Aragonite stromatolitic buildups from Santorini (Aegean Sea,Greece): Geochemical and palaeontological constraints of the caldera palaeoenvironment prior to the Minoan eruption (ca 3600 yr bp)

The pyroclastic deposits of the Minoan eruption (ca 3600 yr bp ) in Santorini contain abundant xenoliths. Most of these deposits are calcareous blocks of laminated‐botryoidal, stromatolite‐like buildups that formed in the shallow waters of the flooded pre‐Minoan caldera; they consist of (i) light laminae, of fibrous aragonite arranged perpendicular to layering, and (ii) dark laminae, with calcified filaments of probable biological origin. These microstructures are absent in the light laminae, suggesting a predominant inorganic precipitation of aragonite on substrates probably colonized by microbes. Internal cavities contain loose skeletal grains (molluscs, ostracods, foraminifera and diatoms) that comprise taxa typical of shallow marine and/or lagoon environments. Most of these forms are typical of warm water environments, although no typical taxa from hydrothermal vents have been observed. Past gasohydrothermal venting is recorded by the occurrence of barite, pyrolusite and pyrite traces. The most striking features of the stable isotopic data set are: (i) an overall wide range in δ¹³C_PDB (0·16 to 12·97‰) with a narrower variation for δ¹⁸O_PDB (?0·23 to 4·33‰); and (ii) a relatively uniform isotopic composition for the fibrous aragonite (δ¹³C = 12·40 ± 0·43‰ and δ¹⁸O = 2·42 ± 0·77‰, n = 21). The δ¹³C and δ¹⁸O values from molluscs and ostracods display a covariant trend, which reflects a mixing between sea water and a fluid influenced by volcano‐hydrothermal activity. Accordingly, ⁸⁷Sr/⁸⁶Sr from the studied carbonates (0·708758 to 0·709011 in fibrous aragonite and 0·708920 to 0·708991 in molluscs) suggests that the aragonite buildups developed in sea water under the influence of a hydrothermal/volcanic source. Significant differences in trace elements have been detected between the fibrous aragonite and modern marine aragonite cements. The caldera water from which the fibrous aragonite crusts formed received an input from a volcano‐hydrothermal system, probably producing diffuse venting of volcanogenic CO₂ gas and of a fluid enriched in Ca, Mn and Ba, and depleted in Mg and probably in Sr.     

Salinity reflux and dolomitization of southern Australian slope sediments: the importance of low carbonate saturation levels

Anomalously saline waters in Ocean Drilling Program Holes 1127, 1129, 1130, 1131 and 1132, which penetrate southern Australian slope sediments, and isotopic analyses of large benthic foraminifera from southern Australian continental shelf sediments, indicate that Pleistocene–Holocene meso‐haline salinity reflux is occurring along the southern Australian margin. Ongoing dolomite formation is observed in slope sediments associated with marine waters commonly exceeding 50‰ salinity. A well‐flushed zone at the top of all holes contains pore waters with normal marine trace element contents, alkalinities and pH values. Dolomite precipitation occurs directly below the well‐flushed zone in two phases. Phase 1 is a nucleation stage associated with waters of relatively low pH (ca 7) caused by oxidation of H₂S diffusing upward from below. This dolomite precipitates in sediments < 80 m below the sea floor and has δ¹³C values consistent with having formed from normal sea water (? 1‰ to + 1‰ Vienna Pee Dee Belemnite). The Sr content of Phase 1 dolomite indicates that precipitation can occur prior to substantial metastable carbonate dissolution (< 300 ppm in Holes 1129 and 1127). Dolomite nucleation is interpreted to occur because the system is undersaturated with respect to the less stable minerals aragonite and Mg‐calcite, which form more readily in normal ocean water. Phase 2 is a growth stage associated with the dissolution of metastable carbonate in the acidified sea water. Analysis of large dolomite rhombs demonstrates that at depths > 80 m below the sea floor, Phase 2 dolomite grows on dolomite cores precipitated during Phase 1. Phase 2 dolomite has δ¹³C values similar to those of the surrounding bulk carbonate and high Sr values relative to Phase 1 dolomite, consistent with having formed in waters affected by aragonite and calcite dissolution. The nucleation stage in this model (Phase 1) challenges the more commonly accepted paradigm that inhibition of dolomitization by sea water is overcome by effectively increasing the saturation state of dolomite in sea water.     

