Time calibration of sedimentary sections based on insolation cycles using combined cross-correlation: dating the gone Badenian stratotype (Middle Miocene, Paratethys, Vienna Basin, Austria) as an example

Cross-correlation between insolation intensities and a combination of sedimentary characters is introduced to obtain precise time calibration of sedimentary cycles. The first step is to transfer the section scale into ages using power spectra comparing the main periods with orbital cycles, while in the second step the standardized values of sedimentary signals are cross-correlated with the standardized insolation curve. As an example for the applicability of the method, we investigated calcium carbonate, organic carbon in a 9-m sampled section from the historical Badenian stratotype at Baden/Sooss (Lower Austria). Comparing courses of geochemical parameters between the historical stratotype and a nearby drilled 102-m scientific core resulted in continuation of the core section into the stratotype. Cross-correlation between magnetic susceptibility (MS) combined with the negatively correlated calcium carbonate content of the drilled section on the one side and summer solar insolation at 65° northern latitude on the other resulted in an extremely significant correlation between −14.221 and −13.982 Ma. This is younger than the before estimated time frame (−14.379 to −14.142 Ma) based on cross-correlation between MS and the orbital 100-kyr eccentricity and 41-kyr obliquity cycles. The direct continuation of the drilled section by the stratotype covering a time span of 17.7 kyr consequently dates the Badenian stratotype between −13.982 and −13.964 Ma. Therefore, the upper limit of the stratotype, assigned to the Early Badenian, puts it close to the Langhian/Seravallian boundary at −13.82 Ma, demonstrating the need for revising the Badenian stratigraphic subdivision based on orbital cycles, especially the middle Badenian Wielician substage.     

Paleoceanography and climate of the Badenian (Middle Miocene, 16.4–13.0 Ma) in the Central Paratethys based on foraminifera and stable isotope (δ18O and δ13C) evidence

Benthic foraminifera and stable isotopes analyses revealed changes emerging in the paleoceanographic scenery in the Paratethys. The percentage of inbenthic, oxyphylic taxa and diversity in the benthic foraminiferal assemblage showed increasing food supply (organic matter), decreasing oxygen level and growing stress on the sea floor. Oxygen isotopes measured in planktonic and benthic foraminifera pointed to strengthening stratification during the Badenian period. The carbon isotopes indicated intensified accumulation of light marine organic matter. This increasing stratification trend is especially pronounced by Late Badenian (13.5–13 Ma) when surface water oxygen isotope values are rather negative. A simple two-layer circulation model was worked out for the Badenian Paratethys explaining these characteristic environmental changes. An antiestuarine (lagoonal) circulation is assumed for the Central Paratethys during the Early (16.4–15 Ma) and mid Badenian (15–13.5 Ma). The mid Badenian period of time comprises the short episode of evaporite formation in the Carpathian Foredeep and the Transylvanian Basin. Evidence presented here supported a reversal of circulation to estuarine type after the deposition of salts by Late Badenian (13.5–13 Ma). The Early Badenian antiestuarine circulation is suggested to associate with the high temperatures of the Mid-Miocene Climatic Optimum, and the Late Badenian estuarine circulation with the cooler period following it.     

Trace metals (Cd,Pb, Cu,Zn and Ni) in sediment of the submarine pit Dragon ear (Soline Bay,Rogoznica, Croatia)

Vertical profiles of trace metal (Cd, Pb, Zn, Cu, Ni) concentrations, organic matter content, carbonate content and granulometric composition were determined in two sediment cores from the submarine pit Dragon Ear (Middle Adriatic). Concentrations of the analyzed metals (Cd: 0.06–0.12 mg kg⁻¹, Pb: 28.5–67.3 mg kg⁻¹, Zn: 17.0-65.4 mg kg⁻¹, Cu: 21.1–51.9 mg kg⁻¹, Ni: 27.8–40.2 mg kg⁻¹) were in usual range for Adriatic carbonate marine sediments. Nevertheless, concentrations of Cu, Zn, and especially Pb in the upper layer of sediments (top 12 cm) were higher than in bottom layer, while Cd and Ni concentration profiles were uniform. Regression analysis and principal component analysis were used to interpret distribution of trace metals, organic matter and carbonate content in sediment cores. Results of both analysis showed that concentrations of all trace metals in the core below the entrance to the pit were significantly positively correlated with organic matter and negatively correlated with carbonate, while in the core more distant from the entrance only Pb showed significant positive correlation with organic matter. Obtained results indicated that, except for lead which was enriched in surface sediment, in the time of sampling (before the building of the nautical marina) investigated area belonged to unpolluted areas.     

