried at 105 and 205°C, respectively. The recovery rate and isotopic composition of the extracted water were analysed. Our results show that conventional oven-drying (105°C) was not sufficient to liberate tightly bound water from soils but oven-drying at temperatures above 205°C was. Part of the tightly bound water in soil was extracted by CVE, because the extraction capacity of CVE (heating at 95°C) was equivalent to oven-drying at temperature between 105 and 205°C. Moreover, the two pretreatments yielded markedly differences in water recovery rates. And with increasing ratios of clay contents to water contents, the recovery rates of the pretreated soil at 105°C trended upward above 100%, but that of 205°C trended downward below 100%. Further, the ²H and ¹⁸O signatures of the extracted water from the soil pretreated at 205°C were both depleted relative to reference water, but the pretreatment at 105°C showed enriched ¹⁸O and depleted ²H. This suggests that oxygen isotope exchange may have occurred between tightly bound water and soil minerals, resulting in enriched ¹⁸O in water for the 105°C pretreatments. For the 205°C pretreatment, pre-existing soil water was completely removed and relative to spiking water, isotopic signatures of the extracted water followed equilibrium fractionation law due to incomplete extraction. Therefore, our results suggested that the biased isotopic signatures of water extracted by CVE may be partially due to incomplete extraction and mixture of added water with the residual tightly bound water that pre-exists before spiking.     

Nitrogen contents and isotopic ratios of clasts from the enstatite chondrite Abee

Nitrogen contents and isotopic ratios have been determined for three clasts from the enstatite chondrite Abee by stepwise heating. The clasts possess a wide range in nitrogen content, ranging from 254 to 850 ppm, whereas the nitrogen isotopic ratios are nearly identical atδ¹⁵N= ?29.2±0.6‰. A refractory inorganic nitrogen-bearing phase contains about 90% of the nitrogen which is released at temperatures of 1000°C and above. The stepwise heating experiments suggest the possible existence of two other distinct nitrogen components, released at low (770°C) and high (1500°C) temperatures.     

Effect of degassing on sulfur contents and δ34S values in Somma-Vesuvius magmas

Sulfur contents and δ³⁴S values of Somma-Vesuvius magmas are consistent with syneruptive, open-system degassing at temperatures of 800–850°C for Plinian pumices and 1100–1200°C for lavas. The extent of degassing appears to be greater in lavas than in pumices. The key parameter controlling the ³⁴S/³²S ratio of Somma-Vesuvius volcanics is the average magma oxidation state, which generally varies from 0.85 to 1.20 Δ NNO units for lavas and from 1.20 to 1.40 Δ NNO units for pumices. Consequently, S contents and δ³⁴S values of magmas constitute a potentially valuable tool in estimating their average redox conditions. The results of this study may help in risk mitigation when the Vesuvius magmatic system evolves toward eruptive conditions. Received: 20 January 1998 / Accepted: 5 May 1998     

Geochemistry of basalts from the Indian Ocean triple junction: implications for the generation and evolution of Indian Ocean ridge basalts

Basalts dredged from ridge axes within 70 km of the Indian Ocean triple junction in the western Indian Ocean have many geochemical and petrologic characteristics in common with depleted mid-ocean ridge basalts (MORBs) from the Atlantic and Pacific. For example there is overlap in major and trace element abundances, and in diagnostic ratios such as K/Rb (700–925) and La/Sm (less than chondritic). Also, glass inclusions in calcic plagioclase (An_89–90) provide evidence for a primitive high Mg/Fe, low TiO₂ melt. In contrast, basalts dredged from 250 to 400 km southwest of the triple junction on the Southwest Indian Ridge are compositionally distinct from depleted MORB. They are nepheline-normative or slightly hypersthene normative and have higher alkali metal and incompatible element abundances than depleted MORBs with similar MgO contents.All of these Indian Ocean basalts have Sr, Nd and Pb isotope ratios which corroborate previous studies showing that relative to depleted Atlantic and Pacific MORB, many Indian Ocean MORBs have low²⁰⁶Pb/²⁰⁴Pb and high⁸⁷Sr/⁸⁶Sr. However, individual Indian Ocean ridges have different radiogenic isotope characteristics, and basalts from the vicinity of the triple junction have unusually high⁸⁷Sr/⁸⁶Sr (∼ 0.7032) at low²⁰⁶Pb/²⁰⁴Pb ratios (17.3–18.2). Moreover, the shallow axial region of the Central Indian Ridge from ∼ 12°S to the triple junction (26°S) has high⁸⁷Sr/⁸⁶Sr (> 0.7030). Apparently, the depleted component of Indian Ocean MORBs has been contaminated by an isotopically unusual component which does not occur in Pacific and Atlantic MORBs, and is not dominant in basalts from many Indian Ocean islands. The degree of this contamination is not uniform in western Indian Ocean MORB; the most contaminated basalts occur from 12°S on the Central Indian Ridge to the triple junction (∼ 26°S) and easterly along the Southeast Indian Ridge to ∼ 72°E.     

