Trace/minor element:calcium ratios in cultured benthic foraminifera. Part II: Ontogenetic variation

Ontogenetic (developmental stage) measurements of Mg/Ca and Sr/Ca were made on the benthic foraminifer Bulimina aculeata, which were cultured under controlled physicochemical conditions of temperature, pH, alkalinity, salinity, and trace- and minor-element concentrations. We utilized two methods of ontogenetic sampling—whole specimens progressively increasing in length and laser microdissection of a single specimen with subsequent analysis of dissected portions. A novel high-resolution laser-microdissection (HRLM) method allowed for precise (10 μm) cuts of the foraminiferal tests (shells) along the geometrically complex sutures distinguishing individual chambers. This new microdissection method limited sample loss and cross-contamination between foraminiferal chambers. Little or no variation in D_Sr was observed at different foraminiferal developmental stages. Conversely, D_Mg was enriched during a mid-developmental stage of whole-specimen samples (150-225 μm D_Mg = 1.6 × 10⁻³) compared to earlier and later stages (<150 μm, >225 μm D_Mg = 8.3 × 10⁻⁴). Further analysis of HRLM ontogenetic samples showed a larger, age-dependent D_Mg signature variation. This increase in shell Mg/Ca may contribute substantially to the measured inter-individual variability in Mg/Ca temperature prediction for cultured B. aculeata. Due to relatively large Mg/Ca inter- and intra-individual variability, measuring similar-size foraminiferal samples may improve the precision of paleotemperature prediction. Additionally, partial dissolution of the highest ontogenetically Mg-enriched calcite (D_Mg = 1.3 × 10⁻²-1.6 × 10⁻²) may occur in undersaturated bottom-water environments or during reductive cleaning procedures. Thus, the calcite phases remaining after partial dissolution by either natural or laboratory cleaning processes may not accurately represent the calcification environment.     

Controls on calcium isotope fractionation in cultured planktic foraminifera, Globigerinoides ruber and Globigerinella siphonifera

Specimens of two species of planktic foraminifera, Globigerinoides ruber and Globigerinella siphonifera, were grown under controlled laboratory conditions at a range of temperatures (18-31 °C), salinities (32-44 psu) and pH levels (7.9-8.4). The shells were examined for their calcium isotope compositions (δ^44/40Ca) and strontium to calcium ratios (Sr/Ca) using Thermal Ionization Mass Spectrometry and Inductively Coupled Plasma Mass Spectrometry. Although the total variation in δ^44/40Ca (∼0.3‰) in the studied species is on the same order as the external reproducibility, the data set reveals some apparent trends that are controlled by more than one environmental parameter. There is a well-defined inverse linear relationship between δ^44/40Ca and Sr/Ca in all experiments, suggesting similar controls on these proxies in foraminiferal calcite independent of species. Analogous to recent results from inorganically precipitated calcite, we suggest that Ca isotope fractionation and Sr partitioning in planktic foraminifera are mainly controlled by precipitation kinetics. This postulation provides us with a unique tool to calculate precipitation rates and draws support from the observation that Sr/Ca ratios are positively correlated with average growth rates. At 25 °C water temperature, precipitation rates in G. siphonifera and G. ruber are calculated to be on the order of 2000 and 3000 μmol/m²/h, respectively. The lower δ^44/40Ca observed at ?29 °C in both species is consistent with increased precipitation rates at high water temperatures. Salinity response of δ^44/40Ca (and Sr/Ca) in G. siphonifera implies that this species has the highest precipitation rates at the salinity of its natural habitat, whereas increasing salinities appear to trigger higher precipitation rates in G. ruber. Isotope effects that cannot be explained by precipitation rate in planktic foraminifera can be explained by a biological control, related to a vacuolar pathway for supply of ions during biomineralization and a pH regulation mechanism in these vacuoles. In case of an additional pathway via cross-membrane transport, supplying light Ca for calcification, the δ^44/40Ca of the reservoir is constrained as −0.2‰ relative to seawater. Using a Rayleigh distillation model, we calculate that calcification occurs in a semi-open system, where less than half of the Ca supplied by vacuolization is utilized for calcite precipitation. Our findings are relevant for interpreting paleo-proxy data on δ^44/40Ca and Sr/Ca in foraminifera as well as understanding their biomineralization processes.     