Contribution of a Dense Population of the Brittle Star <Emphasis Type="Italic">Acrocnida brachiata</Emphasis> (Montagu) to the Biogeochemical Fluxes of CO<Subscript>2</Subscript> in a Temperate Coastal Ecosystem

The production of organic matter and calcium carbonate by a dense population of the brittle star Acrocnida brachiata (Echinodermata) was calculated using demographic structure, population density, and relations between the size (disk diameter) and the ash-free dry weight (AFDW) or the calcimass. During a 2-year survey in the Bay of Seine (Eastern English Channel, France), organic production varied from 29 to 50 g_AFDW m⁻² year⁻¹ and CaCO₃ production from 69 to 104 g_CaCO3 m⁻² year⁻¹. Respiration was estimated between 1.7 and 2.0 mol_CO2 m⁻² year⁻¹. Using the molar ratio (ψ) of CO₂ released: CaCO₃ precipitated, this biogenic precipitation of calcium carbonate would result in an additional release between 0.5 and 0.7 mol_CO2 m⁻² year⁻¹ that represented 23% and 26% of total CO₂ fluxes (sum of calcification and respiration). The results of the present study suggest that calcification in temperate shallow environments should be considered as a significant source of CO₂ to seawater and thus a potential source of CO₂ to the atmosphere, emphasizing the important role of the biomineralization (estimated here) and dissolution (endoskeletons of dead individuals) in the carbon budget of temperate coastal ecosystems.     

Decorative marbles from the Krkonoše-Jizera Terrane (Bohemian Massif,Czech Republic): provenance criteria

Marbles from western part of the Krkonoše-Jizera Terrane (northern part of the Bohemian Massif) have been studied to obtain mineropetrographic and chemical reference data for provenance studies. Samples from six different quarries were analysed by mineralogical-petrographic and geochemical methods (optical microscopy, X-ray diffraction, stable isotope ratio analysis, cathodoluminescence, bulk magnetic susceptibility). Petrographic characteristics permit a distinction between fine-grained to medium-grained marbles from the Jizera Mts (amphibolite metamorphic facies) and fine-grained marbles from the Ještěd Mts (low-grade greenschist facies). The samples studied are mainly calcitic, with the exception of those from Raspenava in which dolomite is abundant in two types. The mineralogical composition of the insoluble residues is clinochlore ± serpentine ± tremolite ± diopside ± pyrite + magnetite in case of the locality Raspenava and clinochlore + muscovite ± quartz ± pyrite ± rutile ± haematite in case of the localities from the Ještěd Mts. δ¹³C and δ¹⁸O variations in primary and secondary carbonate phases allow to distinguish genetically different carbonate veins and permit quarry separation in one case (Raspenava, Jizera Mts). The δ¹³C and δ¹⁸O values of the groundmass range from −1 to +3‰ and from −8 to −20‰ (PDB), respectively. The δ¹³C and δ¹⁸O values of secondary carbonate veins decrease to −3‰ and reach more negative values up to −26‰ in case of δ¹⁸O. The fabric of cathodomicrofacies allows the distinction between calcite and dolomite, except three localities (Pilínkov, Horní Hanychov, Jitrava—rose type) with majority of quenchers (high content of iron in carbonate). The genetically different calcite is characterised by a pale and dark orange luminescence distribution. Serpentine, tremolite, forsterite, opaque minerals and quartz have no luminescence and very dull luminescence, respectively. The majority of studied marbles exhibits low values of the bulk magnetic susceptibility, with the exception of those from Raspenava rich in magnetite.     