Sulfur isotope systematics at the 21°N site,East Pacific Rise

Hydrogen sulfide in hydrothermal vent fluid at the 21°N site is enriched in ³⁴S relative to Mid-Ocean Ridge basalts, probably by addition of H₂S reduced from seawater sulfate by FeO-bearing basalt. Metalliferous sulfides are depleted in ³⁴S relative to the fluid from which they apparently precipitated, the degree of depletion reflecting the microenvironment in which each mineral crystallised and/or kinetic effects. Isotopic compositions of coexisting sulfides in a basal mound are consistent with equilibration at around 445°C, though heating to such a high temperature seems unlikely. Similar sulfides in a black smoker and in a dead chimney are out of isotopic equilibrium at any temperature, apparently reflecting a complex series of replacement mineralisations and post-depositional oxidation, respectively.     

Stable and radiogenic isotopes as tracers for the origin,mixing and subsurface history of fluids in submarine shallow-water hydrothermal systems

The shallow-water hydrothermal system in Tutum Bay on the west side of Ambitle Island, Papua New Guinea provides us with an exceptional opportunity to study isotope systematics in a near shore setting. Compared to seawater, the hydrothermal fluids in Tutum Bay have lower values for δD, δ¹⁸O, δ¹³C, and ⁸⁷Sr and higher values for ³H, δ³⁴S(SO₄) and δ¹⁸O(SO₄). The δ¹⁸O and δD records for vents 1 and 4 indicate that fluid compositions remained stable over an extended period. Interpretation of isotope data clearly demonstrates the predominantly meteoric origin of Tutum Bay hydrothermal fluids, despite their location in a marine environment. δ¹⁸O and δD values are identical to mean average annual precipitation in eastern Papua New Guinea. The hypothesis that these fluids are a simple product of mixing between seawater and onshore hydrothermal fluids from the Waramung (W-1) and Kapkai (W-2) thermal areas has been rejected, because the observed δ³⁷Cl, ³H, δ³⁴S(SO₄) and δ¹⁸O(SO₄) values cannot be explained by a simple mixing model. The application of δ¹⁸O(SO₄) and δ¹³C thermometers in combination with ³H values corroborates the three-step model of Pichler et al. [Pichler, T., Veizer, J., Hall, G.E.M., 1999. The chemical composition of shallow-water hydrothermal fluids in Tutum Bay, Ambitle Island, Papua New Guinea and their effect on ambient seawater. Marine Chemistry 64 (3) 229–252], where (1) phase separation in the deep reservoir beneath Ambitle Island produces a high temperature vapor that rises upward and subsequently reacts with cooler ground water to form a low pH, CO₂-rich water of approximately 150–160 °C, (2) caused by the steep topography, this CO₂-rich fluid moves laterally towards the margin of the hydrothermal system where it mixes with the marginal upflow of the deep reservoir fluid. This produces a dilute chloride water of approximately 165 °C, and (3) possibly the entrainment of minor amounts of ground or seawater during its final ascent.     

