Depositional system and palaeoclimatic interpretations of Middle to Late Pleistocene travertines: Kocabaş, Denizli,south‐west Turkey

Travertine deposits in western Turkey are very well‐exposed in the area of Kocaba?, in the eastern part of the Denizli Basin. The palaeoclimatic significance of these travertines is discussed using U/Th dates, stable isotope data and palynological evidence. The Kocaba? travertine occurrences are characterized by successions of depositional terraces associated with palaeosols and karstic features. The travertines have been classified into eight lithotypes and one erosional horizon, namely: laminated, coated bubble, reed, paper‐thin raft, intraclasts, micritic travertine with gastropods, extra‐formational pebbles and a palaeosol layer. The analysed travertines mostly formed between 181 ka and 80 ka (Middle to Late Pleistocene) during a series of climatic changes including glacial and interglacial intervals; their δ¹³C and δ¹⁸O values indicate that the depositional waters were mainly of basinal thermal origin, occasionally mixed with surficial meteoric water. Palynological results obtained from the palaeosols showed an abundance of non‐arboreal percentage and xerophytic plants (Oleaceae and Quercus evergreen type) indicating that a drought occurred. Marine Isotope Stage 6 is represented by grassland species but Marine Isotope Stage 5 is represented by Pinaceae–Pinus and Abies, Quercus and Oleaceae. Uranium/thorium analyses of the Kocaba? travertines show that deposition began in Marine Isotope Stage 6 (glacial) and continued to Marine Isotope Stage 4 (glacial), but mostly occurred in Marine Isotope Stage 5 (interglacial). The travertine deposition continued to ca 80 ka in the south‐west of the study area, in one particular depression depositional system. Palaeoenvironmental indicators suggest that the travertine depositional evolution was probably controlled by fault‐related movements that influenced groundwater flow. Good correlation of the stable isotope values and dates of deposition of the travertines and palynological data of palaeosols in the Kocaba? travertines serve as a starting point for further palaeoclimate studies in south‐west Turkey. Additionally, the study can be compared with other regional palaeoclimate archives.     

Determination and significance of the Mn(II) Zero-Field Splitting (ZFS) interaction in the geochemistry of travertines

An analytical approach, based on the electron paramagnetic resonance (EPR) spectroscopy of Mn(II) in travertines, has been developed in order to obtain relevant information about the local inhomogeneity of calcite and about the thermodynamic conditions which control the formation of travertine deposits. This information is crucial to constrain the precipitation of travertine under different geochemical contexts. An empirical correlation between the spectral features and the zero-field splitting (ZFS) interaction has been established through numerical simulations of EPR spectra. The variability of the investigated parameters and the applicability of the method have been tested on several travertines from Central Italy.     

Travertines of the northern Caucasus

Mineralogical and isotope-chemical characteristics of carbonate travertines of the Greater Caucasus are investigated. It is shown that concentrations of many chemical elements, which predominantly precipitate together with iron hydroxides, decrease along the strike of the travertine dome. At the same time, δ¹³C and ¹⁸O values in carbonates systematically increase due to kinetic effects of isotope fractionation. This leads to the formation of isotopically heavy calcite (δ¹³C up to 16.3‰) near the travertine dome base. Concentrations of other elements (Mg, Sr, Ba, Na, S, and Li), which form a isomorphic part of calcite crystal lattice, almost do not change along the strike of the dome. Comparison of concentrations of these elements in travertines and initial water solutions makes it possible to get ideas on trends of their redistribution in the carbonate-water system. Correlations found in this work define not only TDS content and concentration of some ions, but also REE spectra and formation temperatures of ancient fluid systems.     