Abundance and Chemical Speciation of Phosphorus in Sediments of the Mackenzie River Delta, the Chukchi Sea and the Bering Sea: Importance of Detrital Apatite

Utilizing a sequential extraction technique this study provides the first quantitative analysis on the abundance of sedimentary phosphorus and its partitioning between chemically distinguishable phases in sediments of the Bering Sea, the Chukchi Sea and the Mackenzie River Delta in the western Arctic Ocean. Total sedimentary phosphorus (TSP) was fractionated into five operationally defined phases: (1) adsorbed inorganic and exchangeable organic phosphorus, (2) Fe-bound inorganic phosphorus, (3) authigenic carbonate fluorapatite, biogenic apatite and calcium carbonate-bound inorganic and organic phosphorus, (4) detrital apatite, and (5) refractory organic phosphorus. TSP concentrations in surface sediments increased from the Chukchi Sea (18 μmol g⁻¹ of dried sediments) to the Bering Sea (22 μmol g⁻¹) and to the Mackenzie River Delta (29 μmol g⁻¹). Among the five pools, detrital apatite phosphorus of igneous or metamorphic origin represents the largest fraction (~43%) of TSP. The second largest pool is the authigenic carbonate fluorapatite, biogenic apatite as well as CaCO₃ associated phosphorus (~24% of TSP), followed by the Fe-bound inorganic phosphorus, representing ~20% of TSP. The refractory organic P accounts for ~10% of TSP and the readily exchangeable adsorbed P accounts for only 3.5% of TSP. Inorganic phosphorus dominates all of phosphorus pools, accounting for an average of 87% of the TSP. Relatively high sedimentary organic carbon and total nitrogen contents and low δ¹³C values in the Mackenzie River Delta together with the dominance of detrital apatite in the TSP demonstrate the importance of riverine inputs in governing the abundance and speciation of sedimentary phosphorus in the Arctic coastal sediments.     

Integrated stratigraphy and 40Ar/39Ar chronology of the early to middle Miocene Upper Freshwater Molasse in western Bavaria (Germany)

A detailed integrated stratigraphic study (biostratigraphy and magnetostratigraphy) was carried out on five sections from the western part of the Bavarian Upper Freshwater Molasse of the North Alpine Foreland Basin (NAFB), greatly improving the chronostratigraphy of these sediments. The sections belong to the lithostratigraphic units Limnische Untere Serie (UL) and Fluviatile Untere Serie (UF) and contain 19 (mostly new) small-mammal bearing levels, significantly refining the local biostratigraphy. Radiometric ages obtained from glass shards from tuff horizons are used together with the biostratigraphic information for constructing and confirming the magnetostratigraphic correlation of the studied sections to the Astronomical Tuned Time Scale (ANTS04; Lourens et al. in Geologic Time Scale 2004, Cambridge University Press, 2004). This correlation implies that the UL lithostratigraphic unit corresponds to the latest Ottnangian and the Early Karpatian, whereas the UF corresponds to the Karpatian and the Early Badenian. This indicates that the Brackish- to Freshwater Molasse transition already occurred during the late Ottnangian. The pre-Riesian hiatus occurred in the latest Karpatian and lower Early Badenian in Eastern Bavaria and Bohemia and in the Late Karpatian and earliest Badenian in Western Bavaria. The geochemical and Ar–Ar data of volcanic ashes suggest that highly evolved silicic magmas from a single volcano or volcanic center, characterized by a uniform Nd isotopic composition, erupted repetitively over the course of at least 1.6 Myr. Three phases of eruptive activity were identified at 16.1 ± 0.2 Ma (Zahling-2), 15.6 ± 0.4 Ma (Krumbad), and 14.5 ± 0.2 Ma (Heilsberg, Hegau). The correlation of the local biostratigraphic zonation to the ANTS04 enables further the characterization of both the Ottnangian–Karpatian and Karpatian–Badenian boundaries in the NAFB by small-mammal biostratigraphy. According to these results the Ottnangian–Karpatian boundary is contemporaneous with the first appearance datum of Megacricetodon bavaricus (in the size of the type population) and the first common occurrence of Keramidomys thaleri, whereas Ligerimys florancei, Melissiodon dominans and Prodeinotherium aff. bavaricum have been already disappeared during the late Ottnangian. The Karpatian–Badenian boundary is characterized by a significant size increase of the large Megacricetodon lineage and possibly a (re-)immigration of Prodeinotherium bavaricum.     