Origin of blocky aragonite cement in Cenozoic glaciomarine sediments,McMurdo Sound,Antarctica

Inorganic aragonite occurs in a wide spectrum of depositional environments and its precipitation is controlled by complex physio-chemical factors. This study investigates diagenetic conditions that led to aragonite cement precipitation in Cenozoic glaciomarine deposits of McMurdo Sound, Antarctica. A total of 42 sandstones that host intergranular cement were collected from the CIROS-1 core, located proximal to the terminus of Ferrar Glacier. Standard petrography, Raman spectroscopy and electron microprobe analysis reveal a prominent aragonite cement phase that occurs as a pore-filling blocky fabric throughout the core. Oxygen isotope compositions (δ¹⁸O = −30·0 to −8·6‰ Vienna Pee-Dee Belemnite) and clumped isotope temperatures (TΔ₄₇ = 13·1 to 31·5°C) determined from the aragonite cements provide precise constraints on isotopic compositions (δ¹⁸O_w) of the parent fluid, which mostly range from −10·8 to −7·2‰ Vienna Standard Mean Ocean Water. The fluid δ¹⁸O_w values are consistent with those of pore water, previously identified as cryogenic brine in the nearby AND-2A core. Petrographic and geochemical data suggest that aragonite cement in the CIROS-1 core precipitated from a similar brine. The brine likely formed and infiltrated sediments in flooded glacial valleys along the western margin of McMurdo Sound during the middle Miocene Climatic Transition, and subsequently flowed basinward in the subsurface. Consequently, the brine forms as a longstanding subsurface fluid that has saturated Cenozoic sediments below southern McMurdo Sound since at least the middle Miocene. Aragonite cementation in the CIROS-1 core is interpreted to reflect its proximal position to sites of brine formation and greater likelihood of experiencing brines with sustained high carbonate saturation states and Mg/Ca ratios. This unusual occurrence expands the range of known natural occurrences of aragonite cement. Given the potential for cryogenic brine formation in glaciomarine settings, blocky aragonite, as the end member of the spectrum of aragonite cement morphology, may be more widespread in glaciomarine sediments than currently thought.     

Shoreline tufa and tufaglomerate from Pleistocene Lake Bonneville,Utah, USA: stable isotopic and mineralogical records of lake conditions,processes, and climate

Shoreline carbonate deposits of Pleistocene Lake Bonneville record the conditions and processes within the lake, including the evaporative balance as well as vertical and lateral chemical and isotopic gradients. Tufas (swash‐zone) and tufaglomerates (cemented, subaqueous colluvium or beachrock) on multiple, well‐developed shorelines near the Silver Island Range, Utah, also present an opportunity to examine physicochemical lake processes through time. Three shorelines are represented by carbonate deposits, including the 23–20 ka Stansbury stage, 15–14.5 ka Bonneville stage, and 14.5–14 ka Provo stage. Mean δ¹⁸O_VSMOW values of all three shorelines are statistically indistinguishable ( ～ 27 ± 1‰), when a few Bonneville samples of unusual composition are neglected. However, differences in primary carbonate mineralogy indicate that the correspondence is an artefact of the different fractionation factors between calcite or aragonite and water. Second, in order to sustain a much smaller, shallower lake during the colder Stansbury stage, the climate must have also been relatively dry. Third, δ¹⁸O values in tufa are higher than tufaglomerate by ～ 0.5‰, consistent with greater evaporative enrichment of lake water in the swash zone. Fourth, mean δ¹³C values for the Provo, Stansbury and Bonneville shorelines (4.4, 5.0 and 5.2‰, respectively) show that carbon species were dominated by atmospheric exchange, with the variations produced by differences in the oxidation of organic matter. Comparisons of shoreline carbonates with deep‐lake marls of the same approximate age indicate that shoreline carbonate was much higher in δ¹³C and δ¹⁸O values (both ～ 2.5‰) during Bonneville time, whereas isotopic differences were minor (both ～ 1‰) in Stansbury time. In particular, the Bonneville stage may have sustained large vertical or lateral isotopic gradients due to evaporative enrichment effects on δ¹⁸O values. In contrast, the lake during the much shallower Stansbury stage may have been well mixed. Differences in the primary mineralogy (Stansbury and Bonneville, aragonite > calcite; Provo, calcite > aragonite) reflect profound differences in lake chemistry in terms of open versus closed‐basin lakes. The establishment of a continuous outlet during Provo time probably reduced the Mg²⁺/Ca²⁺ ratio of lake water. Curiously, regardless of primary mineralogy, tufaglomerate cements are enriched in Na⁺ and Cl^? and depleted in Mg²⁺ relative to capping tufa of the same age. This probably reflects vital or kinetic effects in the swash zone (tufa). We suspect that ‘abiotic’ effects may have been important in the dark pore space of developing tufaglomerate, where the absence of light suppressed photosynthesis. Copyright © 2005 John Wiley & Sons, Ltd.     

