Carbonate-rich Environments Research Articles

Warm, not cold temperatures contributed to a Late Miocene reef decline in the Coral Sea

Evidence shows that in the modern ocean, coral reefs are disappearing, and these losses are tied to climate change. However, research also shows that coral reefs can adapt rapidly to changing conditions leading some researchers to suggest that some reef systems will survive future climate change through adaptation. It is known that there were changes in the area covered by coral reefs in the past. Therefore, it is important to investigate the long-term response of coral reefs to environmental changes and high sea-surface temperatures (SSTs). However, because of diagenetic issues with SST proxies in neritic, metastable carbonate-rich environments, there is an incomplete and sometimes even incorrect understanding of how changes in SSTs affect carbonate reef systems. A good example is the Queensland Plateau offshore northeast Australia next to the threatened Great Barrier Reef. In the Late Miocene, between 11 and 7 Ma, a partial drowning caused the reef area on the Queensland Plateau to decline by ~ 50% leading to a Late Miocene change in platform geometry from a reef rimmed platform to a carbonate ramp. This reef decline was interpreted to be the result of SSTs at the lower limit of the modern reef growth window (20–18 °C). This article presents a new Late Miocene—ased SST record from the Coral Sea based on the TEX86H molecular paleothermometer, challenging this long held view. Our new record indicates warm tropical SSTs (27–32 °C) at the upper end of the modern reef growth window. We suggest that the observed temperatures potentially exceeded the optimal calcification temperatures of corals. In combination with a low aragonite supersaturation in the ocean, this could have reduced coral growth rates and ultimately lowered the aggradation potential of the reef system. These sub-optimal growth rates could have made the coral reefs more susceptible to other stressors, such as relative sea-level rise and/or changes in currents leading to reef drowning. Given that these changes affected coral reefs that were likely adapted to high temperature/low aragonite saturation conditions suggests that reefs that have adapted to non-ideal conditions may still be susceptible to future climate changes due to the interaction of multiple stressors associated with climate change.

Effect of carbonates on the formation of magnesium silicate hydrates

The effect of carbonates on the formation of magnesium silicate hydrate phases (M-S-H) was investigated in paste experiments. At molar ratio Mg/Si = 1.5, M-S-H pastes were synthesised from silica fume and MgO or MgO/hydromagnesite in a sodium carbonate-rich environment (dissolved 1.7 g of Na2CO3 for 100 g of binder). Thermogravimetric analysis, X-ray diffraction, and 29Si MAS NMR data showed that M-S-H phases formed much faster in the presence of carbonates, which destabilised brucite. 23Na MAS NMR data, cation exchange capacity measurements, thermogravimetric analysis coupled with infrared exhaust gas analysis, and 13C MAS NMR data showed that traces of sodium and carbonates were sorbed on M-S-H. However, no evidence of the formation of Mg-carbonate phases was observed in crystalline or amorphous form. Thermodynamic modelling carried out with an updated database for Mg-phases indicated that M-S-H and hydromagnesite should be stable, in contrast to the observed partial destabilisation of hydromagnesite.

Technetium immobilization by chukanovite and its oxidative transformation products: Neural network analysis of EXAFS spectra

The uptake of the fission product technetium (Tc) by chukanovite, an FeII hydroxy carbonate mineral formed as a carbon steel corrosion product in anoxic and carbonate-rich environments, was studied under anoxic, alkaline to hyperalkaline conditions representative for nuclear waste repositories in deep geological formations with cement-based inner linings. The retention potential of chukanovite towards TcVII is high in the pH range 7.8 to 12.6, evidenced by high solid-water distribution coefficients, log Rd ~ 6, and independent of ionic strength (0.1 or 1 M NaCl). Using Tc K-edge X-ray absorption spectroscopy (XAS) two series of samples were investigated, Tc chukanovite sorption samples and coprecipitates, prepared with varying Tc loadings, pH values and contact times. From the resulting 37 XAS spectra, spectral endmembers and their dependence on chemical parameters were derived by self-organizing (Kohonen) maps (SOM), a neural network-based approach of machine learning. X-ray absorption near-edge structure (XANES) data confirmed the complete reduction of TcVII to TcIV by chukanovite under all experimental conditions. Consistent with mineralogical phases identified by X-ray diffraction (XRD), SOM analysis of the extended X-ray absorption fine-structure (EXAFS) spectra revealed the presence of three species in the sorption samples, the speciation predominately controlled by pH: Between pH 7.8 and 11.8, TcO2-dimers form inner-sphere sorption complexes at the surface of the initial chukanovite as well as on the surface of secondary magnetite formed due to redox reaction. At pH ≥ 11.9, TcIV is incorporated in a mixed, chukanovite-like, Fe/Tc hydroxy carbonate precipitate. The same species formed when using the coprecipitation approach. Reoxidation of sorption samples resulted in a small remobilization of Tc, demonstrating that both the original chukanovite mineral and its oxidative transformation products, magnetite and goethite, contribute to the immobilization of Tc in the long term, thus strongly attenuating its environmental transport.