Phosphorite-hosted zinc and lead mineralization in the Sekarna deposit (Central Tunisia)

The Sekarna Zn–Pb deposit is located in Central Tunisia at the northeastern edge of the Cenozoic Rohia graben. Mineralization comprises two major ore types: (1) disseminated Zn–Pb sulfides that occur as lenses in sedimentary phosphorite layers and (2) cavity-filling zinc oxides (calamine-type ores) that crosscut Late Cretaceous and Early Eocene limestone. We studied Zn sulfide mineralization in the Saint Pierre ore body, which is hosted in a 5-m-thick sedimentary phosphorite unit of Early Eocene age. The sulfide mineralization occurs as replacements of carbonate cement in phosphorite. The ores comprise stratiform lenses rich in sphalerite with minor galena, Fe sulfides, and earlier diagenetic barite. Laser ablation–inductively coupled plasma mass spectrometry analyses of sphalerite and galena show a wide range of minor element contents with significant enrichment of cadmium in both sphalerite (6,000–20,000 ppm) and galena (12–189 ppm). The minor element enrichments likely reflect the influence of the immediate organic-rich host rocks. Fluid inclusions in sphalerite give homogenization temperatures of 80–130°C. The final ice melting temperatures range from −22°C to −11°C, which correspond to salinities of 15–24 wt.% NaCl eq. and suggest a basinal brine origin for the fluids. Sulfur isotope analyses show uniformly negative values for sphalerite (−11.2‰ to −9.3‰) and galena (−16‰ to −12.3‰). The δ³⁴S of barite, which averages 25.1‰, is 4‰ higher than the value for Eocene seawater sulfate. The sulfur isotopic compositions are inferred to reflect sulfur derivation through bacterial reduction of contemporaneous seawater sulfate, possibly in restricted basins where organic matter was abundant. The Pb isotopes suggest an upper crustal lead source.     

Diel Aquatic CO<Subscript>2</Subscript> System Dynamics of a Bermudian Mangrove Environment

Mangrove ecosystems play an important, but understudied, role in the cycling of carbon in tropical and subtropical coastal ocean environments. In the present study, we examined the diel dynamics of seawater carbon dioxide (CO₂) and dissolved oxygen (DO) for a mangrove-dominated marine ecosystem (Mangrove Bay) and an adjacent intracoastal waterway (Ferry Reach) on the island of Bermuda. Spatial and temporal trends in seawater carbonate chemistry and associated variables were assessed from direct measurements of dissolved inorganic carbon, total alkalinity, dissolved oxygen (DO), temperature, and salinity. Diel pCO₂ variability was interpolated across hourly wind speed measurements to determine variability in daily CO₂ fluxes for the month of October 2007 in Bermuda. From these observations, we estimated rates of net sea to air CO₂ exchange for these two coastal ecosystems at 59.8 ± 17.3 in Mangrove Bay and 5.5 ± 1.3 mmol m⁻² d⁻¹ in Ferry Reach. These results highlight the potential for large differences in carbonate system functioning and sea-air CO₂ flux in adjacent coastal environments. In addition, observation of large diel variability in CO₂ system parameters (e.g., mean pCO₂: 390–2,841 μatm; mean pH_T: 8.05–7.34) underscores the need for careful consideration of diel cycles in long-term sampling regimes and flux estimates.     

Planktonic and whole system metabolism in a nutrient-rich estuary (the Scheldt estuary)

Planktonic gross primary production (GPP), community respiration (CR), and nitrification (NIT) were measured monthly in the Scheldt estuary by the oxygen incubation method in 2003. No significant evolution of planktonic GPP was observed since the 1990s with high rates in the freshwater area (salinity 0; 97±65 mmol C m⁻² d⁻¹) decreasing seaward (22–37 mmol C m⁻² d⁻¹). A significant decrease of NIT was observed with regard to previous investigations although this process still represents up to 20% of total organic matter production in the inner estuary. Planktonic CR was highest in the inner estuary and seemed to be mainly controlled by external organic matter inputs. Planktonic net community production was negative most of the time in the estuary with values ranging from −300 to 165 mmol C m⁻² d⁻¹. Whole estuary net ecosystem production (NEP) was investigated on an annual scale using the results mentioned above and published benthic metabolic rates. A NEP of −39±8 mmol C m⁻² d⁻¹ was estimated, which confirms the strong heterotrophic status of this highly nutrified estuary. NEP rates were computed from June to December 2003 to compare with results derived from the Land-Ocean Interaction in the Coastal Zone budgeting procedure applied to dissolved inorganic phosphorus and carbon (DIP and DIC). DIP budgets failed to provide realistic estimates in the inner estuary where abiotic processes account for more than 50% of the nonconservative DIP flux. DIC budgets predicted a much lower NEP than in situ incubations (−109±31 versus −42±9 mmol C m⁻² d⁻¹) although, as each approach is associated with several critical assumptions, the source of this discrepancy remains unclear.     