The quaternary travertine deposits of Europe and Asia Minor

A summary is provided of the published information relating to all aspects of Quaternary travertine formation in Europe west of the Ural Mountains. The deposits have been divided into two broad groups, the meteogene travertines, which result primarily from the degassing of soil-borne aqueous CO₂, and thermogene deposits resulting from the degassing of thermally generated CO₂. Meteogene deposits are rare above latitude 58°N, and in regions where the mean annual air temperature is below 5°C. A significant positive correlation exists between mean air temperature and travertine deposit thickness. The combined effects of temperature and rainfall are used to provide a zoned map showing the travertine-forming potential of limestones within the region. Information from ¹⁴C dating indicates that deposition reached a maximum in the period 5–10 ka BP) and is currently limited by land and water management practices in the populated areas. Thermogene deposits occur in regions of high CO₂ discharge resulting from tectonic activity, such as Italy and Turkey where there is much vulcanism. These travertines are frequently more massive and less readily weathered than meteogene deposits. Fully referenced information is provided for 320 important, mostly well studied sites (227 meteogene, 93 thermogene), of which 156 are currently active.     

O/O and D/H ratios of pedogenic kaolinite in a North American Cenomanian laterite: Paleoclimatic implications

Kaolinite, gibbsite and quartz are the dominant minerals in samples collected from two outcrops of a Cenomanian (∼95 Ma) laterite in southwestern Minnesota. A combination of measured yields and isotope ratios permitted mass balance calculations of the δD and δ¹⁸O values of the kaolinite in these samples. These calculations yielded kaolinite δD values of about −73‰ and δ¹⁸O values of about +18.7‰. The δD and δ¹⁸O values appear to preserve information on the ancient weathering system.If formed in hydrogen and oxygen isotope equilibrium with water characterized by the global meteoric water line (GMWL), the kaolinite δD and δ¹⁸O values indicate a crystallization temperature of 22 (±5) °C. A nominal paleotemperature of 22 °C implies a δ¹⁸O value for the corresponding water of −6.3‰. The combination of temperature and meteoric water δ¹⁸O values is consistent with relatively intense rainfall at that mid-paleolatitude location (∼40°N) on the eastern shore of the North American Western Interior Seaway. The inferred Cenomanian paleosol temperature of ∼22 °C is in general accord with published mid-Cretaceous continental mean annual temperatures (MAT) estimated from leaf margin analyses of fossil plants.When compared with results from a published GCM-based Cenomanian climate simulation which specifies a latitudinal sea surface temperature (SST) gradient that was either near modern or smaller-than-modern, the kaolinite paleotemperature of 22 °C is closer to the GCM-predicted MAT for a smaller equator-to-pole temperature difference in the mid-Cretaceous. Moreover, the warm, kaolinite-derived, mid-paleolatitude temperature of 22 °C is associated with proxy estimates of high concentrations of atmospheric CO₂ in the Cenomanian. The overall similarity of proxy and model results suggests that the general features of Cenomanian continental climate in that North American locale are probably being revealed.     

Fossil findings from the Sıcak Çermik fissure ridge-type travertines and possible hominid tracks,Sivas, Central Turkey

S?cak Çermik (Sivas) is an important geothermal and recent travertine formation area in Central Anatolia. The majority of travertines found in the region comprise fissure-ridge type travertines according to morphological classification. At the location called Tepe Çermik within the travertine area, fill containing fossil bone fragments of Equus sp., Bovidae and other abundant animals formed within the fracture axis of a N–S striking fissure-ridge travertine developed under control of tectonic forces. The finds of these fossils in fissure-ridge travertines linked to tectonic forces indicates formation of a unique fossil environment created under the control of these forces. The Accelerator Mass Spectrometry Radiocarbon Dating analyses of fossils from the study area determined the fills were older than 43,000 years. The U/Th age of a sample from the most recently-formed banded travertine in the axis of the fracture was identified as 278,540 ± 18,436 years. As a result, the ages of fossils found within this fill are thought to be between 43,000 and 278,540 ± 18,436 years old. The high amount of perissodactyla and artiodactyla fossils found within fill in the axis of the fissure-ridge travertine probably indicates the presence of hominids who chose the region for hunting or settlement. The Equus sp. and Bovidae fossil samples found in the axis of the fracture indicate that in the dry and cold glacial period the paleogeography in a large portion of Anatolia comprised desert-like steppe.     