Trace element partitioning and substitution mechanisms in calcium perovskites

We have determined the partition coefficients of a large number of trace elements between CaTiO₃ perovskite and anhydrous silicate melts at atmospheric pressure and 3 GPa. Determination of the concentration limits of Henrys law behaviour in the CaO-Al₂O₃–SiO₂–TiO₂ system reveals that the incorporation of rare earth elements (REE) and tetravalent large ion lithophile elements (LILE⁴⁺ such as U and Th) at the Ca-site of CaTiO₃ perovskite occurs with charge compensation through Ca-vacancy formation rather than by coupled substitution of Al for Ti. When melt composition is varied, we find that partition coefficients for REE and Th are strong functions of the CaO content of the melt. The observed trends are in excellent agreement with those predicted from the Ca-vacancy model. Given that they adopt the same crystal structure and have similar trace element partitioning behaviour, CaTiO₃ perovskite and the deep mantle phase CaSiO₃ perovskite can be considered analogous to one another. When the analogy is pursued in detail, we find that partitioning into both phases follows the composition-dependence predicted by the Ca-vacancy model. Thus, substitution of REE, U⁴⁺ and Th into CaSiO₃ in the lower mantle also occurs with Ca-vacancy formation to balance charge. Furthermore when 2+, 3+ and 4+ partition coefficients for both phases are plotted as functions of CaO melt content, the trends for CaSiO₃ and CaTiO₃ appear to be continuous. This surprising result means that partitioning into Ca-perovskite is independent of pressure and temperature and also of whether or not the host is CaSiO₃ or CaTiO₃. One implication is that CaSiO₃ crystallising from a peridotitic magma ocean may have partition coefficients for Th and U up to about 400. Crystallisation and sequestration of as little as 0.25 volume% of this phase in the lower mantle early in earth history would make a significant contribution to current mantle heat production.Electronic Supplementary Material Supplementary material is available for this article at     

Intra-shell oxygen isotope ratios in the benthic foraminifera genus Amphistegina and the influence of seawater carbonate chemistry and temperature on this ratio

Using secondary ion mass spectrometry (SIMS) we looked at the natural variability in the oxygen isotope ratio of the shallow water, symbionts-bearing foraminiferan Amphistegina lobifera. Live foraminifera were collected in February 2005 in the Gulf of Eilat, Israel. Vertical section exposing the knob area of this species represents the growth history of this species from August 2004 to February 2005. SIMS profile at a resolution of ∼15 μm (representing about 2 weeks considering the size of the knob area and the life span of ≈6 months of this foraminifera species) yielded δ¹⁸O changes of ∼1.5‰ that are compatible with the known temperature changes for the Gulf of Eilat for this period (21-27 °C). Natural variability between primary and secondary calcite at the knob area were obtained on horizontal section of the upper knob area. This section is semi-tangential to the growth lines and exposes relatively wide belts of the primary calcite which could be analysed using the SIMS (beam size of 10 × 20 μm). The primary calcite δ¹⁸O value is on average more than 3‰ lower than the secondary calcite that represents the bulk of the skeleton (more than 95% by weight). A vertical profile at the knob was obtained by rastering an area of 50 × 50 μm at vertical steps of roughly 1 μm. The profile revealed a narrow zone of lower δ¹⁸O compared to the higher values above and below it. The difference between the lowest δ¹⁸O and the highest one was also close to 2‰. The δ¹⁸O in the margin - keel area of A. lobifera is also lower compared to the bulk secondary calcite. Specimens that were cultured in the laboratory at a constant temperature and inorganic carbon but at different pH have increased their CaCO₃ weight by roughly a factor of 8. Single specimen from each pH (ranging between 7.90 and 8.45) were investigated with the SIMS at the knob area. While there is some variability within each specimen (perhaps related to the primary calcite), the general trend was a decrease in δ¹⁸O with increasing pH (or CO₃²⁻ concentration), in agreement with previous studies on planktonic foraminifera. Some other specimens grown at different temperatures (between 21 and 33 °C) were also measured with the SIMS at the knob area. For each temperature, we observed also some variability, nevertheless the trend of −0.2‰/°C in δ¹⁸O is observed.     