Vertical patterns of stable carbon isotope in soils and particle-size fractions of karst areas, Southwest China

Taking limestone soil and yellow soil, the two major soil types in karst areas as examples, analyzing stable carbon isotope composition (δ¹³C value) of soil organic matter (SOM) in bulk soils and particle-size fractions of four soil profiles under three vegetable forms, the following results are reached: in the limestone soil profile, soil organic carbon contents are all above 1.0%, the highest value is 7.1% in the surface soil; however, they are between 0.3% and 4.6% in the three yellow soil profiles. From the surface to the bottom of the soil profiles, the variation of δ¹³C value of soil organic carbon for limestone soil profile is only between −24.1‰ and −23.0‰, however, it’s between −24.8‰ and −21.1‰ for yellow soil profiles. The variation range of δ¹³C value of soil organic carbon associated with particle-size separates is slight for limestone soil but is considerable for yellow soil. The contrast research indicates that the changes between the contents and the δ¹³C value of soil organic carbon with depth are complex. The vertical patterns of stable carbon isotope in soil organic matter have a distinct regional characteristic in karst areas.     

Dynamics of transparent exopolymeric particles (TEP) and particle-associated carbohydrates in the Dona Paula bay, west coast of India

Surface seawater samples were collected over a period of 27 months at a shallow water station in Dona Paula bay from 1998–2000. The samples were analyzed to assess the seasonal variations, inter-annual variability and the contributions of:

Soil organic carbon storage changes in Yangtze Delta region,China

Soil carbon sequestration plays an essential role in mitigating CO₂ increases and the global greenhouse effect. This paper calculates soil organic carbon (SOC) storage changes during the course of industrialization and urbanization in Yangtze Delta region, China, based on the data of the second national soil survey (1982–1985) and the regional geochemical survey (2002–2005), with the help of remote sensing images acquired in periods of 1980, 2000, 2005. The results show that soils in the top 0–20 and 0–100 cm depth in this region demonstrate the carbon sink effect from the early 1980s to the early 2000s. The SOC storage in 0–20 cm depth has resulted in increase from 213.70 to 238.65 Tg, which corresponds to the SOC density increase from 2.94 ± 1.08 to 3.28 ± 0.92 kg m⁻², and mean carbon sequestration storage and rate are 1.25 Tg a⁻¹, 17.14 g m⁻² a⁻¹, respectively. The SOC storage in 0–100 cm depth has resulted in increase from 690.26 to 792.65 Tg, which corresponds to the SOC density increase from 9.48 ± 4.22 to 10.89 ± 3.42 kg m⁻², and mean carbon sequestration storage and rate are 5.12 Tg a⁻¹, 70.32 g m⁻² a⁻¹, respectively. Urban area in Yangtze Delta region, China, increased more than 3,000 km² and the urban growth patterns circled the central city region in the past 20 years. The SOC densities in 0–20 cm depth decrease gradually along urban–suburban–countryside and the urban topsoil is slightly enriched with SOC. Compared to the data of the second national soil survey in the early 1980s, the mean SOC density in urban area increased by 0.76 kg m², or up 25.85% in the past 20 years. With the characteristics of SOC storage changes offered, land-use changes, farming system transition and ecological city construction are mainly attributed to SOC storage increases. Because of lower SOC content in this region, it is assumed that the carbon sink effect will go on in the future through improved soil management.     

