Alteration of the oceanic crust: Implications for geochemical cycles of lithium and boron

Fresh tholeiitic basalt glass has been reacted with seawater at 150°C, (water/rock mass ratio of 10), and fresh diabase has been reacted with a Na-K-Ca-Cl fluid at 375°C (water/rock mass ratios of 1, 2, and 5) to understand better the role of temperature, basalt composition, and water/rock mass ratio on the direction and magnitude of B and Li exchange during basalt alteration. At 150°C, slight but nevertheless significant amounts of B and Li were removed from seawater and incorporated into a dominantly smectite alteration phase. At 375°C, however, B and Li were leached from basalt. B behaved as a “soluble” element and attained concentrations in solution limited only by the B concentration in basalt and the water/rock mass ratio. Li, however, was less mobile. For example, at water/rock mass ratios of 1, 2, and 5, the percent of Li leached from basalt was 58, 70, and 92% respectively. This suggests some mineralogic control on Li mobility during hydrothermal alteration of basalt, especially at low-water/rock mass ratios. In general, these results, as well as those for B, are consistent with the temperature-dependent chemistry of altered seafloor basalt and the chemistry of ridge crest hydrothermal fluids.Based on the distribution and chemistry of products of seafloor weathering, low (≤ 150°C) and high-temperature hydrothermal alteration of basalt, and the chemistry of ridge crest hydrothermal fluids, it was estimated that alteration of the oceanic crust is a Li source for seawater. This is not true for B, however, since the hot spring flux estimated for B is balanced by low-temperature basalt alteration. These data, coupled with B and Li flux estimates for other processes (e.g., continental weathering, clay mineral adsorption, authigenic silicate formation and formation of siliceous skeletal material) yield new insight into the B and Li geochemical cycles. Calculations performed here indicate relatively good agreement between the magnitude of B and Li sources and sinks. The geochemical cycle of B, however, may be affected by serpentinization of mantle derived peridotite in oceanic fracture zones. Serpentinites are conspicuously enriched in B and if the B source for these rocks is seawater, then an additional B sink exists which must be integrated into the B geochemical cycle. However, until more data are available in terms of areal extent of serpentinization, serpentite chemistry and isotopic composition, the importance of B in these rocks with respect to the B geochemical cycle remains speculative at best.     

Spatial geochemical variation of major and trace elements in the marine sediments of Mumbai Harbor Bay

The resulting concentration data sets of major (Na, K, Mg, Ca and Fe) and trace elements (Cu, Ni, Co and Mn) in bed and suspended sediments were used to evaluate the enrichment factor for anthropogenic influences and principal component analysis for identifying the origin of source contributions in the studied area. Normalization of metals to Fe indicated that high enrichment factors in the bed sediment were in the order of Co > Cu > Na > Ca > Ni except Mg, K and Mn while for suspended sediments, only Co has a high enrichment factor. High enrichment of Co and Cu reflected the contamination of sediments from anthropogenic sources. The high influence of Na and Ca in sediments may be caused for seawater salinization factor. A significant positive correlation among enrichment factors of various elements of interest suggests a common origin/identical behavior during transport in the sediment system.     

The kinetic treatment of geochemical cycles

Treating geochemical cycles as complex kinetic chemical reactions, we have applied recent kinetic techniques to the classical concepts employed in geochemical cycles. Matrix algebra serves as a powerful tool to give insight into the response and stability of a linear geochemical cycle. Several important theorems are proven which are pertinent to this development. Extension of the method allows also an analysis of the more interesting non-linear coupled geochemical cycles. The approach is similar to that used by Prigogine and coworkers in the irreversible thermodynamics of complex reactions and of periodic phenomena. Important results concerning the stability of a coupled system are treated for the special case of the C-O cycle and for a general two-reservoir system.     

Importance of geochemical transformations in determining submarine groundwater discharge-derived trace metal and nutrient fluxes

Seasonal (Spring and Summer 2002) concentrations of dissolved (<0.22 μm) trace metals (Ag, Al, Co, Cu, Mn, Ni, Pb), inorganic nutrients (NO₃, PO₄, Si), and DOC were determined in groundwater samples from 5 wells aligned along a 30 m shore-normal transect in West Neck Bay, Long Island, NY. Results show that significant, systematic changes in groundwater trace metal and nutrient composition occur along the flowpath from land to sea. While conservative mixing between West Neck Bay water and the groundwaters explains the behavior of Si and DOC, non-conservative inputs for Co and Ni were observed (concentration increases of 10- and 2-fold, respectively) and removal of PO₄ and NO₃ (decreases to about half) along the transport pathway. Groundwater-associated chemical fluxes from the aquifer to the embayment calculated for constituents not exhibiting conservative behavior can vary by orders of magnitude depending on sampling location and season (e.g. Co, 3.4 × 10²– 8.2 × 10³ μmol d⁻¹). Using measured values from different wells as being representative of the true groundwater endmember chemical composition also results in calculation of very different fluxes (e.g., Cu, 6.3 × 10³ μmol d⁻¹ (inland, freshwater well) vs. 2.1 × 10⁵ μmol d⁻¹(seaward well, S = 17 ppt)). This study suggests that seasonal variability and chemical changes occurring within the subterranean estuary must be taken into account when determining the groundwater flux of dissolved trace metals and nutrients to the coastal ocean.     