Incorporation of uranium in modern corals

Uranium occurs in corals at three sites: 1, in organic matter; 2, adsorbed on the surfaces of skeletal aragonite; and 3, in the aragonite lattice. Organic matter incorporates from sea water by chelation 40–70 ppm uranium; skeletal aragonite incorporates only 3 ppm. However, as the organic fraction is low (0·1%), its high concentration of uranium does not significantly affect the total concentration of uranium in the coral. A negligible concentration of uranium, 40–60 ppb, is adsorbed on skeletal aragonite from which it is readily leached or exchanged. This low concentration of adsorbed uranium (<2% of the total uranium in skeletal aragonite) is related to the very small specific surface area (1·5–1·8 m²/g of the corals.     

Physical and chemical growth conditions of Ordovician organogenic deep-water dolomite concretions: implications for the δ18O of Early Palaeozoic sea water

The estimated depth of formation of authigenic dolomite concretions in the Middle Ordovician Cloridorme Formation, Quebec, ranges from < 1 m to 150–200 m below sea floor (mbsf) (mostly between < 1 and 25 mbsf), based on centre‐to‐margin variations in minus‐cement porosity (80–90% to 45–75%). Formation depths are > 350 mbsf (25–17% porosity) in the Lower Ordovician Levis Formation. Outward‐decreasing δ¹³C_VPDB values (10·2–0·8‰) suggest precipitation in the methane generation zone with an increasing contribution of light carbonate derived by advection from thermocatalytic reactions at depth. Anomalously low δ¹⁸O_VPDB values (centre‐to‐margin variations of ?0·4 to ?7·5‰) give reasonable temperatures for the concretion centres only if the δ¹⁸O of Ordovician sea water was negative (?6‰) and the bottom water was warm (> 15 °C). The 3–5‰ lower values for the concretion margins compared with the centres can be explained if, in addition, volcanic‐ash alteration, organic‐matter decomposition and/or advection of ¹⁸O‐depleted water lowered the δ¹⁸O of the pore water further by 2·0–4·0‰ during the first 25–200 m of burial. Reasonable growth temperatures for the margins of 17–20 °C are compatible with a lowering of the isotopic ratios by 1 to < 1·3‰ as a temperature effect. The systematic concentric isotope zonation of the concretions suggests that the well‐ordered near‐stoichiometric dolomite is a primary feature and not the result of recrystallization. Diagenetic dolomite beds of the Cloridorme Formation appear to have formed by coalescence of concretions, as shown by randomly sampled traverses that indicate formation at different subsurface depths. Growth of the Cloridorme dolomites was probably limited by calcium availability, at least 50% of which was derived from connate water, and the remainder by diffusion from sea water. Dolomite precipitation was favoured over calcite by very high sedimentation rates, the abundance of marine organic matter in the host sediment and a correspondingly thin sulphate reduction zone. Deep‐seated concretion growth in the Levis Formation required either internal sources for the participating ions (carbonate dissolution event) or porewater advection along faults.     

Radiocarbon Ages Constraints on the Origin and Shedding of Bank-Top Sediment in the Bahamas during the Holocene

Great quantities of fine-sized aragonite needles are produced in the shallow waters that cover the tops of the Bahama Banks and then exported to the bank margins where they accumulate with shells of pelagic organisms. To better understand these processes, we investigated Holocene-aged sediments in a core from the southwestern margin of Little Bahama Bank. The aragonite content of the sediments, ??¹⁸O of planktonic foraminifera shells, and radiocarbon ages of aragonite-rich <63 ??m sediments and coexisting planktonic foraminifera shells were determined. Sediment deposition was rapid overall, and a significant increase in deposition rate occurred 3,500?C4,000 years ago, shortly after rising sea level flooded the bank top with seawater and caused a dramatic increase in the shallow water area where aragonite production occurred. During the latest Holocene when high deposition rates minimize effects of bioturbation, aragonite-rich <63 ??m sediments are 400?C600 years older than coexisting foraminifera. This difference indicates the net age of aragonite when it was exported from the bank top. It is consistent with expectations of the ??hip-hop??n?? model (Morse et al. in Geochimica et Cosmochimica Acta 67: 2819?C2826, 2003) whereby aragonite needles on the bank top, formed initially by biologic or other processes, continue to grow for hundreds of years via precipitation of epitaxial carbonate cement from seawater. Earlier in the Holocene, when sea level was lower and the top of Little Bahama Bank was subaerially exposed, the deposition rate and aragonite content of the sediments were less, and the aragonite-rich <63 ??m sediments are about 1,000 years younger than coexisting foraminifera. This age difference can be explained by downward mixing of latest-Holocene <63 ??m material into older early-Holocene sediments.     