Assessing the impact of diagenesis on foraminiferal geochemistry from a low latitude, shallow-water drift deposit

Due to their large heat and moisture storage capabilities, the tropics are fundamental in modulating both regional and global climate. Furthermore, their thermal response during past extreme warming periods, such as super interglacials, is not fully resolved. In this regard, we present high-resolution (analytical) foraminiferal geochemical (δ18O and Mg/Ca) records for the last 1800 kyr from the shallow (487 m) Inner Sea drift deposits of the Maldives archipelago in the equatorial Indian Ocean. Considering the diagenetic susceptibility of these proxies, in carbonate-rich environments, we assess the integrity of a suite of commonly used planktonic and benthic foraminifera geochemical datasets (Globigerinoides ruber (white), Globigerinita glutinata (with bulla), Pulleniatina obliquiloculata (with cortex) and Cibicides mabahethi) and their use for future paleoceanographic reconstructions.Using a combination of spot Secondary Ion Mass Spectrometer, Electron Probe Micro-Analyzer and Scanning Electron Microscope image data, it is evident that authigenic overgrowths are present on both the external and internal test (shell) surfaces, yet the degree down-core as well as the associated bias is shown to be variable across the investigated species and proxies. Given the elevated authigenic overgrowth Mg/Ca (∼12–22 mmol/mol) and δ18O values (closer to the benthic isotopic compositions) the whole-test planktonic G. ruber (w) geochemical records are notably impacted beyond ∼627.4 ka (24.7 mcd). Yet, considering the setting (i.e. bottom water location) for overgrowth formation, the benthic foraminifera δ18O record is markedly less impacted with only minor diagenetic bias beyond ∼790.0 ka (28.7 mcd). Even though only the top of the G. ruber (w) and C. mabahethi records (whole-test data) would be suitable for paleo-reconstructions of absolute values (i.e. sea surface temperature, salinity, seawater δ18O), the long-term cycles, while dampened, appear to be preserved. Furthermore, planktonic species with thicker-tests (i.e. P. obliquiloculata (w/c)) might be better suited, in comparison to thinner-test counter-parts (i.e. G. glutinata (w/b), G. ruber (w)), for traditional whole-test geochemical studies in shallow, carbonate-rich environments. A thicker test equates to a smaller overall bias from the authigenic overgrowth. Overall, if the diagenetic impact is constrained, as done in this study, these types of diagenetically altered geochemical records can still significantly contribute to studies relating to past tropical seawater temperatures, latitudinal scale ocean current shifts and South Asian Monsoon dynamics.

Size-related mineralogical and surface physicochemical properties of the mineral particles from the recent sediments of the Eastern Adriatic Sea

The mineral composition and surface physico-chemical properties, i.e., specific surface area (SSA), cation exchange capacity (CEC), and surface charge of recent sediments and their submicron mineral fractions from different sedimentological environments of the Eastern Adriatic were investigated. The influence of organic matter on these properties was also investigated. It was shown that illite and mixed-layered clay minerals (MLCM) were ubiquitous and showed no size-related preferences while the occurrence of smectites, chlorites, and kaolinites varied. The smectites content increased and the chlorites decreased slightly with decreasing particle size. The sediments from the carbonate-rich environment contained no smectites or chlorites and had the highest kaolinite content. For the first time, in the recent sediments of the Adriatic Sea the poorly- and the well-crystallised kaolinite (Kl and KlD) were distinguished. While Kl predominates in the submicron-sized fraction, KlD occurred only in micron-sized fractions. Authigenic aragonite of submicron-sized was determined in a distinct environment of the semi-enclosed marine lake. The differences in mineral composition and particle size of sediments and their separated fractions were reflected in a wide range of the SSA and CEC values obtained. The highest values of SSA and CEC were determined in the phyllosilicates-rich submicron-sized fractions range, 109 m2g-1 and 87.4 cmol+kg−1, respectively. The submicron-sized fraction from aragonite-rich marine lake showed the lowest values of SSA (56.4 m2g-1) and CEC (38.8 cmol+kg−1), which are still unexpectedly high for carbonate-rich environments. The removal of organic matter resulted in a significant increase in SSA and CEC, up to 150% and 76%, respectively.