Anisotropic P-wave attenuation measured from a multi-azimuth surface seismic reflection survey

A system of aligned vertical fractures produces azimuthal variations in stacking velocity and amplitude variation with offset, characteristics often reported in seismic reflection data for hydrocarbon exploration. Studies of associated attenuation anisotropy have been mostly theoretical, laboratory or vertical seismic profiling based. We used an 11 common‐midpoint‐long portion of each of four marine surface‐seismic reflection profiles, intersecting each other at 45° within circa 100 m of a common location, to measure the azimuthal variation of effective attenuation, Q⁻¹_eff and stacking velocity, in a shallow interval, about 100 m thick, in which consistently orientated vertical fracturing was expected due to an underlying salt diapirism. We found qualitative and quantitative consistency between the azimuthal variation in the attenuation and stacking velocity, and published amplitude variation with offset results. The 135° azimuth line showed the least apparent attenuation (1000 Q⁻¹_eff= 16 ± 7) and the fastest stacking velocity, hence we infer it to be closest to the fracture trend: the orthogonal 45° line showed the most apparent attenuation (1000Q⁻¹_eff= 52 ± 15) and slowest stacking velocity. The variation of Q⁻¹_eff with azimuth φ is well fitted by 1000Q⁻¹_eff = 34 − 18cos[2(φ+40°)] giving a fracture direction of 140 ± 23° (±1SD, derived from ‘bootstrapping’ fits to all 11⁴ combinations of individual common‐midpoint/azimuth measurements), compared to 134 ± 47° from published amplitude variation with offset data. The effects of short‐window spectral estimation and choices of spectral ratio bandwidth and offset ranges used in attenuation analysis, individually give uncertainties of up to ±13° in fracture direction. This magnitude of azimuthal variation can be produced by credible crack geometries (e.g., dry cracks, radius 6.5 m, aspect ratio 3 × 10⁻⁵, crack density 0.2) but we do not claim these to be the actual properties of the interval studied, because of the lack of well control (and its consequences for the choice of theoretical model and host rock physical properties) and the small number of azimuths available here.     

Determination of the absolute32S/34S ratio of IAEA-S-1 reference material and V-CDT sulfur isotope standard

The absolute³²S/³⁴S ratios of IAEA-S-1 reference material and V-CDT standard are determined. For cross-checking, two sets of synthetic isotope mixtures are prepared from high purity³²S and³⁴S-enriched materials in different forms: the first set is prepared from BaSO₄ whereas the second is prepared from Ag₂S. The sulfur isotope analyses are done by using SF₆ method with a MAT-251 EM mass spectrometer. The resulting³²S/³⁴S ratio of IAEAS-1 reference material is 22. 656 4 ±0.006 0, and that of V-CDT is 22.649 6 ± 0.006 0. Project supported by the National Natural Science Foundation of China (Grant No. 86020341).     

Characteristics of Cd isotopic compositions and their genetic significance in the lead-zinc deposits of SW China

Up to now, the evaporation and condensation, as well as the biological absorption and inorganic absorptions, have been proved to be major factors in Cd isotope fractionation. And Cd isotopes have been widely applied in studies on the universal evolution and marine environment and so on. However, only a few researches have been conducted in applying Cd isotopes to trace the source of metallogenic material and the evolution of the ore-forming fluid in a complex mineralization environment, especially in a hydrothermal ore-formation system. We measured the Cd isotopic compositions of sphalerite, galena, and ores from five lead-zinc deposits in SW China, and found that the δ ^114/110Cd values varied from ?1.53‰ to 0.34‰, with a total range of 1.87‰, which is greater than most of measured geological samples. Meanwhile, through contrasting the Cd content with Cd isotopic compositions of different deposits, it may be concluded that different genetic lead-zinc deposits have different Cd content and isotopic compositions, which could be a tool for the studies on the origin of ore deposits. Also, the biomineralization and crystal fractionation may also result in Cd isotope fractionation. In a word, although the research of Cd isotopes is presently at the preliminary stage (especially in hydrothermal ore-formation system), this study demonstrated that Cd isotopes can give a clue in tracing the evolution of ore-forming fluid and metallogenic environment.     