U/Th dating of the travertine deposited at transfer zone between two normal faults and their neotectonic significance: Cambazli fissure ridge travertines (the Gediz Graben-Turkey)

Abstract

The neotectonic characteristics of the travertines that outcrop near Cambazli Village to the west of the Gediz Graben in the Western Anatolia and the age determination of the travertine were carried out using the ²³⁰Th/^234,238U disequilibrium method. The Cambazli fissure ridge travertines represent the travertine depositions that develop at a transfer zone. The extent of these travertines is at NW-SE and NE-SW orientations and the ridge crest-trend of these travertines range between approximately 55° and 82° and they are located at an intersecting position. The evaluation of the fissure ridge travertine directions indicated that the compression stress that was responsible for the deposition of the Cambazli travertine was determined to be in the N-S orientation and the extensional stress was determined to be in the E-W orientation. The orientation of the dominant extension in Western Anatolia during the neotectonic period was N-S and this orientation is not in accordance with the directions of stress for the travertines. This situation indicates that the travertines were deposited along a transfer zone in N10W orientation between two normal faults. The travertines were determined to be active since the Upper Pleistocene as indicated by the age determination conducted using the ²³⁰Th/^234,238U disequilibrium method. The dilation rate of the travertines during dilation and the post-dilation period and the average dilation rate of the Cambazli travertines to the north of the Gediz Graben were calculated as 0.01–0.02 mm yr^?1 during deposition and as 0.05 mm yr^?1 during the post-dilation period. These dilation rates indicate lower tectonic activity along the northern ridge of the Gediz Graben than along the southern ridge.

© 2011 Lavoisier SAS. All rights reserved     

Studying travertines for neotectonics investigations: Middle–Late Pleistocene syn-tectonic travertine deposition at Serre di Rapolano (Northern Apennines, Italy)

Middle–Late Pleistocene tectonic activity has been inferred through studies on travertine deposits exposed in a tract of the hinterland Northern Apennines. A detailed study on the relationships between tectonics and travertine deposition coupled with ²³⁰Th/²³⁴U age determination of travertines at Cava Oliviera quarry, located close to Serre di Rapolano village (southern Tuscany, Northern Apennines), allowed us to recognise Pleistocene faults, whose activity has been referred to 157–24 ka, at least. Travertine deposition was tectonically controlled by WSW-ENE striking, oblique and normal faults, associated to a main fault (named as the Violante Fault). This structure dissected a regional normal fault (known as the Rapolano Fault) Early–Middle Pliocene in age, which bounded the eastern side of the Pliocene Siena Basin, and gave rise to space accommodation for clayey and sandy marine sediments. Hydrothermal circulation (and related travertine deposition) was favoured by the damaging enhancement due to the fault–fault intersection. Tectonic activity has been also documented by deformation recorded by travertines, which suggest a main tectonic event between 64 ± 5 and 40 ± 5 ka. The tectonic activity described for the study area agrees with the Quaternary tectonic evolution documented in the surrounding areas (e.g. Mt. Amiata and Mt. Vulsini), as well as the Tyrrhenian margin of the Central Apennines, indicating that a widespread tectonic activity affected the inner part of the Apennines until the latest Quaternary.     

Effects of diagenesis on paleoclimate reconstructions from modern and young fossil corals