Isotopic constraints on growth conditions of multiphase calcite–pyrite–barite concretions in Carboniferous mudstones

Carbonate concretions in the Lower Carboniferous Caton Shale Formation contain diagenetic pyrite, calcite and barite in the concretion matrix or in different generations of septarian fissures. Pyrite was formed by sulphate reduction throughout the sediment before concretionary growth, then continued to form mainly in the concretion centres. The septarian calcites show a continuous isotopic trend from δ¹³C=?28·7‰ PDB and δ¹⁸O=?1·6‰ PDB through to δ¹³C=?6·9‰ PDB and δ¹⁸O=?14·6‰ PDB. This trend arises from (1) a carbonate source initially from sulphate reduction, to which was added increasing contributions of methanogenic carbonate; and (2) burial/temperature effects or the addition of isotopically light oxygen from meteoric water. The concretionary matrix carbonates must have at least partially predated the earliest septarian cements, and thus used the same carbonate sources. Consequently, their isotopic composition (δ¹³C=?12·0 to ?10·1‰ PDB and δ¹⁸O=?5·7 to ?5·6‰ PDB) can only result from mixing a carbonate cement derived from sulphate reduction with cements containing increasing proportions of carbonate from methanogenesis and, directly or indirectly, also from skeletal carbonate. Concretionary growth was therefore pervasive, with cements being added progressively throughout the concretion body during growth. The concretions contain barite in the concretion matrix and in septarian fissures. Barite in the earlier matrix phase has an isotopic composition (δ³⁴S=+24·8‰ CDT and δ¹⁸O=+16·4‰ SMOW), indicating formation from near‐surface, sulphate‐depleted porewaters. Barites in the later septarian phase have unusual isotopic compositions (δ³⁴S=+6 to +11‰ CDT and δ¹⁸O=+8 to +11‰ SMOW), which require the late addition of isotopically light sulphate to the porewaters, either from anoxic sulphide oxidation (using ferric iron) or from sulphate dissolved in meteoric water. Carbon isotope and biomarker data indicate that oil trapped within septarian fissures was derived from the maturation of kerogen in the enclosing sediments.     

Speleothem‐derived Asian summer monsoon variations in Central China, 54–46 ka

The oxygen isotope signature (δ¹⁸O) of stalagmite SI3 collected from Shizi Cave in north‐east Sichuan Province provides an Asian Summer Monsoon (ASM) record in Central China for the period 54–46 ka. The SI3 δ¹⁸O record clearly shows a negative δ¹⁸O excursion centred around 49.4 ka, which was reported in Hulu Cave in East China but not identified in the speleothem records from South‐west China. As a whole, this record displays a higher coherence with the two Hulu records from East China than with the speleothem δ¹⁸O records from South‐west China, suggesting that at 54–46 ka, Central China was influenced more by the East Asian Summer Monsoon than by the Indian Summer Monsoon. It also displays a significant negative δ¹⁸O excursion at 47.5–46.6 ka, which is not clearly documented in two other speleothem δ¹⁸O records previously reported from South‐west China. This suggests that details of the Greenland interstadial 12 warrant further investigations in future in monsoonal China. The SI3 δ¹⁸O record displays more significant centennial‐scale variations than the other four speleothem δ¹⁸O records from East and South‐west China, which may be due to the fact that the study site is closer to the north‐west boundary of the ASM and more sensitive to variations of the ASM than East and South‐west China. Copyright © 2011 John Wiley & Sons, Ltd.     

Ostracod palaeoecology and environmental change in the Laptev and Kara seas (Siberian Arctic) during the last 18 000 years

Fossil ostracod assemblages were investigated in five AMS ¹⁴ C‐dated cores from various water depths of the Laptev and Kara seas ranging from the upper continental slope (270 m) to the present‐day shelf depth (40 m). Six fossil assemblages were distinguished. These represent the varying environmental conditions at the North Siberian continental margin since about 18 ka. In the cores from the shelf the ostracod assemblages reflect the gradual transition from an estuarine brackish‐water environment to modern marine conditions since 12.3 ka, as induced by the regional early Holocene transgression. The core from the upper continental slope dates back to c. 17.6 ka and contains assemblages that are absent in the shelf cores. The assemblage older than 10 ka stands out as a specific community dominated by relatively deep‐water Arctic and North Atlantic species that also contains euryhaline species. Such an assemblage provides evidence for past inflows of Atlantic‐derived waters from as early as c. 17.2 ka, probably facilitated by upwelling in coastal polynyas, and a considerable riverine freshwater influence with enhanced surface water stratification owing to the proximity of the palaeocoastline until early Holocene times. In all studied cores, relative increases in euryhaline species dominant in the inner‐shelf regions are recorded in the mid–late Holocene sediments (<7 ka), which otherwise already contain modern‐like ostracod assemblages with relatively deep‐water species. This observation suggests euryhaline species to be largely sea‐ice‐ and/or iceberg‐rafted and therefore may provide evidence for a climate cooling trend.     