87Sr/86Sr ratios in hydrothermal waters and deposits from the East Pacific Rise at 21°N

⁸⁷Sr/⁸⁶Sr ratios of three hydrothermal waters collected on the East Pacific Rise at 21°N define a mixing line between seawater and a hydrothermal end-member at 0.7030 which is derived by seawater-basalt interaction at ca. 350°C and water/rock ratio of about 1.5. Sr concentrations are not affected in the process while Mg uptake from seawater is almost complete. Up to2/3 of this hydrothermal component is involved in anhydrite precipitation while the Sr isotopic ratio in sulfides (chalcopyrite + sphalerite) cannot be distinguished from that of sulfate. It is estimated that ca. 1 × 10¹⁰ moles of strontium are yearly cycled in the hydrothermal systems of mid-oceanic ridges, thereby affecting the⁸⁷Sr/⁸⁶Sr budget of seawater. Mass balance between river runoff, limestone precipitation and ridge basalt alteration suggests that the⁸⁷Sr/⁸⁶Sr ratios of the river runoff are in the range 0.7097–0.7113, and are largely dominated by limestone alteration.     

Carbon monoxide on the primitive earth

The reaction of CO + OH^? in aqueous solution to give formate was studied as a carbon monoxide sink on the primitive earth and in the present ocean. The reaction is first order in OH^? and first order in the molar CO concentration. The second order rate constant is given by log k(M^?1hr^?1) = 15.83?4886/T between 25°C and 60°C. Using the solubility of CO in sea water, and assuming a pH of 8 for a primitive ocean of the present size, the halflife of CO in the atmosphere is calculated to be 12 × 10⁶ yr at 0°C and 5.5 × 10⁴ yr at 25°C.Three other CO sinks would have been important in the primitive atmosphere: CO + H₂ → H₂CO driven by various energy sources, CO + OH → CO₂ + H, and the Fischer-Tropsch reaction of CO + H₂ → hydrocarbons, etc. It is concluded that the lifetime of a CO atmosphere would have been very short on the geological time scale although the relative importance of these four CO sinks is difficult to estimate.The CO + OH^? reaction to give formate is a very minor CO sink on the earth at the present time.     

Sources of ore-forming fluids and metallic materials in the Jinwozi lode gold deposit,eastern Tianshan Mountains of China

This paper presents gas compositions and H-, O-isotope compositions of sulfide- and quartz-hosted fluid inclusions, and S-, Pb-isotope compositions of sulfide separates collected from the principal Stage 2 ores in Veins 3 and 210 of the Jinwozi lode gold deposit, eastern Tianshan Mountains of China. Fluid inclusions trapped in quartz and sphalerite are dominantly primary. H-and O-isotopic compositions of pyrite-hosted fluid inclusions indicate two major contributions to the ore-forming fluid that include the degassed magma and the meteoric-derived but rock ¹⁸O-buffered groundwater. However, H- and O-isotopic compositions of quartz-hosted fluid inclusions essentially suggest the presence of groundwater. Sulfide-hosted fluid inclusions show considerably higher abundances of gaseous species CO₂, N₂, H₂S, etc. than quartz-hosted ones. The linear trends among inclusion gaseous species reflect the mixing tendency between the gas-rich magmatic fluid and the groundwater. The relative enrichment of gaseous species in sulfide-hosted fluid inclusions, coupled with the banded ore structure indicating alternate precipitation of quartz with sulfide minerals, suggests that the magmatic fluid has been inputted to the ore-forming fluid in pulsation. Sulfur and lead isotope compositions of pyrite and galena separates indicate an essential magma derivation for sulfur but the multiple sources for metallic materials from the mantle to the bulk crust.

     

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.     

Experimental hydrogen isotope studies,II. Fractionations in the systems epidote-NaCl-H2O,epidote-CaCl2-H2O and epidote-seawater,and the hydrogen isotope composition of natural epidotes

The hydrogen isotope fractionation factors between epidote and aqueous 1 M and 4 M NaCl, 1 M CaCl₂ solutions, and between epidote and seawater, have been measured over the temperature range 250–550°C over which the degree of dissociation of dissolved species varies significantly. Measured fractionations at 350°C are decreased by up to 12‰, 9‰ and 7‰ relative to pure water in seawater, 1 M CaCl₂ and 1 M NaCl respectively, while above 500°C fractionations are not measurably dependent on fluid composition. Water—solution fractionation factors are derived which are generally applicable to the correction of mineral—water hydrogen isotope fractionations for the composition of the fluid phase.The hydrogen isotope compositions of natural epidotes are interpreted in the light of experimental fractionation data for situations where temperature, δD (fluid), and, in some cases, fluid chemistry, are independently known. Epidotes from active geothermal systems have hydrogen isotope quench temperatures consistent with or close to measured well temperatures unless the measured temperature has declined substantially since epidote formation or there is uncertainty in the D/H ratio of the water associated with the epidote because of isotopic heterogeneity in the well waters. Hydrothermal and metamorphic epidotes show closure temperatures of 175–225°C and 200–250°C. There is no evidence that retrograde metamorphic fluids, if present, are isotopically different from prograde fluids.The water-solution fractionations indicate strong solute-solvent interactions between 250 and 450°C and imply that both dissociated and associated species contribute to the fractionation effects through modification of the orientations and structure of the water molecules. Solute-solvent interactions become negligible at temperatures around 550°C.     

