Phosphorus in foraminiferal sediments from North Atlantic Ridge cores and in pure limestones

Samples of foraminiferal ooze from two North Atlantic cores were cleaned and progressively dissolved. Most of the P, Fe, and Mn was released during the first of two reductive cleaning steps. Most of the remainder of these elements and most of the Ca were released during the final acid dissolution step. The P in these samples is present largely in Fe- and Mn-rich coatings, not as a constituent of the foraminiferal shells themselves. Our results are consistent with those of earlier studies.The concentration of P in carbonate oozes in which it is clearly associated with coatings is similar to that of modern calcareous sediments in general, and with that of reasonably pure limestones of all ages. Phosphorus is apparently associated with (Fe, Mn)-oxide coatings in many carbonate sediments. The rate of removal of P from the oceans as a constituent of such sediments depends on the rate of formation of (Fe, Mn) coatings, not on the rate of incorporation of P into calcium carbonate.     

Sr,Cd, Mn and Co distribution coefficients in calcite as a function of calcite precipitation rate

Distribution coefficients, as a function of precipitation rate, were determined for the metals Sr²⁺, Co²⁺, Mn²⁺ and Cd²⁺in calcite. A pH-stat was used to maintain a constant degree of-saturation, and hence precipitation rate, during each coprecipitation run. The precipitation rate was proportional to the degree of supersaturation and the mass of seed crystal introduced. Distribution coefficients (λ) as a function of rate were determined using radioactive isotopes for solutions with saturations $\text{Ω = 1}$ to $\text{Ω = 5.5}$. Strontium distribution coefficients increased with increasing precipitation rate, while Co, Mn and Cd distribution coefficients decreased with increasing precipitation rate. The following rate expressions (at 25°C) were derived: logλ_Sr = 0.249 log R ?1.57logλ_Mn = ?0.266 log R + 1.35logλ_Co = ?0.173 log R + 0.68logλ_Cd = ?0.194 log R + 1.46 where R is the observed precipitation rate in nmoles CaCO₃ per mg seed crystal per min.In separate experiments the uptake of radioactive isotopes was monitored during the recrystallization of calcite seed crystals. Rates of recrystallization were from 100 to 10, 000 times slower than the pH-stat experiments, but yielded distribution coefficients consistent with the above rate expressions.Using gross estimates of biogenic crystal growth rates, aragonite to calcite transformation rates, and the above Sr rate expression, biogenic calcite and diagenetic calcite Sr contents are estimated. These experiments indicate that in addition to solution composition, precipitation rate is a significant factor influencing the trace metal content of naturally occurring calcite.     

Climate proxies from Sr/Ca of coccolith calcite: calibrations from continuous culture of Emiliania huxleyi

Continuous culture of the coccolithophorid Emiliania huxleyi reveals that coccolith Sr/Ca ratios depend on temperature and growth rate. At a constant temperature of 18°C, coccolith Sr/Ca ratios increased nearly 15% as growth rate increased from 0.1 to 1.5 divisions per day and calcification rate increased from 1.5 to 50 pg calcite per cell per day. When temperature increased from 7 to 26°C, Sr/Ca ratios increased by more than 25% (i.e., 1%/1°C), although the range in growth and calcification rates was the same as for experiments at constant temperature. The temperature dependence of Sr/Ca ratios in coccoliths is consistent with that observed in planktonic foraminifera and abiogenic calcites, suggesting that it is controlled by thermodynamic processes. However, the positive correlation of coccolith Sr/Ca with temperature contrasts with field studies in the equatorial Pacific, where Sr/Ca ratios are highest at the locus of maximum upwelling and productivity despite depressed temperatures. This paradox may reflect different calcification rate effects between E. huxleyi and the other species dominating assemblages in the equatorial Pacific sediments, which may be resolved by new techniques for separation of monospecific coccolith samples from sediments. Models of crystal growth indicate that kinetic effects on Sr partitioning in calcite due to surface enrichment could explain the Sr/Ca variations observed in constant temperature experiments but not the larger amplitude calcification rate effects observed in equatorial Pacific sediments. Despite the dual influence of temperature and growth rate on coccolith Sr/Ca, coccolith Sr/Ca correlates with “b,” the slope of the dependence of carbon isotope fractionation in biomarkers (ε_p) on CO₂(aq) at a range of growth rates and temperatures. Consequently, using coccolith Sr/Ca in combination with alkenone ε_p may improve paleo-CO₂ determinations.     