Multiphase inclusions associated with residual carbonate in a transition zone diamond from Juina (Brazil)

Super-deep diamonds and their mineral inclusions preserve very precious information about Earth’s deep mantle. In this study, we examined multiphase inclusions entrapped within a diamond from the Rio Vinte e um de Abril, São Luiz area (Juina, Brazil), using a combination of non-destructive methods. Micro-Computed X-ray Tomography (μ-CXRT) was used to investigate the size, shape, distribution and X-Ray absorption of inclusions and mapping by micro X-ray Fluorescence (μ-XRF), μ-Raman Spectroscopy and micro-Fourier Transform Infrared Spectroscopy (μ-FTIR) were used to determine the chemical and mineralogical composition of the inclusions. Four large inclusions enclosed in the N-rich diamond core consist of dominant ferropericlase–magnesiowüstite and locally exsolved magnesioferrite. FTIR maps, obtained integrating the band at 1430 cm−1, show also the presence of carbonates. A fifth large inclusion (ca 100 μm) was remarkable because it showed a very unusual flask shape, resembling a fluid/melt inclusion. Based on μCXRT tomography and μ-Raman mapping, the flask-shaped inclusion is polyphase and consists of magnetite and hematite partly replacing a magnesiowüstite core and small-volume of gas/vacuum. μ-Raman spectra on the same inclusion revealed local features that are ascribed to post-spinel polymorphs, such as maohokite or xieite, which are stable at P ≥ 18 GPa, and to huntite, a carbonate with formula CaMg3(CO3)4. This represents the first finding of maohokite and huntite in diamond. We interpret the composition of the inclusions as evidence of formation of ferropericlase–magnesiowüstite and diamond in a carbonate-rich environment at depths corresponding at least to the Transition Zone, followed by oxidation of ferropericlase–magnesiowüstite by reaction with relatively large-volume entrapped melt during diamond ascent.

Uranium and Cesium sorption to bentonite colloids under carbonate-rich environments: Implications for radionuclide transport

In the context of geological disposal of radioactive waste, one of the controlling mechanisms for radionuclide migration through subsurface strata is sorption to mobile colloidal bentonite particles. Such particles may erode from the repository backfill or bentonite buffer and yield measurable (0.01–0.1 g/L) concentrations in natural groundwater. The extent of sorption is influenced by colloid concentration, ionic strength, radionuclide concentration, and the presence of competing metals. Uranium (VI) and cesium sorption to bentonite colloids was investigated both separately and together in low ionic strength (2.20 mM) artificial rainwater (ARW) and high ionic strength (169 mM) artificial groundwater (AGW; representative of a fractured carbonate rock aquitard). Sorption experiments were conducted as a factor of colloid concentration, initial metal concentration and opposing metal presence. It was shown that both U(VI) and Cs sorption were significantly reduced in AGW in comparison to ARW. Additionally, the sorption coefficient Kd of both metals was found to decrease with increasing colloid concentration. Competitive sorption experiments indicated that at high colloid concentration (1–2 g/L), Cs sorption was reduced in the presence of U(VI), and at low colloid concentration (0.01–0.5 g/L), both Cs and U(VI) Kds were reduced when they were present together due to competition for similar sorption sites. The results from this study imply that in brackish carbonate rock aquifers, typical of the Israeli northern Negev Desert, both U(VI) and Cs are more likely to be mobile as dissolved species rather than as colloid-associated solids.

Hydrochemical and stable isotope indicators of pyrite oxidation in carbonate-rich environment; the Hamersley Basin, Western Australia