Origins of cold-wet-oxidizing to hot-dry-reducing rhyolite magma cycles and distribution in the Taupo Volcanic Zone, New Zealand

Slab-derived aqueous fluid components (Ba, Cl) correlate well with oxygen fugacity, and other well-defined characteristics of silicic magmas in the Taupo Volcanic Zone (TVZ) between a cold-wet-oxidizing magma type [R1: amphibole ± biotite; high Sr, low Zr and FeO*/MgO, depleted middle rare-earth elements (MREE)] and a hot-dry-reducing magma type (R2: orthopyroxene ± clinopyroxene; low Sr, high Zr, and FeO*/MgO, less depleted MREE). Oxygen fugacity was obtained from analysis of Fe–Ti oxides and ranges between −0.04 and +2.1 log units (ΔQFM, where QFM = quartz + fayalite + magnetite buffer) and is positively correlated with the bulk-rock Ba/La ratio, indicating that slab-derived fluid is the oxidizing agent in the rhyolites. Chlorine contents in hornblende also correlate with the bulk-rock Ba/La ratio. Hence, high-fluid flux typically correlates with the R1 and low-fluid flux with R2 rhyolite magma types. A geochemical evolution and distribution can be tracked in time and space throughout the central region of the TVZ from 550 ka to present and has revealed two distinct magmatic cycles that vary in length. The first cycle included widespread R1 type magmatism across the central TVZ beginning ca. 550 ka and was directly associated with previously unreported dome-building and ignimbrite-forming volcanism, and led to a voluminous (>3,000 km³) ignimbrite ‘flare-up’ between ca. 340 and 240 ka. The second cycle began roughly 180 ka, erupting ca. 800 km³ of magma, and continues to the present. The duration, rate, and composition of magma production within these cycles appears to be governed by the flux of fluid released from the subducting slab, while the distribution of magmas may be governed more by extension along the central rift axis. Shorter cycles have also been identified and are unrelated to subduction processes, but occur following large, caldera-forming events.     

Trends in phosphatase activity along a successional gradient of tidal freshwater marshes on the Cooper River South Carolina

Phosphatase activity was measured in sediments from tidal freshwater habitats adjacent to the Cooper River in South Carolina representing different stages of ecological succession. It was found that sediment (0–5 cm) acid phosphatase activity, alkaline phosphatase activity and phosphodiesterase activity increased with increasing successional stage and phytomass. Acid phosphatase activity in creased from 7.5±1.2 (±1 SD) in subtidal sediment from a shallow open water habitat without vegetation to 61.2±4.9 μmol g⁻¹ hr⁻¹ (μmol of p-nitrophenol released per gram of dry sediment per hour) in intertidal sediments colonized by emergent macrophytes, while alkaline phosphatase activity increased from 2.1±0.1 to 19.01±1.5 μmol g⁻¹ hr⁻¹. Phosphodiesterase activity increased from 1.8±0.1 to 20.2±2.0 μmol g⁻¹ hr⁻¹ along the same gradient. Acid phosphatase activity was highly correlated (R²=0.92, P<0.001) with the organic matter content of the sediment. A study of phosphatase kinetics showed that V_max of all phosphatases also increased along the successional gradient. Trends in phosphatase activity and V_max correlated positively with plant biomass and negatively with concentrations of soluble reactive phosphorus in porewater, sediment extractable phosphorus, and total phosphourus. The porewater N∶P atom ratio decreased along the succession gradient from 25.3 in an early stage, open water community to 13.0 in a community dominated by emergent vegetation. The data also show that the distribution of the forms of phosphorus changed with successional stage. The change in distribution and the increased biological demand for phosphorus that paralleled succession were mediated by the activity of phosphatase enzymes.     