A 1000-year record of Mg/Li and Li/Ca ratios of ostracod shells in Lake Qinghai,NE Tibetan Plateau

正1 Introduction Lake Qinghai,famous as the largest inland saline lake in China,located on the high-altitude northeastern Tibetan Plateau,and four junctional zones of the East Asian summer monsoon(EASM),Indian summer monsoon(ISM),East Asian winter monsoon and the westerly jet stream prevail,making it sensitive to global climate change     

Mg/Ca, Sr/Ca, and stable isotopes in modern and Holocene Protothaca staminea shells from a northern California coastal upwelling region

This study explores the potential of intertidal Protothaca staminea shells as high-resolution geochemical archives of environmental change in a coastal upwelling region. Mg/Ca and Sr/Ca ratios were analyzed by excimer laser ablation-inductively coupled plasma mass spectrometry (LA-ICP-MS) at sub-weekly temporal resolution in shells growing ∼1 mm per month. Growth patterns of a modern P. staminea shell from Humboldt Bay, California, collected in December 1999 made it possible to infer a lifespan from 1993 to 1998. Growth hiatuses in the shell may have excluded records of extreme events. Mg/Ca ratios appeared to be partly controlled by water temperature; the correlation coefficient between temperature and Mg/Ca was r = 0.71 in one of four growth increments. Significant year-to-year differences in the sensitivity of Mg/Ca to temperature in P. staminea could not be explained, however. Sr/Ca ratios appeared to be more closely related to shell growth rate. Oxygen isotopes, measured at 2-week temporal resolution in the same shell, did not show a clear relation to local temperature in summer, possibly because temperatures were higher and less variable at the King Salmon mudflat, where the shell was collected, than in the main channel of Humboldt Bay, where water properties were monitored. Negative shell δ¹³C values (<−0.5‰) marked spring and summer coastal upwelling events.The Mg contents of P. staminea midden shells dated to ∼3 ka and ∼9 ka were significantly lower than in the modern shell. This may have resulted from degradation of a Mg-rich shell organic matrix and precluded quantitative interpretation of the older high-resolution records. Elevated δ¹³C values in the ∼3 ka shell suggested that the individual grew in highly productive or stratified environment, such as a shallow coastal embayment or lagoon.     

Geochemistry of porewater and sulfate-reducing bacteria in sediment cores from the Chianan Plain, Taiwan

High concentrations of arsenic and humic substances in groundwater from the southwestern coastal plain of Taiwan were well known for their probable relationships with black-foot disease. In order to realize the relationships between the concentrations of humic substances and arsenic in this area, 24 well water samples were analyzed. After filtered through 0.45 μm glass fiber membrane in the field, samples were kept in the dark at 4℃ and then separated into six fractions with varying range of molecular weight （〈0.5, 0.5-1, 1-5, 5-10, 10-50 and 〉50 k Da） by ultrafiltration apparatus （Molecular/Por Stirred Cell system） in the lab. Concentrations of humic substances were measured by fluorescence spectrometer （HITACHI F-2000, ex=370, em=445） and arsenic by FIAS-AA （Perkin Elmer AAnalyst 100, FIAS-400）. On average, only 6.2% of the total arsenic in water existed in the fraction of 〉0.5 k Da. and the others were complexed with humic substances （including humic acid and fulvic acid）. The results demonstrated a distinct positive correlation between the concentrations of humic substances and arsenic.     

Ecological consideration of trace element contamination in sediment cores from Sundarban wetland,India

This article reports on the concentration of selected trace elements (Mn, Zn, Cr, Cu, Ba, As, B, V, and Hg) and major elements (Fe and Al) from the intertidal sediment cores from Sundarban wetland, India. This is a typical meso-macrotidal estuarine area affected by domestic and industrial activities located upstream. The overall concentrations range is low to moderate, indicating the environmental conditions in the outfall zone (grain size, hydrodynamic regime, and confinement), which favors the in situ accumulation of pollutants. The extent of contamination from trace elements in Sundarban core sediments is evaluated through a two-pronged approach: (i) by determining the metal enrichment in the sediments through the calculation of Pollution Load Index (PLI), Enrichment Factor (EF) and Index of Geoaccumulation (I _geo), and (ii) by defining a potential level of biological risk by the use of quality criteria such as Threshold Effect Level (TEL) and Effects Range-Low (ERL) benchmarks. On the basis of the calculated indices, sediments are particularly enriched with Cr, Cu, B, V, and As. Those enrichments seem to be due to the fine granulometry of the regions with Fe and Mn oxi-hydroxides being the main metal carriers. Trace Elements input to the Sundarban wetland need to be kept under strict control in future specially with reference to As since, according to TEL and ERL benchmarks, it already appears to be associated with a potential biological risk.     