Sulphur (S) is a commonly occurring element in most aquifers, primarily in oxidised (sulphates) and reduced (sulphides) forms. Sulphides often constitute a risk to groundwater quality due to acid rock drainage, especially in catchments that are subject to mining excavations or groundwater injection. However, in semi-arid regions detection of the acid rock drainage risk can be challenging and traditional methods based on observations of increasing SO4 concentrations or SO4/Cl ratios in surface and groundwater, are not necessarily applicable. In addition, decreasing pH, usually accompanying pyrite oxidation, can be masked by the high pH-neutralisation capacity of carbonate and silicate minerals.Analysis of 73 surface and groundwater samples from different water bodies and aquifers located in the Hamersley Basin, Western Australia found that most of the samples are characterised by neutral pH but there was also a large spatial variability in the dissolved sulphate (SO4) concentrations that ranged from 1mg/L to 15,000mg/L. Not surprisingly, groundwater in aquifers that contained pyrite had high sulphate concentrations (>1000mg/L). This was associated with low δ34SSO4 values (+1.2‰ to +4.6‰) and was consistent with the values obtained from aquifer matrix pyritic rock samples (−1.9‰ to +4.4‰). It was also found that the SO4 concentrations and acidity levels were not only dependent on δ34SSO4 values and existence of pyrite but also on the presence of carbonate minerals in the aquifer matrix. The groundwater in aquifers containing both pyrite and carbonate minerals had a neutral pH and was also saturated with respect to gypsum and had high magnesium concentrations of up to 2200mg/L suggesting de-dolomitisation as the process buffering the acidity generated by pyrite oxidation.Based on the findings from this study, a classification scheme has been developed for identification of the acid rock drainage contribution to groundwater that encompasses a myriad of geochemical processes that occur in aqueous systems. The classification uses five proxies (SO4, SO4/Cl, SI of calcite, δ34SSO4 and δ18OSO4) to improve assessment of the oxidation of sulphide potential contribution to overall sulphate ion concentrations regardless of acidity levels of the aqueous system.

Organic geochemical characteristics of the Mesoproterozoic Hongshuizhuang Formation from northern China: Implications for thermal maturity and biological sources

The Mesoproterozoic Hongshuizhuang Formation (∼1.4Ga) from northern China consists of organic-rich sediments which record important environmental and biological information from that time. Organic and element geochemistry techniques were used to assess the syngeneity and indigeneity of hydrocarbons, and the thermal maturity and biological sources of the organic matter in the Hongshuizhuang Formation. Results from a slice-extraction experiment indicate that the exterior of the core was subjected to contamination from drilling, sampling and storage, whereas the organic matter in the interior shale core slices was indigenous. The organic matter in the interior argillaceous dolomite core slices might have been affected by the migration of oil. It is important to remove the outside of the core prior to solvent extraction, as this increases the possibility of analysis of indigenous hydrocarbons.The source rocks of the oil are the black shales of the Hongshuizhuang Formation. Aliphatic and aromatic hydrocarbon distributions indicate that the Hongshuizhuang Formation samples have a low thermal maturity in the early to middle oil window (0.6–0.8%Ro equivalent), based on comparison with middle Velkerri Formation rocks of about the same age in the McArthur Basin, northern Australia. These data are consistent with results based on the values of Tmax and protobitumen reflectance, and suggest that the samples contain well preserved organic matter that has not been thermally destroyed. The redox conditions indicated by the pristane/phytane (Pr/Ph) ratios are not consistent with other evidence. The correlations between n-C20−/n-C21+, major elements and Pr/Ph indicate that the Pr/Ph ratios are influenced by biological sources and mineralogy, rather than by redox conditions. Pr and Ph may have been derived not only from chlorophyll-a, but also from archaea. The short and long chain n-alkanes in the Hongshuizhuang Formation were derived from anoxic clay-rich environments and oxic carbonate-rich environments, respectively. The biomarkers observed in the Hongshuizhuang Formation indicate that the organic matter was primarily derived from prokaryotes.

Parádsasvárite, a new member of the malachite-rosasite group from Parádsasvár, Mátra Mountains, Hungary

Paradsasvarite (IMA No. 2012-077) was found in the Nagy-Lapafő area, Paradsasvar, Matra Mountains, Hungary. It forms pale beige, globular aggregates up to 0.2 mm in diameter on calcite. Associated secondary minerals are smithsonite, hemimorphite, hydrozincite, aurichalcite and rosasite. The mineral was formed as an alteration product of sphalerite and chalcopyrite in a carbonate-rich environment. Paradsasvarite is translucent with a weakly vitreous, dull or silky lustre and white streak. Its Mohs hardness is about 2–3, cleavage and parting were not observed. It is brittle; the fracture is finely fibrous. Average of nine electron-microprobe analyses gave ZnO 58.08, CuO 12.60, PbO 1.27, CO2 (calc.) 19.50, H2O (calc.) 7.94, total 99.39 wt.%, corresponding to the empirical formula (Zn0.62Cu0.36Pb0.01)Σ0.99Zn1.00(CO3)(OH)2. The seven strongest lines in the X-ray powder diffraction pattern are [dhkl in A (Iobs %, hkl)] 6.054 (67, 200), 5.085 (100, 210), 3.703 (87, 310 and 220), 3.021 (25, 400 and 130), 2.971 (25, −211 and 001), 2.603 (62, −221) and 2.539 (36, 420). According to its X-ray powder diffraction data and chemical formula, paradsasvarite belongs to the malachite-rosasite group and it is isostructural with rosasite. It is monoclinic, space group P21/a, a = 12.92(1), b = 9.372(7), c = 3.159(4) A, β = 110.4(1)°, V = 358.5(5) A3, Z = 4.