Sub‐arctic Holocene climatic and oceanographic variability in Stjernsund,northern Norway: evidence from benthic foraminifera and stable isotopes

A high‐resolution record, covering 9.3–0.2 ka BP, from the sub‐arctic Stjernsund (70°N) was studied for benthic foraminiferal faunas and stable isotopes, revealing three informally named main phases during the Holocene. The Early‐ to Mid‐Holocene (9.3–5.0 ka BP) was characterized by the strong influence of the North Atlantic Current (NAC), which prevented the reflection of the Holocene Climatic Optimum (HCO) in the bottom‐water temperature. During the Mid‐Holocene Transition (5.0–2.5 ka BP), a turnover of benthic foraminiferal faunas occurred, Atlantic Water species decreased while Arctic‐Polar species increased, and the oxygen isotope record showed larger fluctuations. Those variations correspond to a period of global climate change, to spatially more heterogeneous benthic foraminiferal faunas in the Nordic Seas region, and to regionally diverging terrestrial temperatures. The Cool Late Holocene (2.5–0.2 ka BP) was characterized by increased abundances of Arctic‐Polar species and a steady cooling trend reflected in the oxygen isotopes. In this period, our record differs considerably from those on the SW Barents Sea shelf and locations farther south. Therefore, we argue that regional atmospheric cooling triggered the late Holocene cooling trend. Several cold episodes centred at ～8.3, ～7.8, ～6.5, ～4.9, ～3.9 and ～3.3 ka BP were identified from the benthic foraminiferal faunas and the δ¹⁸O record, which correlated with marine and atmospherically driven proxy records. This suggests that short‐term cold events may result from reduced heat advection via the NAC or from colder air temperatures.     

Determination of element/Ca ratios in foraminifera and corals using cold- and hot-plasma techniques in inductively coupled plasma sector field mass spectrometry

We have developed a rapid and precise procedure for measuring multiple elements in foraminifera and corals by inductively coupled plasma sector field mass spectrometry (ICP-SF-MS) with both cold- [800 W radio frequency (RF) power] and hot- (1200 W RF power) plasma techniques. Our quality control program includes careful subsampling protocols, contamination-free workbench spaces, and refined plastic-ware cleaning process. Element/Ca ratios are calculated directly from ion beam intensities of ²⁴Mg, ²⁷Al, ⁴³Ca, ⁵⁵Mn, ⁵⁷Fe, ⁸⁶Sr, and ¹³⁸Ba, using a standard bracketing method. A routine measurement time is 3–5 min per dissolved sample. The matrix effects of nitric acid, and Ca and Sr levels, are carefully quantified and overcome. There is no significant difference between data determined by cold- and hot-plasma methods, but the techniques have different advantages. The cold-plasma technique offers a more stable plasma condition and better reproducibility for ppm-level elements. Long-term 2-sigma relative standard deviations (2-RSD) for repeat measurements of an in-house coral standard are 0.32% for Mg/Ca and 0.43% for Sr/Ca by cold-plasma ICP-SF-MS, and 0.69% for Mg/Ca and 0.51% for Sr/Ca by hot-plasma ICP-SF-MS. The higher sensitivity and enhanced measurement precision of the hot-plasma procedure yields 2-RSD precision for μmol/mol trace elements of 0.60% (Mg/Ca), 9.9% (Al/Ca), 0.68% (Mn/Ca), 2.7% (Fe/Ca), 0.50% (Sr/Ca), and 0.84% (Ba/Ca) for an in-house foraminiferal standard. Our refined ICP-SF-MS technique, which has the advantages of small sample size (2–4 μg carbonate consumed) and fast sample throughput (5–8 samples/hour), should open the way to the production of high precision and high resolution geochemical records for natural carbonate materials.     

Finite element formulation and algorithms for unsaturated soils. Part I: Theory

This paper presents a complete finite‐element treatment for unsaturated soil problems. A new formulation of general constitutive equations for unsaturated soils is first presented. In the incremental stress–strain equations, the suction or the pore water pressure is treated as a strain variable instead of a stress variable. The global governing equations are derived in terms of displacement and pore water pressure. The discretized governing equations are then solved using an adaptive time‐stepping scheme which automatically adjusts the time‐step size so that the integration error in the displacements and pore pressures lies close to a specified tolerance. The non‐linearity caused by suction‐dependent plastic yielding, suction‐dependent degree of saturation, and saturation‐dependent permeability is treated in a similar way to the elastoplasticity. An explicit stress integration scheme is used to solve the constitutive stress–strain equations at the Gauss point level. The elastoplastic stiffness matrix in the Euler solution is evaluated using the suction as well as the stresses and hardening parameters at the start of the subincrement, while the elastoplastic matrix in the modified Euler solution is evaluated using the suction at the end of the subincrement. In addition, when applying subincrementation, the same rate is applied to all strain components including the suction. Copyright © 2003 John Wiley & Sons, Ltd.     