The integrity of coral-based reconstructions of past climate variability depends on a comprehensive knowledge of the effects of post-depositional alteration on coral skeletal geochemistry. Here we combine millimeter-scale and micro-scale coral Sr/Ca data, scanning electron microscopy (SEM) images, and X-ray diffraction with previously published δ¹⁸O records to investigate the effects of submarine and subaerial diagenesis on paleoclimate reconstructions in modern and young sub-fossil corals from the central tropical Pacific. In a 40-year-old modern coral, we find secondary aragonite is associated with relatively high coral δ¹⁸O and Sr/Ca, equivalent to sea-surface temperature (SST) artifacts as large as −3 and −5 °C, respectively. Secondary aragonite observed in a 350-year-old fossil coral is associated with relatively high δ¹⁸O and Sr/Ca, resulting in apparent paleo-SST offsets of up to −2 and −4 °C, respectively. Secondary Ion Mass Spectrometry (SIMS) analyses of secondary aragonite yield Sr/Ca ratios ranging from 10.78 to 12.39 mmol/mol, significantly higher compared to 9.15 ± 0.37 mmol/mol measured in more pristine sections of the same fossil coral. Widespread dissolution and secondary calcite observed in a 750-year-old fossil coral is associated with relatively low δ¹⁸O and Sr/Ca. SIMS Sr/Ca measurements of the secondary calcite (1.96-9.74 mmol/mol) are significantly lower and more variable than Sr/Ca values from more pristine portions of the same fossil coral (8.22 ± 0.13 mmol/mol). Our results indicate that while diagenesis has a much larger impact on Sr/Ca-based paleoclimate reconstructions than δ¹⁸O-based reconstructions at our site, SIMS analyses of relatively pristine skeletal elements in an altered coral may provide robust estimates of Sr/Ca which can be used to derive paleo-SSTs.     

Wet-dry seasonal and spatial variations in the δC and δO values of the modern endogenic travertine at Baishuitai, Yunnan, SW China and their paleoclimatic and paleoenvironmental implications

Seasonal and spatial variations in the δ¹³C and δ¹⁸O values of the modern endogenic (thermogene) travertine deposited in a calcite-depositing canal at Baishuitai, Yunnan, SW China were examined to understand their potential for paleoclimatic and paleoenvironmental implications. The sampling sites were set in the upstream, middle reach and downstream of the canal, and the modern endogenic travertine samples were collected semimonthly to measure their δ¹³C and δ¹⁸O values. It was found that both δ¹³C and δ¹⁸O values of the endogenic travertine were low in the warm rainy season and high in the cold dry season, and correlated with each other. The low δ¹⁸O values in warm rainy season were mainly related to the higher water temperature and the lower δ¹⁸O values of rainwater, and the low δ¹³C values are caused by the dilution effect of overland flow with low δ¹³C values in the warm rainy season and the reduced CO₂-degassing of canal-water caused by the dilution effect of the overland flow. The linear negative correlation between the travertine δ¹⁸O (or δ¹³C) values and rainfall amount may be used for paleo-rainfall reconstruction if one knows the δ¹⁸O (or δ¹³C) values of the fossil endogenic travertine at Baishuitai though the reconstruction was not straightforward. It was also found that there was a progressive downstream increase of the δ¹⁸O and δ¹³C values of the travertine along the canal, the former being mainly due to the preferential evaporation of H₂¹⁶O to the atmosphere and the latter to the preferential release of ¹²CO₂ to the atmosphere during CO₂-degassing. However, the downstream increase of the travertine δ¹⁸O and δ¹³C values was less intensive in rainy season because of the reduced evaporation and CO₂-degassing during the rainy season. To conclude, the downstream travertine sites could be more favorable for the paleo-rainfall reconstruction while the upstream travertine sites are more favorable for the paleo-temperature reconstruction. So, this study demonstrates that endogenic travertine, like epigenic (meteogene) tufa, could also be a good candidate for high-resolution paleoclimatic and paleoenvironmental reconstruction.     

The record of temperature, wind velocity and air humidity in the δD and δO of water inclusions in synthetic and Messinian halites