Radioiodine sorption/desorption and speciation transformation by subsurface sediments from the Hanford Site

During the last few decades, considerable research efforts have been extended to identify more effective remediation treatment technologies to lower the 129I concentrations to below federal drinking water standards at the Hanford Site (Richland, USA). Few studies have taken iodate into consideration, though recently iodate, instead of iodide, was identified as the major species in the groundwater of 200-West Area within the Hanford Site. The objective of this study was thus to quantify and understand aqueous radioiodine species transformations and uptake by three sediments collected from the semi-arid, carbonate-rich environment of the Hanford subsurface. All three sediments reduced iodate (IO3−) to iodide (I−), but the loamy-sand sediment reduced more IO3− (100% reduced within 7 days) than the two sand-textured sediments (∼20% reduced after 28 days). No dissolved organo-iodine species were observed in any of these studies. Iodate uptake Kd values ([Isolid]/[Iaq]; 0.8–7.6 L/kg) were consistently and appreciably greater than iodide Kd values (0–5.6 L/kg). Furthermore, desorption Kd values (11.9–29.8 L/kg) for both iodate and iodide were consistently and appreciably greater than uptake Kd values (0–7.6 L/kg). Major fractions of iodine associated with the sediments were unexpectedly strongly bound, such that only 0.4–6.6 % of the total sedimentary iodine could be exchanged from the surface with KCl solution, and 0–1.2% was associated with Fe or Mn oxides (weak NH2HCl/HNO3 extractable fraction). Iodine incorporated into calcite accounted for 2.9–39.4% of the total sedimentary iodine, whereas organic carbon (OC) is likely responsible for the residual iodine (57.1–90.6%) in sediments. The OC, even at low concentrations, appeared to be controlling iodine binding to the sediments, as it was found that the greater the OC concentrations in the sediments, the greater the values of uptake Kd, desorption Kd, and the greater residual iodine concentrations (non-exchangeable, non-calcite-incorporated and non-Mn, Fe-oxide associated). This finding is of particular interest because it suggests that even very low OC concentrations, <0.2%, may have an impact on iodine geochemistry. The findings that these sediments can readily reduce IO3−, and that IO3− sorbs to a greater extent than I−, sheds light into earlier unexplained Hanford field data that demonstrated increases in groundwater 127I−/127IO3− ratios and a decrease groundwater 129IO3− concentrations along a transect away from the point sources, where iodine was primarily introduced as IO3−. While a majority of the radioiodine does not bind to these alkaline sediments, there is likely a second smaller iodine fraction in the Hanford subsurface that is strongly bound, presumably to the sediment OC (and carbonate) phases. This second fraction may have an impact on establishing remediation goals and performance assessment calculations.

Eelgrass fairy rings: sulfide as inhibiting agent

Distinct ‘fairy rings’ consisting of narrow fringes of eelgrass (Zostera marina L.) expand radially over a bottom of chalk plates outside the calcium carbonate cliffs of the island of Mon, Denmark. We conducted a survey to evaluate possible explanations for the formation of the rings and, more specifically, for the apparent die-off of eelgrass shoots on the inner side of the rings. The fairy rings were up to 15 m in diameter consisting of 0.3- to 1-m-wide zones of sea grass shoots at densities of up to 1,200 shoots m−2 and rooted in an up to 10-cm-thick sediment layer. On the outer side, shoots expanded over the bare chalk plates. On the inner side, shoots were smaller, had lower absolute and specific leaf growth, shoot density was lower and the sediment eroded leaving the bare chalk with scattered boulders behind. Sediment organic matter and nutrients and tissue nutrient contents were not different among positions. Sediment pools of acid volatile sulfides and chromium-reducible sulfur increased from outer to the middle positions of the rings, and so did total sulfur content of eelgrass tissues, while tissue δ34S isotope ratios, regardless of position in the fringes, were low reflecting substantial invasion of sulfide from the sediment. Neither the clonal growth pattern of eelgrass, sediment burial of shoots, hydrodynamic forcing nor nutrient limitation could explain the ring-shaped pattern. We conclude that the most likely explanation must be found in invasion of eelgrass shoots by toxic sulfide accumulating in the sediment due to low iron availability in the carbonate-rich environment.