Trace element cycling in a subterranean estuary: Part 2. Geochemistry of the pore water

Submarine groundwater discharge (SGD) is an important source of dissolved elements to the ocean, yet little is known regarding the chemical reactions that control their flux from sandy coastal aquifers. The net flux of elements from SGD to the coastal ocean is dependent on biogeochemical reactions in the groundwater-seawater mixing zone, recently termed the “subterranean estuary.” This paper is the second in a two part series on the biogeochemistry of the Waquoit Bay coastal aquifer/subterranean estuary. The first paper addressed the biogeochemistry of Fe, Mn, P, Ba, U, and Th from the perspective of the sediment composition of cores Charette et al. [Charette, M.A., Sholkovitz, E.R., Hansell, C.M., 2005. Trace element cycling in a subterranean estuary: Part 1. Geochemistry of the permeable sediments. Geochim. Cosmochim. Acta, 69, 2095-2109]. This paper uses pore water data from the subterranean estuary, along with Bay surface water data, to establish a more detailed view into the estuarine chemistry and the chemical diagenesis of Fe, Mn, U, Ba and Sr in coastal aquifers. Nine high-resolution pore water (groundwater) profiles were collected from the head of the Bay during July 2002. There were non-conservative additions of both Ba and Sr in the salinity transition zone of the subterranean estuary. However, the extent of Sr release was significantly less than that of its alkaline earth neighbor Ba. Pore water Ba concentrations approached 3000 nM compared with 25-50 nM in the surface waters of the Bay; the pore water Sr-salinity distribution suggests a 26% elevation in the amount of Sr added to the subterranean estuary. The release of dissolved Ba to the mixing zone of surface estuaries is frequently attributed to an ion-exchange process whereby seawater cations react with Ba from river suspended clay mineral particles at low to intermediate salinity. Results presented here suggest that reductive dissolution of Mn oxides, in conjunction with changes in salinity, may also be an important process in maintaining high concentrations of Ba in the pore water of subterranean estuaries. In contrast, pore water U was significantly depleted in the subterranean estuary, a result of SGD-driven circulation of seawater through reducing permeable sediments. This finding is supported by surface water concentrations of U in the Bay, which were significantly depleted in U compared with adjacent coastal waters. Using a global estimate of SGD, we calculate U removal in subterranean estuaries at 20 × 10⁶ mol U y⁻¹, which is the same order of magnitude as the other major U sinks for the ocean. Our results suggest a need to revisit and reevaluate the oceanic budgets for elements that are likely influenced by SGD-associated processes.     

Trace element cycling in a subterranean estuary: Part 1. Geochemistry of the permeable sediments

Subterranean estuaries are characterized by the mixing of terrestrially derived groundwater and seawater in a coastal aquifer. Subterranean estuaries, like their river water-seawater counterparts on the surface of the earth, represent a major, but less visible, hydrological and geochemical interface between the continents and the ocean. This article is the first in a two-part series on the biogeochemistry of the subterranean estuary at the head of Waquoit Bay (Cape Cod, MA, USA). The pore-water distributions of salinity, Fe and Mn establish the salt and redox framework of this subterranean estuary. The biogeochemistry of Fe, Mn, P, Ba, U and Th will be addressed from the perspective of the sediment composition. A second article will focus on the groundwater and pore-water chemistries of Fe, Mn, U and Ba.Three sediment cores were collected from the head of Waquoit Bay where the coastal aquifer consists of permeable sandy sediment. A selective dissolution method was used to measure the concentrations of P, Ba, U and Th that are associated with “amorphous (hydr)oxides of iron and manganese” and “crystalline Fe and Mn (hydr)oxides.” The deeper sections of the cores are characterized by large amounts of iron (hydr)oxides that are precipitated onto organic C-poor quartz sand from high-salinity pore waters rich in dissolved ferrous iron. Unlike Fe (hydr)oxides, which increase with depth, the Mn (hydr)oxides display midcore maxima. This type of vertical stratification is consistent with redox-controlled diagenesis in which Mn (hydr)oxides are formed at shallower depths than iron (hydr)oxides. P and Th are enriched in the deep sections of the cores, consistent with their well-documented affinity for Fe (hydr)oxides. In contrast, the downcore distribution of Ba, especially in core 3, more closely tracks the concentration of Mn (hydr)oxides. Even though Mn (hydr)oxides are 200-300 times less abundant than Fe (hydr)oxides in the cores, Mn (hydr)oxides are known to have an affinity for Ba which is many orders of magnitude greater than iron (hydr)oxides. Hence, the downcore distribution of Ba in Fe (hydr)oxide rich sediments is most probably controlled by the presence of Mn (hydr)oxides. U is enriched in the upper zones of the cores, consistent with the formation of highly reducing near-surface sediments in the intertidal zone at the head of the Bay. Hence, the recirculation of seawater through this type of subterranean estuary, coupled with the abiotic and/or biotic reduction of soluble U(VI) to insoluble U(IV), leads to the sediments acting as a oceanic net sink of U. These results highlight the importance of permeable sediments as hosts to a wide range of biogeochemical reactions, which may be impacting geochemical budgets on scales ranging from coastal aquifers to the continental shelf.     