Deuterium and oxygen isotope fractionations between liquid and vapor water were experimentally-determined during evaporation of a NaCl solution (35 g L⁻¹) as a function of water temperature and wind velocity. In the case of a null wind velocity, slopes of δD-δ¹⁸O trajectories of residual waters hyperbolically decrease with increasing water temperatures in the range 23-47 °C. For wind velocities ranging from 0.8 to 2.2 m s⁻¹, slopes of the δD-δ¹⁸O trajectories linearly increase with increasing wind velocity at a given water temperature. These experimental results can be modeled by using Rayleigh distillation equations taking into account wind-related kinetics effects. Deuterium and oxygen isotope compositions of water inclusions trapped by the precipitated halite crystals were determined by micro-equilibration techniques.These isotopic compositions accurately reflect those of the surrounding residual waters during halite growth. Isotopic compositions of water inclusions in twenty natural halites from the Messinian Realmonte mine in Sicily suggest precipitation temperatures of that match the homogenization temperatures obtained by microthermometry (median = 34 ± 5 °C). The similarity between the measured and experimental slopes of the δD-δ¹⁸O evaporation trajectories suggests that the effect of wind was negligible during the genesis of these halite deposits. Hydrogen and oxygen isotope compositions of water inclusions from Realmonte halite also define a linear trend whose extrapolation until intersection with the Mediterranean Meteoric Water Line allows the characterization of the water source with δD and δ¹⁸O values of −70 ± 10‰ and −11.5 ± 1.5‰, respectively. These results reveal that the huge amounts of salts deposited in Sicily result from the evaporation of seawater mixed with a dominant fraction (?50%) of meteoric waters most likely deriving from alpine fluvial discharge.     

A laser fluorination method for oxygen isotope analysis of biogenic silica and a new oxygen isotope calibration of modern diatoms in freshwater environments

An empirical calibration for the oxygen isotope fractionation between biogenic silica and water was determined for diatom frustules sampled from living diatom communities in the Jemez Mountains of northern New Mexico, USA. Over a temperature range from 5.1 to 37.8 °C, the silica-water fractionation is defined by the equation 1000 ln α_{(silica-water)} = 2.39(±0.13) × 10⁶T⁻² + 4.23(±1.49). This relationship is in close agreement with other published silica-water fractionation factors for laboratory cultured diatom samples; however, it is as much as 8‰ lower than equilibrium quartz-water fractionations and 3-4‰ lower than observed silica-water fractionations in diatomaceous silica collected from sediment traps and sediment cores. There are three possible explanations for the disparate silica-water fractionation factors observed in diatom silica: (1) silica does not precipitate in equilibrium with ambient water, (2) silica does precipitate in equilibrium with ambient water, but the silica-water fractionation factor for diatom silica is considerably less than the equilibrium fractionation factor for quartz-water, or (3) silica precipitation is influenced by a ‘vital’ effect, where the δ¹⁸O value of the water inside the diatom cell walls is lower than the δ¹⁸O values of ambient water.Post-mortem loss of organic material results in an alteration or ‘maturation’ of diatom silica in which silica reequilibrates with a silica-water fractionation closer to the equilibrium quartz-water fractionation. Alteration is likely to occur rapidly after the diatom frustule loses its organic coating, either as it settles through the water column or at the sediment-water interface; δ¹⁸O values recorded by paleo-diatom silica therefore do not record growing conditions but more likely record conditions at the sediment-water interface. In the case of lacustrine environments, where the bottom water remains at a nearly constant 4 °C, the reequilibration of diatom silica with bottom conditions could reduce or remove the conflating effects of temperature on δ¹⁸O values recorded by paleo-diatom silica and provide direct information on the δ¹⁸O value of the lake water.     

Source and origin of active and fossil thermal spring systems,northern Upper Rhine Graben,Germany

Thermal water samples and related young and fossil mineralization from a geothermal system at the northern margin of the Upper Rhine Graben have been investigated by combining hydrochemistry with stable and Sr isotope geochemistry. Actively discharging thermal springs and mineralization are present in a structural zone that extends over at least 60 km along strike, with two of the main centers of hydrothermal activity being Wiesbaden and Bad Nauheim. This setting provides the rare opportunity to link the chemistry and isotopic signatures of modern thermal waters directly with fossil mineralization dating back to at least 500–800 ka. The fossil thermal spring mineralization can be classified into two major types: barite-(pyrite) fracture filling associated with laterally-extensive silicification; and barite, goethite and silica impregnation mineralization in Tertiary sediments. Additionally, carbonatic sinters occur around active springs. Strontium isotope and trace element data suggest that mixing of a hot (>100 °C), deep-sourced thermal water with cooler groundwater from shallow aquifers is responsible for present-day thermal spring discharge and fossil mineralization. The correlation between both Sr and S isotope ratios and the elevation of the barite mineralization relative to the present-day water table in Wiesbaden is explained by mixing of deep-sourced thermal water having high ⁸⁷Sr/⁸⁶Sr and low δ³⁴S with shallow groundwater of lower ⁸⁷Sr/⁸⁶Sr and higher δ³⁴S. The Sr isotope data demonstrate that the hot thermal waters originate from an aquifer in the Variscan crystalline basement at depths of 3–5 km. The S isotope data show that impregnation-type mineralization is strongly influenced by mixing with SO₄ that has high δ³⁴S values. The fracture style mineralization formed by cooling of the thermal waters, whereas impregnation-type mineralization precipitated by mixing with SO₄-rich groundwater percolating through the sediments.     