Deglaciation and catchment ontogeny in coastal south‐west Greenland: implications for terrestrial and aquatic carbon cycling

Here we present Holocene organic carbon, nitrogen, sulphur, carbon isotope ratio and macrofossil data from a small freshwater lake near Sisimiut in south‐west Greenland. The lake was formed c. 11 cal ka BP following retreat of the ice sheet margin and is located above the marine limit in this area. The elemental and isotope data suggest a complex deglaciation history of interactions between the lake and its catchment, reflecting glacial retreat and post‐glacial hydrological flushing probably due to periodic melting of local remnant glacial ice and firn areas between 11 and 8.5 cal ka BP. After 8.5 cal ka BP, soil development and associated vegetation processes began to exert a greater control on terrestrial–aquatic carbon cycling. By 5.5 cal ka BP, in the early Neoglacial cooling, the sediment record indicates a change in catchment–lake interactions with consistent δ¹³C while C/N exhibits greater variability. The period after 5.5 cal ka BP is also characterized by higher organic C accumulation in the lake. These changes (total organic carbon, C/N, δ¹³C) are most likely the result of increasing contribution (and burial) of terrestrial organic matter as a result of enhanced soil instability, as indicated by an increase in Cenococcum remains, but also Sphagnum and Empetrum. The impact of glacial retreat and relatively subdued mid‐ to late Holocene climate variation at the coast is in marked contrast to the greater environmental variability seen in inland lakes closer to the present‐day ice sheet margin. Copyright © 2012 John Wiley & Sons, Ltd.     

Holocene millennial to centennial carbonate cyclicity recorded in slope sediments of the Great Bahama Bank and its climatic implications

A 38 m long sediment core (MD992201) retrieved from a water depth of 290 m from the leeward margin of the Great Bahama Bank (GBB; 25°53·49′N, 79°16·34′W) has been investigated for changes in aragonite content. The core covers the Mid to Late Holocene (the past 7230 yr). Sediment lightness (L*-values) was used as a proxy for aragonite content, based on a high linear correlation (R = 0·93) between the X-ray diffraction derived aragonite content and L*-values. The resulting time resolution of the L*-values derived aragonite content ranges from 1 yr at the base of the core to 4 yr at the top. Detailed time series analysis using Monte Carlo Singular Spectrum Analysis and spectral analysis (Lomb–Scargle Fourier transform) identifies the presence of seven signals with varying amplitudes and wavelengths that could be traced throughout the past 5500 yr. During the first ∼1600 yr of sedimentation the aragonite record is dominated by the initial flooding of the flat-topped GBB. Superimposed on a multimillennial signal, related to Holocene sea-level changes, a millennial-scale fluctuation and five quasi-periodic oscillations were detected (∼1·3–2 kyr, ∼500–600 yr, ∼380 yr, ∼260 yr, ∼200 yr and ∼100 yr period). Comparisons with other proxies (e.g. tree ring-Δ¹⁴C, ¹⁰Be and δ¹⁸O in ice cores) provides information on the origin and dynamics of the individual signals. The analysis shows that the ∼200 yr and ∼100 yr signals can be attributed to solar forcing. The ∼260 yr, ∼380 yr and the ∼500–600 yr quasi-periodic signals are found to be of climatic origin, whereas the millennial scale fluctuations remain enigmatic, although solar forcing mechanisms seem likely. The data show that variability of solar output as well as past oceanographic and atmospheric changes have modulated the Mid to Late Holocene climate, which in turn controlled sediment input variations found in the Holocene wedge leeward of the GBB. Although these periplatform sediments have a rather uniform appearance, they still contain a large variety of subtle sedimentary variations.     