Recent benthic foraminifera in the southern Kattegat, Scandinavia: distributional pattern and controlling parameters

The southern Kattegat is characterized by a strong halocline at a water depth of 10–20 m. Samples were collected within and below the halocline at 12–58 m. A Q-mode factor analysis identified three major and three minor foraminiferal assemblages, each characterized by one diagnostic species. Linear regression analyses showed that the distribution of assemblages and their diagnostic species is associated with substrate and hydrography. The Bulimina marginata assemblage is connected with fine-grained, organic-rich sediments below the halocline. The Elphidium excavalum and the Eggerelloides scabrus assemblages show weak correlations with substrate and are presumably connected with the halocline. Minor assemblages of Cibicides lobatulus and Textularia bocki are associated with coarse-grained sediments. The Stainforthia fusiformis assemblage has only weak correlation with substrate and hydrography.     

Trace and minor elements in sphalerite: A LA-ICPMS study

Sphalerite is an important host mineral for a wide range of minor and trace elements. We have used laser-ablation inductively coupled mass spectroscopy (LA-ICPMS) techniques to investigate the distribution of Ag, As, Bi, Cd, Co, Cu, Fe, Ga, Ge, In, Mn, Mo, Ni, Pb, Sb, Se, Sn and Tl in samples from 26 ore deposits, including specimens with wt.% levels of Mn, Cd, In, Sn and Hg. This technique provides accurate trace element data, confirming that Cd, Co, Ga, Ge, In, Mn, Sn, As and Tl are present in solid solution. The concentrations of most elements vary over several orders of magnitude between deposits and in some cases between single samples from a given deposit. Sphalerite is characterized by a specific range of Cd (typically 0.2-1.0 wt.%) in each deposit. Higher Cd concentrations are rare; spot analyses on samples from skarn at Baisoara (Romania) show up to 13.2 wt.% (Cd²⁺ ↔ Zn²⁺ substitution). The LA-ICPMS technique also allows for identification of other elements, notably Pb, Sb and Bi, mostly as micro-inclusions of minerals carrying those elements, and not as solid solution. Silver may occur both as solid solution and as micro-inclusions. Sphalerite can also incorporate minor amounts of As and Se, and possibly Au (e.g., Magura epithermal Au, Romania). Manganese enrichment (up to ∼4 wt.%) does not appear to enhance incorporation of other elements. Sphalerite from Toyoha (Japan) features superimposed zoning. Indium-sphalerite (up to 6.7 wt.% In) coexists with Sn-sphalerite (up to 2.3 wt.%). Indium concentration correlates with Cu, corroborating coupled (Cu⁺In³⁺) ↔ 2Zn²⁺ substitution. Tin, however, correlates with Ag, suggesting (2Ag⁺Sn⁴⁺) ↔ 3Zn²⁺ coupled substitution. Germanium-bearing sphalerite from Tres Marias (Mexico) contains several hundred ppm Ge, correlating with Fe. We see no evidence of coupled substitution for incorporation of Ge. Accordingly, we postulate that Ge may be present as Ge²⁺ rather than Ge⁴⁺. Trace element concentrations in different deposit types vary because fractionation of a given element into sphalerite is influenced by crystallization temperature, metal source and the amount of sphalerite in the ore. Epithermal and some skarn deposits have higher concentrations of most elements in solid solution. The presence of discrete minerals containing In, Ga, Ge, etc. also contribute to the observed variance in measured concentrations within sphalerite.     