Isotopic composition of Sr,Nd, and Pb in pirssonite,shortite and calcite carbonatites from Oldoinyo Lengai volcano,Tanzania

Doklady Earth Sciences -     

Mobility of arsenic and trace element inventories in sediment cores from Masuda City,southwestern Japan

The vertical distribution of arsenic and other trace and major elements has been studied in four sediment cores from Masuda City, Nagashima and Okite in the Shimane Prefecture of southwestern Japan. The sediment cores were also subjected to leaching techniques and ¹⁴C dating. The stratigraphic sequences in the cores consist of silt and sandy silt at top, passing downward into gray to black clays. Elevated values of As, Pb, Zn, Cu, Ni, Cr, and V are present in several horizons while abundances of these elements tend to be higher in the black and gray clays, probably due to adsorption onto clay sediments. Higher concentrations of Fe and total sulfur (TS) occur in black clays. The correlations of the trace metals with iron suggest their adsorption onto Fe (oxy)hydroxides, whereas correlations with sulfur in some cores indicate that they were precipitated as Fe-sulfides. Age determinations suggest that clay horizons at ∼5 m depth were deposited at around 5,000 and 6,000 years BP (¹⁴C ages) during the transgressive phase of sea level change. The results of the leaching techniques in the core samples show that higher amounts of As were extracted with deionized water. Even at neutral pH, As can be released from sediments to groundwater, and therefore groundwater pollution is a concern in Masuda City and the surrounding area.     

Cold seeps in Monterey Bay, California: Geochemistry of pore waters and relationship to benthic foraminiferal calcite

An extensive geochemical and biogeochemical examination of CH₄ seeps in the Clam Flats area of Monterey Bay provides insight into the character of relationships between seep geochemistry and benthic foraminiferal geochemistry. The area is characterized by sulfide-rich fluids. Sulfide increases are associated with large increases in alkalinity, as well as small decreases in dissolved Ca and Mg. In addition, only small increases in NH₄ are observed, but values of δ¹³C of dissolved inorganic C are as low as −60‰ at shallow depths (<3 cm). These observations indicate that all these processes are related to the bacterial oxidation of CH₄, which is transported upward by slow seepage of pore fluids. The geochemistry of the pore fluids should be relevant to the geochemistry of the carbonate tests of living and dead foraminifera. However, a profound disequilibrium of approximately an order of magnitude occurs between the δ¹³C values of stained (cytoplasm-containing) foraminiferal carbonate and the C isotope values of ambient pore water dissolved inorganic C. Reasons are unclear for this isotopic disequilibrium, but have important implications for interpretations of foraminiferal carbonate as a paleoenvironmental proxy. Much fine scale work is needed to fully understand the relationships between the biogeochemistry of benthic foraminifera and the geochemistry of the pore waters where they live.     

Modeling bioavailable phosphorus via other phosphorus fractions in sediment cores from Jiulongkou Lake, China

Bioavailable phosphorus (BAP) plays an important role in phosphorus (P) release from lake and river sediments, as well as serves as an indicator for the potential P-release risk in sediment. Developing a feasible model which could predict BAP via other P fractions is needed for the lakes and reservoirs without regular BAP monitoring. The algal available P (AAP), NaHCO₃ extractable P (Olsen-P), water soluble P (WSP) and readily desorption P (RDP) are four fractions of BAP. The vertical and spatial distributions of BAP fractions of three sediment cores from Jiulongkou Lake were analyzed. In addition, the P fractions, including total P (TP), organic P (OP), inorganic P (IP), non-apatite inorganic P (NAIP), and apatite P (AP) were measured to develop a model for predicting BAP. The model for each BAP fraction was developed based on datasets from Jiulongkou Lake and validated by the datasets collected from Wujin and Wugong Lake. The results showed that all of the four BAP fractions decreased with depth, along the direction of contaminant transport. Their rank order was AAP > Olsen-P > WSP > RDP in all samples. The concentration of BAP was affected by the anthropogenic input and aquatic macrophyte growth. Each of the four BAP fractions could be simulated by different P fractions: both AAP and Olsen-P were expressed by NAIP and OP, WSP had a significant relationship with OP, and RDP had significant relationship with IP. NAIP and OP were the major sources of the BAP fraction. The simulated results in two other lakes further illustrated that this model could be used to successfully predict the BAP concentrations in lakes in the study area, and holds promise for predicting the BAP levels in other lakes and reservoirs as well.     