O/O and D/H in goethite from a North American Oxisol of the Early Eocene climatic optimum

An Early Eocene Oxisol in the Ione Formation of California formed in a coastal continental weathering environment at a paleolatitude of ∼38°N. The dominant minerals in the Oxisol are goethite, quartz, and kaolinite. Material balance calculations were applied to new measurements of chemical composition, D/H, and ¹⁸O/¹⁶O ratios of Oxisol samples to determine the δD (−150 ± 3‰) and δ¹⁸O (−2.4 ± 0.3‰) values of the goethite (α-FeOOH). These data, in combination with the global meteoric water line (MWL), yielded an isotopic temperature of 21(±4) °C. The nominal value of 21 °C contrasts with the modern mean annual temperature (MAT) of 16 °C in that area. The warmer temperature is consistent with formation of the goethite during the Early Eocene climatic optimum. The isotopic composition of the goethite and a temperature of 21 °C imply ancient water with a δD value of −61(±4)‰ and a δ¹⁸O value of −8.9(±0.5)‰. This Early Eocene δ¹⁸O (or δD) value is more negative than values in the range of isotopic scatter observed for modern global precipitation at sites with a MAT of 21 °C.At times of warm global climates, the location of a near-surface atmospheric isotherm would generally shift relative to its location under modern climatic conditions. A simple Rayleigh-type condensation model indicates that, if one “follows the isotherm”, the associated scatter in δD and δ¹⁸O of precipitation in very warm global climates should shift (for a given isotherm) to more negative values that may be detectable in proxy records. The isotopic results from the goethite of the Early Eocene Oxisol appear to add to evidence in support of this idea.     

Long-term analog of carbonation in travertine from Uleimat Quarries, Central Jordan

Quaternary travertine capping the metamorphic (cement) zones in Uleimat Quarries, central Jordan, has been precipitated from hyperalkaline paleogroundwaters. Such waters are similar to the cement pore water and to the present day hyperalkaline seepages (pH 12.5) in Maqarin, north Jordan. The isotopic depletions observed in Uleimat travertine, with δ¹³C values as low as −25.45‰, suggest that they have been precipitated during CO₂ uptake by highly alkaline calcium hydroxide waters. The travertine in Uleimat Quarries indicates a long-term analog of carbonation and remobilization of silica in cementitious barriers for radioactive waste repositories. The presence of Cr-rich smectites and relatively high levels of Cr (4.1%), V (657 ppm), Ni (163 ppm), Zn (634 ppm) and U (34 ppm) in the green travertine and the associated opaline silica phases suggests the use of the Uleimat travertines as analogs with the repository disturbed zone. Smectites and silica phases are expected to be a sink for alteration products in the late stage evolution of a high pH plume. Co-precipitation of these elements in mineral phases is of great importance to control the concentration of these elements in groundwater.     