激光剥蚀电感耦合等离子体质谱-电子探针分析白山堂铜矿中的黄铁矿成分

硫化物矿物中元素含量及其分布可示踪硫化物成矿过程、辨别金属来源和沉积过程的物理化学条件,在地质学、矿床学等领域具有重要的应用价值。激光剥蚀电感耦合等离子体质谱（LA-ICP-MS）已成功应用于硫化物矿物元素微区分析研究,但激光与物质作用产生的热效应严重制约分析结果的可靠性。本文建立了一种高精密度、高准确度的低温剥蚀LA-ICP-MS测定硫化物矿物多元素方法。采用自行研制的Peltier低温剥蚀池可有效抑制硫化物矿物LA-ICP-MS分析中的热效应,提高分析结果的精密度和准确度。扫描电子显微镜（SEM）表明：在低温（−30℃）条件下可在一定程度地抑制激光剥蚀引起的热效应,减少样品熔化和气溶胶气相再沉积;而通过气溶胶颗粒分析发现低温剥蚀可以减小样品气溶胶颗粒的平均尺寸,得到的颗粒粒径分布范围也较小。不同元素信号强度的精密度（RSD）从常温下的20.1%～34.4%改善到11.5%～15.8%,元素的检出限为0.054～0.077μg/g。将该低温LA-ICP-MS系统应用于实验室内部标样黄铜矿Ccp-1分析,测定值与参考值之间的标准偏差在7%以内。

     

Model for kinetic effects on calcium isotope fractionation (δCa) in inorganic aragonite and cultured planktonic foraminifera

The calcium isotope ratios (δ⁴⁴Ca = [(⁴⁴Ca/⁴⁰Ca)_sample/(⁴⁴Ca/⁴⁰Ca)_standard −1] · 1000) of Orbulina universa and of inorganically precipitated aragonite are positively correlated to temperature. The slopes of 0.019 and 0.015‰ °C⁻¹, respectively, are a factor of 13 and 16 times smaller than the previously determined fractionation from a second foraminifera, Globigerinoides sacculifer, having a slope of about 0.24‰ °C⁻¹. The observation that δ⁴⁴Ca is positively correlated to temperature is opposite in sign to the oxygen isotopic fractionation (δ¹⁸O) in calcium carbonate (CaCO₃). These observations are explained by a model which considers that Ca²⁺-ions forming ionic bonds are affected by kinetic fractionation only, whereas covalently bound atoms like oxygen are affected by kinetic and equilibrium fractionation. From thermodynamic consideration of kinetic isotope fractionation, it can be shown that the slope of the enrichment factor α(T) is mass-dependent. However, for O. universa and the inorganic precipitates, the calculated mass of about 520 ± 60 and 640 ± 70 amu (atomic mass units) is not compatible with the expected ion mass for ⁴⁰Ca and ⁴⁴Ca. To reconcile this discrepancy, we propose that Ca diffusion and δ⁴⁴Ca isotope fractionation at liquid/solid transitions involves Ca²⁺-aquocomplexes (Ca[H₂O]_n²⁺ · mH₂O) rather than pure Ca²⁺-ion diffusion. From our measurements we calculate that such a hypothesized Ca²⁺-aquocomplex correlates to a hydration number of up to 25 water molecules (490 amu). For O. universa we propose that their biologically mediated Ca isotope fractionation resembles fractionation during inorganic precipitation of CaCO₃ in seawater. To explain the different Ca isotope fractionation in O. universa and in G. sacculifer, we suggest that the latter species actively dehydrates the Ca²⁺-aquocomplex before calcification takes place. The very different temperature response of Ca isotopes in the two species suggests that the use of δ⁴⁴Ca as a temperature proxy will require careful study of species effects.     

The development of acidic groundwaters in coal-bearing strata: Part I. Rare earth element fingerprinting

This study examines the rare earth element (REE) pattern of acidic mine discharges in the Durham basin (NE England) as a means of fingerprinting their sources and understanding the water-rock interactions Although whole rock compositions proved to be unhelpful, mimicking acid mine water generation in a series of selective leachates of the coal and coal-bearing strata gave REE patterns similar to those measured in the emergent waters. REE ratios and anomalies were used as indicators of specific interactions in the development of acidic groundwater. The implications of the findings for the classification and evolution of acid mine discharges are discussed.     