Mobilization of Ag, heavy metals and Eu from the waste deposit of the Las Herrerias mine (Almería, SE Spain)

We studied the mobility of silver, heavy metals and europium in waste from the Las Herrerias mine in Almeria (SE Spain). The most abundant primary mineral phases in the mine wastes are hematite, hydrohematite, barite, quartz, muscovite, anorthite, calcite and phillipsite. The minor phase consisted of primary minerals including ankerite, cinnabar, digenite, magnesite, stannite, siderite and jamesonite, and secondary minerals such as glauberite, szomolnokite, thenardite and uklonscovite. The soils show high concentrations of Ag (mean 21.6 mg kg–1), Ba (mean 2.5%), Fe (mean 114,000 mg kg–1), Sb (mean 342.5 mg kg–1), Pb (mean 1,229.8 mg kg–1), Zn (mean 493 mg kg–1), Mn (mean 4,321.1 mg kg–1), Cd (mean 1.2 mg kg–1) and Eu (mean 4.0 mg kg–1). The column experiments showed mobilization of Ag, Al, Ba, Cu, Cd, Eu, Fe, Mn, Ni, Sb, Pb and Zn, and the inverse modelling showed that the dissolution of hematite, hausmannite, pyrolusite and anglesite can largely account for the mobilization of Fe, Mn and Pb in the leaching experiment. The mobility of silver may be caused by the presence of kongsbergite and chlorargyrite in the waste, while the mobility of Eu seems to be determined by Eu(OH)3, which controls the solubility of Eu in the pH–Eh conditions of the experiments. The mineralogy, pH, Eh and geochemical composition of the mine wastes may explain the possible mobilization of heavy metals and metalloids. However, the absence of contaminants in the groundwater may be caused by the carbonate-rich environment of “host-rocks” that limits their mobility.

Taphonomy and compositional fidelity of Quaternary fossil assemblages of terrestrial gastropods from carbonate-rich environments of the Canary Islands

Quaternary aeolian deposits of the Canary Islands contain well-preserved terrestrial gastropods, providing a suitable setting for assessing the taphonomy and compositional fidelity of their fossil record over ~13 kyr. Nine beds (12, 513 shells) have been analysed in terms of multivariate taphonomic and palaeoecological variables, taxonomic composition, and the stratigraphic and palaeontological context. Shells are affected by carbonate coatings, colour loss and fragmentation. Shell preservation is size-specific: juveniles are less fragmented and show colour preservation more commonly than adults. In palaeosols, the adult shell density correlates negatively with the proportion of fragmented adults, negatively with the proportion of juveniles, and positively with the proportion of adults with coatings. High bioturbation intensity in palaeosols is associated with low shell fragmentation and high proportion of shells with coatings. These relationships imply that high adult density in palaeosols was driven by an increase in shell production rate (related to a decrease in predation rates on adults and a decrease in juvenile mortality) and a decrease in shell destruction rate (related to an increase in durability enhanced by carbonate precipitation). In dunes, the relationships between taphonomic alteration, shell density and bioturbation are insignificant. However, dune assemblages are characterized by a lower frequency of shells with coatings and higher rates of colour loss, indicating lower shell durability in dunes than in palaeosols. Additionally, nonrandom differences in the coating proportion among palaeosols imply substantial temporal variation in the rate of carbonate crust formation, reflecting long-term changes in bioturbation intensity that covaries positively with shell preservation. Dunes and palaeosols do not differ in species abundances despite differences in the degree of shell alteration, suggesting that both weakly and strongly altered assemblages offer data with a high compositional fidelity. Carbonate-rich terrestrial deposits originating in arid conditions can enhance the preservation of gastropods and result in fossil assemblages that are suitable for palaeoecological and palaeoenvironmental studies of terrestrial ecosystems. � Aeolian deposits, Canary Islands, land snail shell assemblages, Quantitative Taphonomy, Quaternary .