Impact of lake‐level changes on the formation of thermogene travertine in continental rifts: Evidence from Lake Bogoria,Kenya Rift Valley

Travertine is present at 20% of the ca 60 hot springs that discharge on Loburu delta plain on the western margin of saline, alkaline Lake Bogoria in the Kenya Rift. Much of the travertine, which forms mounds, low terraces and pool‐rim dams, is sub‐fossil (relict) and undergoing erosion, but calcite‐encrusted artefacts show that carbonate is actively precipitating at several springs. Most of the springs discharge alkaline (pH: 8·3 to 8·9), Na‐HCO₃ waters containing little Ca (<2 mg l^?1) at temperatures of 94 to 97·5°C. These travertines are unusual because most probably precipitated at temperatures of >80°C. The travertines are composed mainly of dendritic and platy calcite, with minor Mg‐silicates, aragonite, fluorite and opaline silica. Calcite precipitation is attributed mainly to rapid CO₂ degassing, which led to high‐disequilibrium crystal morphologies. Stratigraphic evidence shows that the travertine formed during several stages separated by intervals of non‐deposition. Radiometric ages imply that the main phase of travertine formation occurred during the late Pleistocene (ca 32 to 35 ka). Periods of precipitation were influenced strongly by fluctuations in lake level, mostly under climate control, and by related changes in the depth of boiling. During relatively arid phases, meteoric recharge of ground water declines, the lake is low and becomes hypersaline, and the reduced hydrostatic pressure lowers the level of boiling in the plumbing system of the hot springs. Any carbonate precipitation then occurs below the land surface. During humid phases, the dilute meteoric recharge increases, enhancing geothermal circulation, but the rising lake waters, which become relatively dilute, flood most spring vents. Much of the aqueous Ca²⁺ then precipitates as lacustrine stromatolites on shallow firm substrates, including submerged older travertines. Optimal conditions for subaerial travertine precipitation at Loburu occur when the lake is at intermediate levels, and may be favoured during transitions from humid to drier conditions.     

Sources and biological fractionation of Silicon isotopes in the Eastern Equatorial Pacific

Silicon isotopes in dissolved silicic acid were measured in the upper four kilometers between 4°N and 3°S latitude at 110°W longitude in the eastern Equatorial Pacific. Silicon isotopes became progressively heavier with silicic acid depletion of surface water as expected from biological fractionation. The value of ε estimated by applying a steady-state isotope fractionation model to data from all stations between 4°N and 3°S was −0.77 ± 0.12‰ (std. err.). When the analysis was restricted to those stations whose temperature and salinity profiles indicated that they were directly influenced by upwelling of the Equatorial Undercurrent (EUC), the resulting value of ε was −1.08 ± 0.27‰ (std. err.) similar to the value established in culture studies (−1.1‰). When the non steady state Rayleigh model was applied to the same restricted data set the resulting value of ε was significantly more positive, −0.61 ± 0.16‰ (std. err.). To the extent that the equatorial system approximates a steady state these results support a value of −1.1‰ for the fractionation factor for isotopes of Si in the sea. Without the assumption of steady state the value of ε can only be constrained to be between −0.6 and −1.1‰. Silicic acid in Equatorial Pacific Deep Water below 2000 m had a near constant δ³⁰Si of +1.32 ± 0.05‰. That value is significantly more positive than obtained for North Pacific Deep Water at similar depths at stations to the northwest of our study area (0.9-1.0‰) and it is slightly less positive than new measures of the δ³⁰Si of silicic acid from the silicic acid plume centered over the Cascadia basin in the Northeast Pacific (Si(OH)₄ > 180  μM, δ³⁰Si = +1.46 ± 0.12‰ (SD, n = 4). We show that the data from the equator and Cascadia basin fit a general trend of increasing δ³⁰Si(OH)₄ with increasing silicic acid concentration in the deep sea, but that the isotope values from the Northeast Pacific are anomalously light. The observed level of variation in the silicon isotope composition of deep waters from this single ocean basin is considerably larger than that predicted by current models based on fractionation during opal formation with no isotope effect during dissolution. Confirmation of such high variability in deep water δ³⁰Si(OH)₄ within individual ocean basins will require reassessment of the mechanisms controlling the distribution of isotopes of silicon in the sea.     