东海陆架浙闽沿岸泥质区不同属种底栖有孔虫对14C测年的影响及其原因初探

底栖有孔虫是浅海陆架区钻孔岩芯¹⁴C测年的良好材料,但由于其个体细小,为了获得足够的样品量,常常采用不区分属种和大小的混合壳体样品,不利于高分辨率的古环境研究。本研究选择东海陆架浙闽沿岸泥质区的两个钻孔沉积物样品,对其中不同的底栖有孔虫属种壳体化石分别进行¹⁴C测年,结果显示同一沉积物样品中不同的底栖有孔虫属种壳体化石¹⁴C年龄值存在差异,以Quinqueloculina spp.壳体¹⁴C年龄最老,其次是Ammonia comperessiuscula壳体,最年轻的分别为Elphidium spp.壳体和Bolivina cochei壳体。从底栖有孔虫的生态习性和壳体的结构特征等方面分析推测,同层位不同底栖有孔虫属种壳体年龄差异,不能简单地用它们生活时壳体和所处的微生境水体同位素交换来解释;不同属种有孔虫壳壁构造不同可能是产生壳体化石¹⁴C年龄差异的原因。建议为地质钻孔建立高分辨率年代地层挑取底栖有孔虫AMS ¹⁴C测年样品时,尽量选择相同的属种,或微生境相同、个体大小相近、壳壁厚度和壁孔大小密度近一致的类别,以降低属种不同对测年结果产生的影响,为海岸带高分辨率的古环境研究提供高精度的测年数据。

     

The impact of salinity on the Mg/Ca and Sr/Ca ratio in the benthic foraminifera Ammonia tepida: Results from culture experiments

Over the last decade, sea surface temperature (SST) reconstructed from the Mg/Ca ratio of foraminiferal calcite has increasingly been used, in combination with the δ¹⁸O signal measured on the same material, to calculate the δ¹⁸O_w, a proxy for sea surface salinity (SSS). A number of studies, however, have shown that the Mg/Ca ratio is also sensitive to other parameters, such as pH or , and salinity. To increase the reliability of foraminiferal Mg/Ca ratios as temperature proxies, these effects should be quantified in isolation. Individuals of the benthic foraminifera Ammonia tepida were cultured at three different salinities (20, 33 and 40 psu) and two temperatures (10-15 °C). The Mg/Ca and Sr/Ca ratios of newly formed calcite were analyzed by Laser Ablation ICP-MS and demonstrate that the Mg concentration in A. tepida is overall relatively low (mean value per experimental condition between 0.5 and 1.3 mmol/mol) when compared to other foraminiferal species, Sr being similar to other foraminiferal species. The Mg and Sr incorporation are both enhanced with increasing temperatures. However, the temperature dependency for Sr disappears when the distribution factor D_Sr is plotted as a function of calcite saturation state (Ω). This suggests that a kinetic process related to Ω is responsible for the observed dependency of Sr incorporation on sea water temperature. The inferred relative increase in D_Mg per unit salinity is 2.8% at 10 °C and 3.3% at 15 °C, for the salinity interval 20-40 psu. This implies that a salinity increase of 2 psu results in enhanced Mg incorporation equivalent to 1 °C temperature increase. The D_Sr increase per unit salinity is 0.8% at 10 °C and 1.3% at 15 °C, for the salinity interval 20-40 psu.     

Trace element and Pb isotope variability during rainy events in the NW Mediterranean: constraints on anthropogenic and natural sources

Rain samples collected over the period 1995–1999 on the French Mediterranean coast have been analyzed for their trace elements and Pb isotopic compositions, both in the dissolved and particulate loads. Our results show that metal Enrichment Factors (EF) relative to Upper Erodable Crust are high for Cu, Pb, Zn and Cd and comparable to values reported about 10 years ago for North Western Mediterranean rains. Overall unradiogenic Pb isotopic compositions indicate the still visible influence of French gasoline lead on both dissolved and particulate loads. This influence is also seen on aerosols, although more variable. The examination of air mass trajectories allows us to distinguih the Pb isotopic signatures of main sources, in particular Marseille/North Italy/North Africa. Rains collected and analyzed sequentially show intra-rain variations for metal contents, metal EF and Pb isotopes, which may also be related to the main paths and altitudes of the air masses. Metal EFs and Pb isotopic data on rains from Southern France in the late 1990s are similar to recent data published on French aerosols or sediments, which are interpreted as reflecting the phasing out of leaded gasoline in the atmosphere.     