The palaeoenvironmental significance of δ13C of stalagmite BW‐1 from Beijing,China during Younger Dryas intervals inferred from the grey level profile

High‐resolution records of carbon isotope composition and grey level were analysed from a stalagmite, BW‐1, from Beijing, China, deposited between c. 14 and 10.5 ka BP, the δ¹⁸O profile of which has been used to discuss the timing and structure of the Younger Dryas (YD) event in north China. The high grey level and low δ¹³C match the milk‐white coloured locations on the polished stalagmite surface and coincide with enhanced luminescent bands within which the concentration of both impurities and the total organic carbon (TOC) are high. Additionally, the fluorescence of speleothems was derived from organic acids that have been flushed onto the stalagmite surface along with impurities from the overlying soil by heavy summer rain and co‐precipitated with the speleothem calcite. Thus, predominantly low δ¹³C and high grey level values indicate increased summer precipitation that supports abundant vegetation and robust biological productivity. Consequently, three distinct time intervals are defined by the palaeoenvironmental conditions expressed in the δ¹³C and grey level records of stalagmite BW‐1: (i) a warm‐humid stage (Pre‐YD, 13.97 to 12.85 ka BP, including a hiatus from 12.99 to 13.21 ka BP reported before); (ii) a cool‐arid stage (YD, 12.85 to 11.56 ka BP); and (iii) a warm‐humid stage (Post‐YD, 11.56 to 10.39 ka BP). The inferences based on our research are generally consistent with other regional vegetation and climatic records.     

Formation of modern dolomite in hypersaline pans of the Western Cape,South Africa

Authigenic calcite and dolomite and biogenic aragonite occur in Holocene pan sediments in a Mediterranean‐type climate on the western coastal plain of South Africa. Sediment was analysed from a Late Pleistocene coastal pan at Yzerfontein and four Holocene inland pans ranging from brackish to hypersaline. The pans are between 0·08 and 0·14 km² in size. The δ¹⁸O_PDB values of carbonate minerals in the pan sediments range from ?2·41 to 5·56‰ and indicate precipitation from evaporative waters. Covariance of total organic content and percentage carbonate minerals, and the δ¹³C_PDB values of pan carbonate minerals (?8·85 to ?1·54‰) suggest that organic matter degradation is a significant source of carbonate ions. The precipitation of the carbonate minerals, especially dolomite, appears to be mediated by sulphate‐reducing bacteria in the black sulphidic mud zone found in the brine‐type hypersaline pans. The knobbly, sub‐spherical texture of the carbonate minerals suggests that the precipitation of the carbonate minerals, particularly dolomite, is related to microbial processes. The ⁸⁷Sr/⁸⁶Sr ratios of pan carbonate minerals (0·7108 to 0·7116) are slightly higher than modern sea water and indicate a predominantly sea water (marine aerosol) source for calcium (Ca²⁺) ions with relatively minor amounts of Ca²⁺ derived from the chemical weathering of bedrock.     

'Pseudobreccias' revealed as calcrete mottling and bioturbation in the Late Dinantian of the southern Lake District, UK

Two types of ‘pseudobreccia’, one with grey and the other with brown mottle fabrics, occur in shoaling‐upward cycles of the Urswick Limestone Formation of Asbian (Late Dinantian, Carboniferous) age in the southern Lake District, UK. The grey mottle pseudobreccia occurs in cycle‐base packstones and developed after backfilling and abandonment of Thalassinoides burrow systems. Burrow infills consist of a fine to coarse crystalline microspar that has dull brown to moderate orange colours under cathodoluminescence. Mottling formed when an early diagenetic ‘aerobic decay clock’ operating on buried organic material was stopped, and sediment entered the sulphate reduction zone. This probably occurred during progradation of grainstone shoal facies, after which there was initial exposure to meteoric water. Microspar calcites then formed rapidly as a result of aragonite stabilization. The precipitation of the main meteoric cements and aragonite bioclast dissolution post‐date this stabilisation event. The brown mottle pseudobreccia fabrics are intimately associated with rhizocretions and calcrete, which developed beneath palaeokarstic surfaces capping cycle‐top grainstones and post‐date all depositional fabrics, although they may also follow primary depositional heterogeneities such as burrows. They consist of coarse, inclusion‐rich, microspar calcites that are always very dull to non‐luminescent under cathodoluminescence, sometimes with some thin bright zones. These are interpreted as capillary rise and pedogenic calcrete precipitates. The δ¹⁸O values (?5‰ to ?8‰, PDB) and the δ¹³C values (+2‰ to ?3‰, PDB) of the ‘pseudobreccias’ are lower than the estimated δ¹⁸O values (?3‰ to ?1‰ PDB) and δ¹³C values of (+2‰ to +4‰ PDB) of normal marine calcite precipitated from Late Dinantian sea water, reflecting the influence of meteoric waters and the input of organic carbon.     