Adsorption kinetic control of As(III &; V) mobilization and sequestration by Mangrove sediment

Elevated concentrations of arsenic in the sediment and pore water in the Sundarban wetlands pose an environmental risk. Adsorption and desorption are hypothesized to be the major processes controlling arsenic retention in surface sediment under oxic/suboxic condition. This study aims to investigate sorption kinetics of As(III & V) and its feedback to arsenic mobilization in the mangrove sediment. It ranges from sand to silty clay loam and shows the adsorption of As(III & V) following the Langmuir relation. Estimates of the maximum adsorption capacity are 59.11 ± 13.26 μg g⁻¹ for As(III) and 58.45 ± 8.75 μg g⁻¹ at 30°C for As(V) in the pH range 4 to 8 and salinity 15–30 psu. Extent of adsorption decreases with increasing pH from 4 to 8 and desorption is the rate-limiting step in the reaction of arsenic with sediment. Arsenic in the sediment could be from a Himalayan supply and co-deposited organic matter drives its release from the sediment. Arsenic concentration in the sediment is well below its maximum absorption capacity, suggesting the release of sorbed arsenic in pore water by the microbial oxidation of organic matter in the sediment with less feedback of adsorption.     

Geo-chemical Behavior of Uranium in the Sambhar Salt Lake, Rajasthan (India): Implications to "Source" of Salt and Uranium "Sink"

Among several salt lakes in the Thar Desert of western India, the Sambhar is the largest lake producing about 2 × 10⁵ tons of salt (NaCl) annually. The “lake system” (lake waters, inflowing river waters, and sub-surface brines) provides a unique setting to study the geo-chemical behavior of uranium isotopes (²³⁸U, ²³⁴U) in conjunction with the evolution of brines over the annual wetting and evaporation cycles. The concentration of ²³⁸U and the total dissolved solids (TDS) in lake water increase from ~8 μg L⁻¹ and ~8 g L⁻¹ in monsoon to ~1,400 μg L⁻¹ and 370 g L⁻¹, respectively, during summer time. The U/TDS ratio (~1 μg g⁻¹ salt) and the ²³⁴U/²³⁸U activity ratio (1.65 ± 0.05), however, remain almost unchanged throughout the year, except when U/TDS ratio approaches to 3.8 at/or beyond halite crystallization. These observations suggest that uranium behaves conservatively in the lake waters during the annual cycle of evaporation. Also, uranium and salt content (TDS) are intimately coupled, which has been used to infer the origin and source of salt in the lake basin. Furthermore, near uniform ratios in evaporating lake waters, when compared to the ratio in seawater (~0.1 μg g⁻¹ salt and 1.14 ± 0.02, respectively), imply that aeolian transport of marine salts is unlikely to be significant source of salt to the lake in the present-day hydrologic conditions. This inference is further consistent with the chemical composition of wet-precipitation occurring in and around the Sambhar lake. The seasonal streams feeding the lake and groundwaters (within the lake’s periphery) have distinctly different ratios of U/TDS (2–69 μg g⁻¹ salt) and ²³⁴U/²³⁸U (1.15–2.26) compared to those in the lake. The average U/TDS ratio of ~1 μg g⁻¹ salt in lake waters and ~19 μg g⁻¹ salt in river waters suggest dilution of the uranium content by the recycled salt and/or removal processes presently operating in the lake during the extraction of salt for commercial use. Based on mass-balance calculations, a conservative estimate of "uranium sink" (in the form of bittern crust) accounts for ~5 tons year⁻¹ from the lake basin, an estimate similar to its input flux from rivers, i.e., 4.4 tons year⁻¹.     

Sedimentary geochemical record of historical anthropogenic activities affecting Guanabara Bay (Brazil) environmental quality

A sediment core from Guanabara Bay (Brazil) was analyzed for ²¹⁰Pb dating, grain size, total organic carbon (TOC) and total nitrogen, carbon stable isotope ratio (δ¹³C), nitrogen stable isotope ratio (δ¹⁵N) and the metals Fe, Mn, Ni, Co, Cu, Pb, V and Zn, to assess the influence of land use changes on the aquatic system in a region for which large industrial and urban development is expected in the next few decades. To obtain baseline data for improving the monitoring of the expected increase in anthropogenic impacts from surrounding drainage basins, a multivariate analysis of data from different sediment layers was carried out to evaluate the dated sediment record. The geochemical data suggested three different sedimentary phases along the last 200 years. Before the 1880s, the highest clay and TOC contents were observed, where the C/N ratios and the δ¹³C values suggested a mixture of algal and terrestrial organic matter and the lowest concentrations of Co, Cu, Pb, V and Zn, for which background levels were estimated (4.6, 2.7, 14.9, 24.3 and 70.2 mg kg⁻¹, respectively). From the 1880s to the 1950s, the metal concentrations and sand particles increased, but no change in organic matter quality was observed, reflecting a period of land use change, still without significant sewage input. After the 1950s, the sedimentation rate increased from 0.42 to 0.77 cm year⁻¹ and increasing urban sewage input was evidenced by lower C/N ratios, higher δ¹⁵N, decrease of Fe and Mn concentrations and increased fluxes of metals and TOC, which showed a good relationship with population growth data.     