Palaeoenvironmental change in the Gulf of Carpentaria (Australia) since the last interglacial based on Ostracoda

Throughout the last glacial cycle, the region between Australia and New Guinea, which is today known as the Gulf of Carpentaria, has oscillated from open shallow marine conditions to a large, land-locked freshwater lake, including periods of subaerial exposure. Ostracod faunal assemblages and variations in the valve morphology, preserved in the sediments of the gulf, record these changes. A 14.8 m long core (MD972132) extracted from near the centre of the modern Gulf of Carpentaria, spanning the last 130 ka BP provides the basis of this study. Environmental facies were determined by R- and Q-mode cluster analysis of the ostracod assemblage data, including 72 species, and comparison with modern analogues from both the Gulf of Carpentaria and Southeast Asian region. Using these methods, six clearly distinct biofacies were identified: (i) open shallow marine facies, including bairdiids, pectocytherinids and cytherettids; (ii) shallow marine facies, dominated by Cytherella and Hemikrithe; (iii) marginal marine facies, including Xestoleberis and Praemunita; (iv) tidal channel facies, dominated by Loxoconcha; (v) estuarine assemblage, comprising Venericythere and Leptocythere; (vi) non-marine facies a. brackish lagoon/lake facies dominated by Cyprideis and Leptocythere; b. freshwater facies, including Ilyocypris, with Cyprinotus and Cypretta. In addition, morphological variation of valves of the more “plastic” species, in particular Cyprideis australiensis and Leptocythere hartmanni, was observed and related to environmental variables, including salinity and solute composition. These two species occur through more than half of the length of the core and show significant variability. C. australiensis with irregular-shaped sieve pores is associated with heavily reticulated valves of L. hartmanni, around 90–70 ka BP, indicating increased salinity and carbonate-limited environments. Conversely, C. australiensis with round sieve pores occurs with finely reticulated valves of L. hartmanni from around 50 ka BP, in fresher, carbonate-rich environments. The preservation of valves was also noted so as to infer post-depositional effects, revealing shoreline features, channel activity and subaerial exposure. Combined ostracod biofacies and morphological analysis reveals a fluctuating marine environment through Marine Isotope Stage (MIS) 5, terminating in a restricted lagoon around 90 ka BP, followed by an extensive period of subaerial exposure in this region of the gulf. MIS 3 marks a return of marine conditions and an increase in fluvial activity. Lake Carpentaria then appears as a permanent feature, at least to the current 60 m depth contour, from around 40 ka BP, with the freshest water occurring around 16 cal. ka BP, prior to the most recent marine transgression, at 10.8 cal. ka BP. Although the presence of Lake Carpentaria had previously been identified, this study extends the knowledge of the region through the last glacial cycle and provides greater detail of the sequential biofacies.

Palaeoenvironments of vertebrates on the southern shore of Tethys: The nonmarine Early Cretaceous of Tunisia

Through the Late Jurassic and Early Cretaceous, the southern shore of the Tethys Ocean migrated north and south over short distances. These vicissitudes are documented in the ‘continental intercalaire’, a long series of mainly non-marine sediments deposited across North Africa. A combined taxonomic, physical and chemical taphonomic study provides independent lines of evidence for reconstruction of palaeoenvironments within this marginal marine setting. The Douiret, Chenini and Oum ed Diab formations from the Tataouine basin of southern Tunisia span the later part of the Early Cretaceous. Microvertebrates from four sites in these formations show different modes of physical abrasion, time averaging, and mixing, based on a taphonomic analysis using a combination of physical and chemical methods. The taxonomic composition of each assemblage, and trends in rare earth element (REE) compositions of bones, from each locality were used as independent lines of evidence to indicate differences in early depositional environments. The Jebel Boulouha assemblage (Douiret Formation) is interpreted as a terrestrial carbonate-rich environment with relatively little mixing. The Touil el Mra assemblage (Oum ed Diab Formation) suggests a marginal marine environment with some mixing of previously interred bones. The Oued el Khil assemblage (Chenini Formation) and the Oum ed Diab assemblage (Oum Ed Diab Formation) are more equivocal, suggesting mixed freshwater and marine influences. Interpreting salinity in marginal marine settings is difficult, and best attempted from multiple, independent lines of evidence. We suggest that REE geochemistry can contribute to palaeoenvironmental reconstruction when used in combination with other, independent physical, palaeontological and /or geochemical methods.

Use of in situ-produced 10Be in carbonate-rich environments: A first attempt

We have determined the production rate of in situ-produced 10Be in calcite through measurements of 10Be and 36Cl concentrations in the same calcite samples and of 10Be concentrations in depth profiles of flint from the same erosional surface. This yields a 10Be production rate in calcite of 37.9 ± 6.0 at/g/yr at sea level and high latitude, approximately sixfold higher than production in the coexisting flint. We propose that this higher rate of production may be due to high production cross sections for C spallation by cosmic rays with energies below 50 MeV. These results also open the possibility of dating burial events in carbonate-rich environments by differential radioactive decay of 10Be and 36Cl.