Controls, variation, and a record of climate change in detailed stable isotope record in a single bryozoan skeleton

The long-lived (about 20 yr) bryozoan Adeonellopsis sp. from Doubtful Sound, New Zealand, precipitates aragonite in isotopic equilibrium with seawater, exerting no metabolic or kinetic effects. Oxygen isotope ratios (δ¹⁸O) in 61 subsamples (along three branches of a single unaltered colony) range from −0.09 to +0.68‰ PDB (mean = +0.36‰ PDB). Carbon isotope ratios (δ¹³C) range from +0.84 to +2.18‰ PDB (mean = +1.69‰ PDB). Typical of cool-water carbonates, δ¹⁸O-derived water temperatures range from 14.2 to 17.5 °C. Adeonellopsis has a minimum temperature growth threshold of 14 °C, recording only a partial record of environmental variation. By correlating seawater temperatures derived from δ¹⁸O with the Southern Oscillation Index, however, we were able to detect major events such as the 1983 El Niño. Interannual climatic variation can be recorded in skeletal carbonate isotopes. The range of within-colony isotopic variability found in this study (0.77‰ in δ¹⁸O and 1.34 in δ¹³C) means that among-colony variation must be treated cautiously. Temperate bryozoan isotopes have been tested in less than 2% of described extant species — this highly variable phylum is not yet fully understood.     

Aragonite–calcite veins of the ‘Erzberg’ iron ore deposit (Austria): Environmental implications from young fractures

The well‐known Erzberg site represents the largest siderite (FeCO₃) deposit in the world. It consists of various carbonates accounting for the formation of prominent CaCO₃ (dominantly aragonite) precipitates filling vertical fractures of different width (centimetres to decimetres) and length (tens of metres). These commonly laminated precipitates are known as ‘erzbergite’. This study focuses on the growth dynamics and environmental dependencies of these vein fillings. Samples recovered on‐site and from mineral collections were analyzed, and these analyses were further complemented by modern water analyses from different Erzberg sections. Isotopic signatures support meteoric water infiltration and sulphide oxidation as the principal hydrogeochemical mechanism of (Ca, Mg and Fe) carbonate host rock dissolution, mobilization and vein mineralization. Clumped isotope measurements revealed cool formation temperatures of ca 0 to 10°C for the aragonite, i.e. reflecting the elevated altitude Alpine setting, but unexpectedly low for aragonite nucleation. The ²³⁸U–²³⁴U–²³⁰Th dating yielded ages from 285·1 ± 3·9 to 1·03 ± 0·04 kyr bp and all samples collected on‐site formed after the Last Glacial Maximum. The observed CaCO₃ polymorphism is primarily controlled by the high aqueous Mg/Ca ratios resulting from dissolution of Mg‐rich host rocks, with Mg/Ca further evolving during prior CaCO₃ precipitation and CO₂ outgassing in the fissured aquifer. Aragonite represents the ‘normal’ mode of erzbergite formation and most of the calcite is of diagenetic (replacing aragonite) origin. The characteristic lamination (millimetre‐scale) is an original growth feature and mostly associated with the deposition of stained (Fe‐rich) detrital particle layers. Broader zonations (centimetre‐scale) are commonly of diagenetic origin. Petrographic observations and radiometric dating support an irregular nature for most of the layering. Open fractures resulting from fault tectonics or gravitational mass movements provide water flow routes and fresh chemical reaction surfaces of the host rock carbonates and accessory sulphides. If these prerequisites are considered, including the hydrogeochemical mechanism, modern water compositions, young U‐Th ages and calculated precipitation rates, it seems unlikely that the fractures had stayed open over extended time intervals. Therefore, it is most likely that they are geologically young.     

Recurrent spring‐fed rivers in a Middle to Late Pleistocene semi‐arid grassland: Implications for environments of early humans in the Lake Victoria Basin,Kenya