Sources of ore-forming fluids and metallic materials in the Jinwozi lode gold deposit,eastern Tianshan Mountains of China

This paper presents gas compositions and H-, O-isotope compositions of sulfide- and quartz-hosted fluid inclusions, and S-, Pb-isotope compositions of sulfide separates collected from the principal Stage 2 ores in Veins 3 and 210 of the Jinwozi lode gold deposit, eastern Tianshan Mountains of China. Fluid inclusions trapped in quartz and sphalerite are dominantly primary. H-and O-isotopic compositions of pyrite-hosted fluid inclusions indicate two major contributions to the ore-forming fluid that include the degassed magma and the meteoric-derived but rock ¹⁸O-buffered groundwater. However, H- and O-isotopic compositions of quartz-hosted fluid inclusions essentially suggest the presence of groundwater. Sulfide-hosted fluid inclusions show considerably higher abundances of gaseous species CO₂, N₂, H₂S, etc. than quartz-hosted ones. The linear trends among inclusion gaseous species reflect the mixing tendency between the gas-rich magmatic fluid and the groundwater. The relative enrichment of gaseous species in sulfide-hosted fluid inclusions, coupled with the banded ore structure indicating alternate precipitation of quartz with sulfide minerals, suggests that the magmatic fluid has been inputted to the ore-forming fluid in pulsation. Sulfur and lead isotope compositions of pyrite and galena separates indicate an essential magma derivation for sulfur but the multiple sources for metallic materials from the mantle to the bulk crust.     

Stable isotope paleohydrology and chemostratigraphy of the Albian Wayan Formation from the wedge-top depozone,North American Western Interior Basin

Understanding of the role of atmospheric moisture and heat transport in the climate system of the Cretaceous greenhouse world represents a major challenge in Earth system science.Stable isotopic paleohydrologic data from mid-Cretaceous paleosols in North America,from paleoequatorial to paleoArctic latitudes,have been used to constrain the oxygen isotope mass balance of the Albian hydrologic cycle.Over the range from 40°-50°N paleolatitude,sideritic paleosols predominate,indicating paleoenvironments with positive precipitation-evaporation(P-E)balances.Local exceptions occur on leeward side of the Sevier Orogen,where calcic paleosols in the wedge-top depozone record paleoenvironments with negative P-E balances in the orographic rain shadow.Stratigraphic sections in the Wayan Formation of Idaho(WF)were sampled from the wedge-top depozone.The units consist of stacked m-scale mudstone paleosols separated by m-scale sandstone-siltstone beds.Sections were sampled for organic carbon isotope profiles,and B-horizons from 6 well-developed paleosols were sampled for detrital zircons to determine maximum depositional ages.The first of these from the WF has produced a U-Pb concordia age of 101.0±1.1 Ma.This same WF section has produced a stratigraphic trend of upwardly decreasingδ~(13)C values ranging from-24‰upwards to-27‰VPDB,suggesting correlation to the late Albian C15 C-isotope segment.Pedogenic carbonates from the WF principally consist of micritic calcite,with carbon-oxygen isotope values that array along meteoric calcite lines(MCLs)withδ~(18)O values that range from-9.47‰up to-8.39‰VPDB.At approximately 42°N paleolatitude,these MCL values produce calculated paleoprecipitation values of-8.12‰to-7.04‰VSMOW,a range that is consistent with the estimates produced from other proxies at the same paleolatitudes across North America.These results indicate that despite the orographic rain shadow effect,the processes of meridional atmospheric moisture transport in this locale were similar to those in more humid mid-latitude paleoenvironments elsewhere in the continent.