Palynological and oxygen isotope investigations on Late-Glacial sediment cores from Swiss lakes

Results from detailed pollen and ¹⁸O/¹⁶O studies on two sediment profiles from small Swiss lakes are reported. ¹⁸O/¹⁶O records in lacustrine carbonate contain paleoclimatic information because they reflect mainly the isotope ratio in rain and snow which is correlated to temperature. Several transitions between different climatic periods determined palyno-logically are also indicated by marked changes in the isotope ratios in both profiles, namely the transitions Oldest Dryas - Bøiling and Allerød - Younger Dryas - Preboreal. ¹⁸o/¹⁶O was 2 to 3 %0 lower during Younger Dryas than during the adjacent periods, corresponding to a temperature drop of a few degrees Centigrade according to a tentative estimate.     

Origin of anhedral Sr-rich calcite in deep-water mixed sediment, north-east Australia

At burial depths of 800-1000 m, within the epicontinental Queensland Trough of north-east Australia (ODP Site 823), microcrystalline inter- and intraskeletal mosaics of anhedral (loaf-shaped, rounded) calcite have Sr²⁺ values ranging from below microprobe detection limits (<150 ppm) to 8100 ppm. Host rocks are well lithified, fine-grained mixed sediment to clayey wackestone and packstone of Middle and Late Miocene age. Petrography demonstrates that calcite precipitation has spanned shallow to deep burial, overlapping formation of framboidal pyrite in the upper 50 m; shallow-burial dolomitization (<300 m); and dedolomitization during sediment consolidation and incipient chemical compaction at greater (>400–500 m) depths. Petrographic observations illustrate that the calcite microfabric formed through coalescing crystal growth resulting from one or a combination of displacive growth in clay, porphyroid neomorphism of aragonite/vaterite, and clay replacement by calcite. Sr²⁺ mean concentrations in calcite between depths of 800 and 1000 m are similar to an expected equilibrium pore-water concentration, using a D^sr of 0.06, and may indicate active calcite precipitation. However, Sr²⁺ variation (2000–5000 ppm) within and among crystals, and concentrations that range well above predicted equilibrium values for a given depth, illustrate either variable Sr²⁺ retention during recrystallization of shelf-derived aragonite (and authigenic local vaterite) or relative uptake of Sr²⁺ during calcite precipitation with burial. Within the context of calcite formation during burial to 1 km, diagenetic attributes that affect the latter process include increased concentrations of pore-water Sr²⁺ with depth associated with aragonite recrystallization/dissolution; upward migration of Sr-rich pore water; and increased D^Sr related to local variation in precipitation/recrystallization rates, differential crystal sector growth rates and/or microvariation in aragonite distribution.     

87Sr/86Sr ratios in Permo-Carboniferous sea water from the analyses of well-preserved brachiopod shells

Sr isotopic analyses of well-preserved portions of Permo-Carboniferous brachiopods distributed globally confirm the general shape of the Sr isotope age curve established by previous workers for this time interval. There is little variation between the Sr isotopic composition of unaltered portions of brachiopods and that of portions of the same shell interpreted to be diagenetically altered (based on cathodoluminescence, elemental, and stable isotopic data). However, the Sr isotopic composition in diagenetically altered micritic matrix adjacent to the shell is more radiogenic. The Sr isotopic composition in the unaltered portions of calcitic megafossils has potential as a stratigraphie tool.     

ICP-AES法同时测定钛铁矿中钾钠钙镁钡锶锌

采用HCl—HNO3-HF—HClO4,HCl—HNO3-HF—H2SO4敞口和HCl-HNO3-HF—HClO4,HCl-HNO3-HF—H2SO4微波消解4种方法溶矿,利用电感耦合等离子体发射光谱（ICP—AES）测定,建立了钛铁矿中钾、钠、钙、镁、钡、锶、锌等元素的同时测定方法。对电感耦合等离子体发射光谱仪测定的最佳仪器条件及分析谱线进行了选择,并对钛、铁基体的影响、溶矿提取酸度以及溶矿残渣进行了研究。实验结果表明：采用HCl-HNO3-HF-HClO4敞口溶矿,具有检出限低、灵敏度高,操作简便、快速等突出优点。该方法测定值与推荐值基本吻合,分析方法的精密度满足《地质矿产实验室测试质量管理规范》的要求。     

Hydrocarbons in age-dated sediment cores from two basins in the Southern California Bight