Environmental memory and a possible seasonal bias in the stable isotope composition of (U-Th)/He-dated goethite from the Canadian Arctic

Goethite (Ax-2) from Axel Heiberg Island (∼80°N) on the margin of the Arctic Ocean is the dominant mineral in a sample of “petrified” Eocene wood, but U, Th, and He measurements suggest that the goethite (α-FeOOH) crystallized in the latest Miocene/Pliocene (ca. 5.5 to 2.8 Ma). Measured δD and δ¹⁸O values of Ax-2 are −221 (±6)‰ and −9.6 (±0.5)‰, respectively. The inferred δD and δ¹⁸O values of the ancient water were about −139‰ and −18.6‰, respectively, with a calculated temperature of crystallization of 3 (±5)°C, which compares with the modern summer (J-J-A) temperature of 3 °C and contrasts with a modern MAT of −19 °C. Published results from various biological proxies on nearby Ellesmere Island indicate a Pliocene (∼4 Ma) MAT of either −6 or −0.4 °C and corresponding seasonal amplitudes of about 18 or 13 °C. A conductive heat flow model suggests that a temperature of 3 °C could represent goethite crystallization at depths of ∼100-200 cm (for MAT = −6 °C) or ∼250-450 cm (for MAT = −0.4 °C) over seasonally restricted intervals of time.The δ¹⁸O value of the Ax-2 water (−18.6‰) is more positive than the modern J-J-A precipitation (−22‰). In combination, the paleotemperatures and δ¹⁸O values of ancient waters (from Ax-2 and published results from three Eocene or Pliocene proxy sites on Axel Heiberg and Ellesmere Islands) are consistent with a warm season bias in those isotopic proxies. The results are also consistent with higher proportions of J-J-A precipitation in the annual total. If so, this emphasizes the importance of seasonality at high latitudes even in times of warmer global climates, and suggests that the Arctic hydrologic cycle, as expressed in the seasonal distribution and isotopic composition of precipitation (perhaps modified by a warmer Arctic Ocean), differed from modern.The δ¹³C value of the Fe(CO₃)OH component in the Ax-2 goethite is +6.6‰, which is much more positive than expected if crystallizing goethite incorporated CO₂ derived primarily from oxidation of relict Eocene wood with δ¹³C values of about −24‰. This apparent paradox may be resolved if the goethite is a product of oxidation of ¹³C-rich siderite, which had previously replaced wood in an Eocene methanogenic burial environment. Thus, the goethite retains a carbon isotope “memory” of a diagenetic Eocene event, but a δD and δ¹⁸O record of the latest Miocene/Pliocene Arctic climate.     

C-O bonds in carbonate minerals: A new kind of paleothermometer

The abundance of the doubly substituted CO₂ isotopologue, ¹³C¹⁸O¹⁶O, in CO₂ produced by phosphoric acid digestion of synthetic, inorganic calcite and natural, biogenic aragonite is proportional to the concentration of ¹³C-¹⁸O bonds in reactant carbonate, and the concentration of these bonds is a function of the temperature of carbonate growth. This proportionality can be described between 1 and 50 °C by the function: Δ₄₇ = 0.0592 · 10⁶ · T⁻² − 0.02, where Δ₄₇ is the enrichment, in per mil, of ¹³C¹⁸O¹⁶O in CO₂ relative to the amount expected for a stochastic (random) distribution of isotopes among all CO₂ isotopologues, and T is the temperature in Kelvin. This relationship can be used for a new kind of carbonate paleothermometry, where the temperature-dependent property of interest is the state of ordering of ¹³C and ¹⁸O in the carbonate lattice (i.e., bound together vs. separated into different CO₃²⁻ units), and not the bulk δ¹⁸O or δ¹³C values. Current analytical methods limit precision of this thermometer to ca. ± 2 °C, 1σ. A key feature of this thermometer is that it is thermodynamically based, like the traditional carbonate-water paleothermometer, and so is suitable for interpolation and even modest extrapolation, yet is rigorously independent of the δ¹⁸O of water and δ¹³C of DIC from which carbonate grew. Thus, this technique can be applied to parts of the geological record where the stable isotope compositions of waters are unknown. Moreover, simultaneous determinations of Δ₄₇ and δ¹⁸O for carbonates will constrain the δ¹⁸O of water from which they grew.