Carbon and Oxygen Isotopes and Formation Conditions of the Upper Famennian Shale-Bearing Rocks in the Pripyat Trough,Southern Belarus

The behavior of stable carbon and oxygen isotopes in carbonates during the deposition and diagenesis of sediments in the bioproductive Upper Famennian Pripyat Trough (southern Belarus) is discussed. Limestones and clayey limestones (Corg 0.92 ± 0.11%) are characterized by very low δ13C values (–9.6 ± 0.3‰). Parental sediments of these rocks were deposited in the shallow-water zone during slow downwarping episodes of the seafloor. Lithification of the sediments took place in oxidative conditions of the diagenesis zone. Organic matter was actively oxidized by free oxygen. Carbon dioxide with isotopically light organic carbon formed in this process was used during the crystallization of diagenetic carbonates that are visually indiscernible from the sedimentational variety. Marls, clayey marls, and carbonate-bearing clays (Corg 6.02 ± 0.80%) are characterized by δ13C values as high as –3.5 ± 0.6‰. In combustible shales (Corg >10%), δ13C value is ‒1.2 ± 0.6‰). The clayey rocks mark the episodes of sedimentation in relatively deep-water conditions that appear during the uncompensated sagging of the basin floor. The diagenetic zone with free oxygen was significantly decreased or absent at all. Here, oxygen of marine sulfates was the main or single oxidizer of organic matter (sulfate reduction). The sulfate oxygen is a weaker oxidizing agent than free oxygen. Therefore, much more organic matter was retained and fossilized in clayey rocks than in carbonate rocks. Organic carbon released during the sulfate reduction and mobilized later for the diagenetic carbonate formation was insufficient for the significant decrease of δ13C values relative to the marine carbonate standard. Isotopic composition of carbonate oxygen in the studied rocks is invariable and does not depend on the content of clay and organic matter. In these rocks, δ18O values are at the level (approximately –5‰) shown for the Famennian in the Global Chemostratigraphic Chart. This fact is consistent with the supposition that oxygen isotope composition of atmospheric precipitates, which influenced the rock formation via continental flow, is close to that of sea water in low latitudes where the territory of Belarus was located in the Late Devonian.     

<Superscript>210</Superscript>Pb-derived Sedimentation Rates and C<Subscript>org</Subscript> Fluxes in Soledad Lagoon (Cispatá Lagoon System,NW Caribbean Coast of Colombia)

With the aim of evaluating temporal changes in sedimentation and organic carbon (C_org) supplied over the last ~100 years, a sediment core was collected at Soledad Lagoon, a costal ecosystem surrounded by mangroves, located in the Cispatá Estuary (Caribbean coast of Colombia). The core sediments were characterized by low concentrations of calcium carbonate (0.2–2.9%), organic matter (3–8%), total nitrogen (0.11–0.38%), and total phosphorus (0.19–0.65 mg g⁻¹). Fe and Al concentrations ranged from 4% to 5%, and Mn from 356 to 1,047 μg g⁻¹. The ²¹⁰Pb-derived sediment and mass accumulation rates were 1.54 ± 0.18 mm year⁻¹ and 0.08 ± 0.01 g cm⁻² year⁻¹, respectively. The sediment core did not provide evidence of human impact, such as enhancement of primary production or nutrient enrichment, which may result from recent land uses changes or climate change. The C_org fluxes estimated for Soledad Lagoon core lay in the higher side of carbon fluxes to coastal ecosystems (314–409 g m⁻² year⁻¹) and the relatively high C_org preservation observed (~45%) indicate that these lagoon sediments has been a net and efficient sink of C_org during the last century, which corroborate the importance of mangrove areas as important sites for carbon burial and therefore, long-term sequestration of C_org.