The distributions of hydrocarbons in sediment cores dated by ²¹⁰Pb (1845–1977) from San Pedro and San Nicolas Basins in the Southern California Bight have been determined by gas Chromatographic and combined gas chromatographic-mass spectrometric analysis. The chromatograms of the hydrocarbons contain peaks of resolved alkanes and cycloalkanes, as well as an unresolved complex mixture which decrease in content with increasing depth in both of the cores. The concentrations of o,p' andp,p'-DDE are highest in the top 50 mm of the San Pedro core section. The 45–50 mm segment of this core was deposited in the 1945–1950 period when DDT (the precursor of DDE compounds) came into common use. The relatively high content of hydrocarbons and DDE in this core is attributable to the proximity of the site to the San Pedro Harbor which receives petroleum residues from shipping, sewage outfalls and industrial effluents. The presence of only traces of DDE throughout the San Nicolas core, and the low hydrocarbon content are explainable by the greater distance of this basin from anthropogenic inputs and probably a greater rate of degradation of deposited organic matter during bioturbation. δ¹³C, δ¹⁵N and electron-spin resonance analyses of kerogens and humic substances in these cores, indicate that most of this organic matter in these sediments is of a marine origin.     

Tracer diffusion of Mg, Ca, Sr, and Ba in Na-aluminosilicate melts

We employed the thin source technique to investigate tracer diffusion of Mg, Ca, Sr, and Ba in glasses and supercooled melts of albite (NaAlSi₃O₈) and jadeite (NaAlSi₂O₆) compositions. The experiments were conducted at 1 bar and at temperatures between 645 and 1025°C. Typical run durations ranged between 30 min and 35 days. The analysis of the diffusion profiles was performed with the electron microprobe. Diffusivities of Ca, Sr, and Ba were found to be independent of either duration t of the experiment or tracer concentration M, initially introduced into the sample. Mg exhibits a diffusivity depending on run time and concentration and tracer diffusivity is derived by extrapolation to M/√t = 0. Temperature dependence of the diffusivity D can be represented by an Arrhenius equation D = D_o exp(−E_a/RT), yielding the following least-squares fit parameters (with D in m²/s and E_a in kJ/mol): D_Mg = 1.8 · 10⁻⁵ exp(−234 ± 20/RT), D_Ca = 3.5 · 10⁻⁶ exp(−159 ± 6/RT), D_Sr = 3.6 · 10⁻⁶ exp(−160 ± 6/RT), and D_Ba = 6.0 · 10⁻⁶ exp(−188 ± 12/RT) for albite; and D_Mg = 8.3 · 10⁻⁶ exp(−207 ± 18/RT), D_Ca = 3.8 · 10⁻⁶ exp(−153 ± 4/RT), D_Sr = 2.3 · 10⁻⁶ exp(−150 ± 4/RT), and D_Ba = 3.7 · 10⁻⁵ exp(−198 ± 4/RT) for jadeite composition. Ca and Sr diffusivities agree within error in both compositions and exhibit the fastest diffusivities, whereas Mg reveals the lowest diffusivity. The relationship between activation energy and radius shows a minimum at Ca and Sr for albite and jadeite compositions extending the relationship already observed elsewhere for alkalies. With increasing substitution of Si by (Na + Al), diffusivities increase, whereas activation energies decrease. Furthermore, a simple model modified from that of Anderson and Stuart (Anderson O. L. and Stuart D. A., “Calculation of activation energy of ionic conductivity in silica glasses by classical methods,” J. Am. Ceram. Soc.37, 573-580, 1954) is discussed for calculating the activation energies.     

Late Quaternary climate change record from two long sediment cores from Guaymas Basin,Gulf of California

Modern Guaymas Basin (Gulf of California, Mexico) is a region of high diatom productivity where exceptional preservation factors maintain biannually alternating sediment deposition as annual varves. New sediment cores from Guaymas Basin (MD02‐2512 and MD02‐2515) present the opportunity to construct climate records from below the last glacial period. A low‐resolution age model has been constructed from oxygen isotope analysis, correlation with other dated short piston cores from Guaymas Basin and an estimate of sedimentation rate. MD02‐2512 from eastern Guaymas Basin has an age range from the Holocene to late marine isotope stage 6 (MIS 6); MD02‐2515 from western Guaymas Basin has an age range from ～8000 to 40 000 yr. Shipboard analyses of colour reflectance, magnetic susceptibility and sediment density are combined with continuous X‐ray fluorescence scans to reconstruct a picture of glacial climate in the Gulf of California. Eastern Guaymas Basin is affected by glacial sea level fall, which results in a drastic change in productivity rates and sediment type. The laminated record of MIS 5 allows comparison with the Holocene, showing a similarity of sedimentation patterns during deglaciation and a series of very rapid variations just prior to the last glaciation. In western Guaymas Basin there are a series of Younger Dryas‐like events during the glacial, typified by low productivity and high terrigenous input. Long‐term climate and productivity changes appear to be caused by the southward displacement of the Subtropical High pressure zone. Copyright © 2005 John Wiley & Sons, Ltd.