Response of larger foraminifera to mixed carbonate-siliciclastic environments: an example from the Oligocene-Miocene sequence of Kutch, India

Abstract The late Oligocene-early Miocene mixed carbonate-siliciclastic deposits of Kutch developed on the stable shelf of a peri-cratonic rift basin. It hosts a number of larger foraminiferal genera. The depositional environment of the sequence is interpreted and carbonate microfacies analysis has been carried out. The environmental and microfacies distributions of different genera and their response to energy conditions and terrigenous influx are examined. It is interpreted that the sequence was deposited in a wide range of environments, including back-reef lagoon, shallow subtidal seas, intertidal, swamps, tidal channels and supratidal. Larger foraminifera are recorded from the lagoon and shallow subtidal part of the sequence. Heterostegina and Spiroclypeus are found to occur in lagoon while Miogypsina, Lepidocyclina and Operculina occur in both lagoon and shallow subtidal environments. Archaias and Sorites prefer subtidal conditions. The distribution of different genera in relation to carbonate microfacies varies. Miogypsina, Archaias and Sorites occur in more microfacies than Heterostegina, Spiroclypeus, Operculina and Lepidocyclina. Larger foraminifera also differ in their susceptibility to clastic influx in the environment. Spiroclypeus and Sorites prefer a carbonate-rich environment while Miogypsina is most tolerant to terrigenous input. The genera Heterostegina and Spiroclypeus are found to be restricted to low energy environments but Miogypsina, Lepidocyclina, Operculina, Archaias and Sorites can tolerate agitated water conditions. It is interpreted that Heterostegina and Spiroclypeus are extreme K-strategists while Miogypsina tends toward r-mode opportunists. Between the two ends of the spectrum lie Lepidocyclina and Operculina. The life history of Archaias and Sorites is possibly comparable to Miogypsina.

Geoquímica del petróleo de la cuenca del Putumayo

Biomarker fingerprinting of 20 crude oils from Putumayo Basin, Colombia, shows a vertical segregation of oil families. The Lower Cretaceous reservoirs (Caballos and "U" Villeta sands) contain oils that come from a mixture of marine and terrestrial organic matter, deposited in a marginal, "oxic" marine setting. The Upper Cretaceous ("T" and "N" sands) and Tertiary reservoirs contain oils with marine algal input deposited in a reducing, carbonate-rich environment. Lithology, environmental conditions and organic matter type of source rocks as predicted from oil biomarker differences correspond to organic composition of two Cretaceous source rocks. Vertical heterogeneity in the oils, even those from single wells, suggests the presence of two isolated petroleum systems. Hydrocarbons from Lower Cretaceous source rocks charged Lower Cretaceous reservoirs whereas oils from Upper Cretaceous source rocks charged Upper Cretaceous and Tertiary reservoirs. Oil migration from mature source rocks into multiple reservoirs has been stratigraphically updip along the "regional" sandstone units and vertical migration through faults has been limited. Biomarker maturity parameters indicate that all oils were generated from early thermal maturity oil window.

In situ measurements of benthic primary production, respiration and nutrient fluxes in a hypersaline coastal lagoon of SE Brazil

Bentbic oxygen and nutrient ftuxes were measured in a section of the hypersaline carbonate-rich coastal lagoon of Araruama, SE-Brazil. In situ incubations of the sediment surface (Zm - 1.5) were performed at one station with light/dark chambers during september 1993 (early spring period) and april 1995 (earlyautumn period). The carbonate..rich aediments were covered by 1-3 mm thick microalgal mats, dominated by the cyanobaeteria Phormidium sp, Oscillatoria sp, and Lyngbya sp. Benthic net primary production rates were 15.4 ± 0.7 mmolC/m²/d in early spring and 33.8 ± 8.8 mmolC/m²/d in early autumn, total community respiration rates attained 35.3 ± 7.2 and 65.7 ± 16.9 mmolC/m²/d, and pelagic primary production rates 1.7 ± 0.7 and 4.0 ± 1.4 mmolC/m²/d, respectively. Total community metabolism was thus heterauophic and mainly driven by benthic metabolism. The benthic release rates af ammonia were 0.65 ± 0.32 mmolC/m²/day in early spring and 0.58± 0.42mmoVm ldaym early autumn, butwere near to negligible for orthophosphate. Pelagic primaryproduction was limited byphosphorous, in part, by the preferential release of etmmonia over orthophosphate from the sediment-water interface. The benthic primary production and nutrient release rates were within the range of other eury-to hypersaline carbonate-rich environments characterized by non- consolidated algat rats.