Numerical modelling of transient contaminant migration problems in infinite porous fractured media using finite/infinite element technique. Part I: Theory

The leakage effect in porous fissured media has been considered in a general sense by introducing a new expression of the leakage term in this paper. The double porosity concept is employed and the related expressions are formulated using the upwind finite element approach. Considering the infinite extension of the problem domain, a mapped transient infinite element has been presented to simulate the far field of the infinite medium. Since the mass transfer function of the present mapped transient infinite element is dependent on both space and time variables, the mechanism of transient contaminant migration problems in infinite porous fractured media can be rigorously simulated because the property matrices of the element are evaluated at any time of interest. By comparing the current numerical results with the analytical ones, the accuracy, correctness and effectiveness of the present method have been established. Three different time discretization schemes were examined and it was found that either the central difference or the backward difference approximation is suitable for the upwind finite element simulation of transient contaminant migration problems.     

Amino acid ratios in Quaternary molluscs and foraminifera from western Norway: correlation, geochronology and paleotemperature estimates

Isoleucine epimerization (alle/Ue) ratios in the pelecypod Mya truncata and benthic foraminifer Cibicides lobalulus from emerged marine units in western Norway allow construction of a regional relative chronostratigraphy for the Ecmian and Weichselian. Two in situ interglacial sections are considered correlative by the similar biostratigraphy and alle/Ile ratios in C. lobalulus. Overlying sediments at the two sites are of both marine and glacial origin. Neither site contains a complete Weichselian record, but allelic ratios, lithostratigraphy and fauna! changes suggest at least four stadial and three interstadial events occurred along the western Norwegian coast during Early and Middle Weichselian time. Kinetic data defining the relationship between the isoleucine epimerization rate constant and temperature for the species studied allow the estimation of paleotemperatures for samples of known age. Accepting published age estimates for the Eemian interglacial beds, the average Weichselian temperature in western Norway is calculated to have been ca. 4°C below the average Holocene temperature, whereas the last interglacial was 1 to 2°C warmer that the Holocene. The limited temperature depression over this region during the Weichselian implies that coastal western Norway was ice-covered only about 30% of this period, and that Atlantic water, although not necessarily in a warm surface current as today, entered the Norwegian Sea during much of marine isotope stage 5 and intermittently during stage 3. Interpolated amino acid ages date interstadial events at ca. 94 ka, 78 ka and 52 ka, B.P., whereas glacial events are dated ca. 103 ka and bracketed by limiting dates between 78 and 89 ka, between 52 and 63 ka and less than 36 ka B.P.     

Li/Ca in multiple species of benthic and planktonic foraminifera: thermocline, latitudinal, and glacial-interglacial variation

Li/Ca ratios were measured in planktonic and benthic foraminifera from a variety of hydrographic settings to investigate the factors influencing lithium incorporation into foraminiferal tests including temperature, dissolution, pressure, and interspecies differences. Down-core measurements of planktonic (Orbulina universa, Globigerinoides ruber, and Globigerinoides sacculifer) and benthic foraminifera (calcitic Cibicides wuellerstorfi and aragonitic Hoeglandina elegans) show a systematic variation in Li/Ca with δ¹⁸O through the last glacial-interglacial transition. All species examined exhibit an increase in Li/Ca between 14 to 50% from the Holocene to the last glacial maximum. Li/Ca generally increases with decreasing temperature as seen in a latitudinal transect of planktonic O. universa and down-slope benthic species along the Bahama Bank margins. Postdepositional dissolution possibly causes a decrease in planktonic foraminiferal Li/Ca along the Sierra Leone Rise, and increased water depth causes a decrease in benthic foraminiferal Li/Ca in the deep Caribbean. However, none of these effects are sufficient to account for the observed glacial-interglacial changes. Physiological factors such as calcification rate may affect the Li/Ca content of foraminiferal calcite. The calcification rate in turn may be a function of carbonate ion concentration of ambient ocean water. This work shows that incorporation of lithium by foraminifera appears to be influenced by factors other than seawater composition and does not appear to be dominated by changes in temperature, dissolution, or pressure. We hypothesize that the consistent increase in foraminiferal Li/Ca during the last glacial maximum may be linked to changes in seawater carbonate ion concentration. Important parameters to be tested include calcification rate and foraminiferal test size and weight. If foraminiferal Li/Ca is dominantly controlled by calcification rate as a function of seawater carbonate ion concentration, then Li/Ca may act as a proxy of past atmospheric CO₂.