The effect of changing palaeoclimate and palaeoenvironment on human evolution during the Pleistocene is debated, but hampered by few East African records directly associated with archaeological sites prior to the Last Glacial Maximum. Middle to Late Pleistocene deposits on the shoreline of eastern Lake Victoria preserve abundant vertebrate fossils and Middle Stone Age arte‐facts associated with riverine tufas at the base of the deposits, which are ideal for palaeoenvironmental reconstructions. New data from tufas identified on Rusinga Island and on the mainland near Karungu, Kenya are provided from outcrop, thin sections, mineralogical, stable isotopic and U‐series dating analyses. Tufa is identified in four sites: Nyamita (94·0 ± 3·3 and 111·4 ± 4·2 ka); Kisaaka, Aringo (455 ± 45 ka); and Obware. The age ranges of these tufa deposits demonstrate that spring‐fed rivers were a recurrent, variably preserved feature on the Pleistocene landscape for ca 360 kyr. Poor sorting of clastic facies from all sites indicates flashy, ephemeral discharge, but these facies are commonly associated with barrage tufas, paludal environments with δ¹³C values of ca 10‰ indicative of C₃ plants and fossil Hippopotamus, all of which indicate a perennial water source. Other tufa deposits from Nyamita, Obware and Aringo have a mixed C₃/C₄ signature consistent with a semi‐arid C₄ grassland surrounding these spring‐fed rivers. The δ¹⁸O values of tufa from Nyamita are on average ca 1‰ more negative than calcite precipitated from modern rainfall in the region, suggesting greater contribution of depleted monsoonal input, similar to the Last Glacial Maximum. Microdebitage and surface‐collected artefacts indicate that early modern humans were utilizing these spring‐fed rivers. The presence of spring?fed rivers would have afforded animals a reliable water source, sustaining a diverse plant and animal community in an otherwise arid environment.     

Isotopic signature of burial diagenesis and primary lithological contrasts in periplatform carbonates (Miocene, Great Bahama Bank)

The stable isotope geochemistry of Miocene sediments from the leeward margin of the Great Bahama Bank was examined to investigate burial diagenetic processes in periplatform carbonates. Data indicate that, in addition to differences in bulk proportions of neritic and pelagic carbonate along the slope, rhythmic variation in primary carbonate content has controlled patterns of burial diagenesis and associated geochemical signatures throughout much of the succession examined. The present study focuses on Ocean Drilling Program Sites 1006 and 1007, the most distal of five sites drilled from marginal to deep basin environments during Leg 166. These Miocene sections are characterized by their cyclic appearance, manifest as decimetre‐ to metre‐scale alternations between light‐coloured ooze/chalk/limestone and dark‐coloured marl/marlstone. The section at Site 1006 contains a high proportion of pelagic carbonate and is unlithified to a subbottom depth of ～675 m. Fluctuations in δ¹⁸O and δ¹³C values at this site are independent of lithological variation and reflect primary conditions. At Site 1007, located at the toe‐of‐slope and composed of a mixture of bank‐derived and pelagic carbonate, limestones are densely cemented, show little evidence of compaction and have δ¹⁸O values up to 2‰ higher than coeval sediments at Site 1006. Marlstones at Site 1007 are poorly cemented, exhibit an increase in compaction‐related features with depth and have lower and more variable δ¹⁸O values that are similar to those of coeval sediments at Site 1006. Isotopic and petrographic characteristics of limestone interbeds result from cement precipitation from cold sea water during the first ～100 m of burial. Higher proportions of insoluble materials and pelagic carbonate seem to have inhibited diagenetic alteration in adjacent marlstones; in spite of significant compaction and pressure solution during burial, original isotopic compositions appear to be best preserved in these intervals at Site 1007. The documented contrasts in petrographic and isotopic patterns illustrate the role of primary sediment composition in controlling lithification processes in periplatform carbonates and stress the importance of considering such factors when interpreting geochemical data from ancient shelf and slope limestones.     

Lead,Sulfur, and Oxygen Isotope Systematics in Hydrothermal Precipitates from the 14°S Hydrothermal Field,South Mid‐Atlantic Ridge

At the inside corner between the South Mid‐Atlantic Ridge (SMAR) and the Cardno fracture zone, the 14°S hydrothermal field, with its abundant silica‐rich sulfides, was identified as a volcanic massif, which provided the first opportunity to study inside corner‐related hydrothermal mineralization. S, Pb, and O isotopes were measured in hydrothermal sulfide samples from the two sites (volcanic top and slope sites) in the 14°S field. The homogeneous Pb isotope values (²⁰⁷Pb/²⁰⁴Pb = 15.466 ? 15.472; ²⁰⁶Pb/²⁰⁴Pb = 18.242 ? 18.252) and the δ³⁴S values (top site, +6.3 to +6.85‰; slope site, +2.37 to +3.36‰) suggest that the source of metals and most of the sulfur is the upper crust, whereas some sulfur is sourced from downward‐penetrating seawater, especially in the top site. The calculated oxygen isotope equilibration temperatures from quartz and seawater are between 94 and 144°C for the top site and between 179 and 196°C for the slope site. These isotopic proxies, together with geological background survey data, have an important implication: Discrepancies between the sites may result from variations in crust permeability, which also affect the mixing level between downward‐penetrating seawater and upward hydrothermal end‐member fluids and determine the various mineralization types.