Electron paramagnetic resonance spectroscopy: A suggested approach to trace metal analysis in marine environments

Electron paramagnetic resonance (EPR) spectroscopy analysis of marine samples from different environments appears to differentiate between adsorbed and structural Mn (II) and Fe (III) sites in the sediment. This suggests that EPR may provide a means of distinguishing different environmental influences on sediment. Acid extract solutions from sediment samples exhibit clearly defined EPR spectra due to Mn(II), Ti(III), Fe(III), and VO(IV), which are amenable to qualitative and quantitative analysis at concentrations below one part per million. Spectra of several shellfish vary considerably, both between species, and within a species, depending on sampling localities. Resonances from Mn(II), Mo(V), and Fe(III) can be obtained. Mn(II) is substituted for Ca(II) in the calcite structure of some shells. The low detection limits, small sample size, required and identification of oxidation states by EPR complement other analytical techniques and may prove useful in marine systems.     

GEOTRACES - An international study of the global marine biogeochemical cycles of trace elements and their isotopes

Trace elements serve important roles as regulators of ocean processes including marine ecosystem dynamics and carbon cycling. The role of iron, for instance, is well known as a limiting micronutrient in the surface ocean. Several other trace elements also play crucial roles in ecosystem function and their supply therefore controls the structure, and possibly the productivity, of marine ecosystems. Understanding the biogeochemical cycling of these micronutrients requires knowledge of their diverse sources and sinks, as well as their transport and chemical form in the ocean.Much of what is known about past ocean conditions, and therefore about the processes driving global climate change, is derived from trace-element and isotope patterns recorded in marine deposits. Reading the geochemical information archived in marine sediments informs us about past changes in fundamental ocean conditions such as temperature, salinity, pH, carbon chemistry, ocean circulation and biological productivity. These records provide our principal source of information about the ocean's role in past climate change. Understanding this role offers unique insights into the future consequences of global change.The cycle of many trace elements and isotopes has been significantly impacted by human activity. Some of these are harmful to the natural and human environment due to their toxicity and/or radioactivity. Understanding the processes that control the transport and fate of these contaminants is an important aspect of protecting the ocean environment. Such understanding requires accurate knowledge of the natural biogeochemical cycling of these elements so that changes due to human activity can be put in context.Despite the recognised importance of understanding the geochemical cycles of trace elements and isotopes, limited knowledge of their sources and sinks in the ocean and the rates and mechanisms governing their internal cycling, constrains their application to illuminating the problems outlined above. Marine geochemists are poised to make significant progress in trace-element biogeochemistry. Advances in clean sampling protocols and analytical techniques provide unprecedented capability for high-density sampling and measurement of a wide range of trace elements and isotopes which can be combined with new modelling strategies that have evolved from the World Ocean Circulation Experiment (WOCE) and Joint Global Ocean Flux Study (JGOFS) programmes. A major new international research programme, GEOTRACES, has now been developed as a result of community input to study the global marine biogeochemical cycles of trace elements and their isotopes. Here, we describe this programme and its rationale.     

Particulate trace metal speciation in stream sediments and relationships with grain size: Implications for geochemical exploration

Sediment samples were collected from streambeds in an undisturbed watershed in eastern Quebec (Gaspé Peninsula). Two sampling sites were located on a stream draining an area of known mineralization (Cu, Pb, Zn) and two on a control stream. The sediment samples were separated into 8 distinct size classes in the 850 μm to <1 μm size range by wet sieving, gravity sedimentation or centrifugation. Each sediment subsample was then subjected to a sequential extraction procedure designed to partition the particulate heavy metals into five fractions: (1) exchangeable; (2) specifically adsorbed or bound to carbonates; (3) bound to Fe-Mn oxides; (4) bound to organic matter; (5) residual. The following metals were analyzed in each extract: Cu, Pb, Zn; Fe, Mn.Comparison of samples from the mineralized area with control samples revealed the expected increase in total concentrations for Cu, Pb and Zn. Non-detrital metals were mainly associated with Fe oxides (specifically adsorbed; occluded) and with organic matter or resistant sulfides. For a given sample, variation of trace metal levels in fractions 2 and 3 with grain size reflected changes in the available quantities of the inorganic scavenging phase (FeOx/MnOx); normalization with respect to Fe and Mn content in fraction 3 greatly reduced the apparent dependency on grain size.The results of this study suggest that a single reducing extraction (NH₂OH.HCl) could be used advantageously to detect anomalies in routine geochemical surveys. A second leaching step with acidified H₂O₂ could also be included, as the trace metal concentrations in fraction 4, normalized with respect to organic carbon content, also showed high {anomaly/background} ratios.     

Holocene history of Ob River discharge according to lithological and geochemical data

Riverine water and sediment discharge to the Arctic Ocean is among the most important parameters influencing Arctic climate. It is clear that the evaluation of Arctic paleoclimate requires information on the paleodischarge of major rivers entering the sedimentation basin. Presently, the water discharge of the Ob River accounts for about 12% of the total input of river water into the Arctic Ocean. During the investigation of the Kara Sea in the framework of the Russian-German SIRRO Project, the history of Yenisei discharge received much attention in a number of publications. This paper presents the results of lithological and geochemical investigations with application to the Holocene discharge of the Ob River. Qualitative (SiO₂, Al₂O₃, K₂O, and some modules) and quantitative (sedimentation rates and absolute masses of sedimentary material) parameters were used to characterize the history of the Ob sediment discharge. It was shown that the investigated paleochannels of the Ob were initiated at the Pleistocene-Holocene boundary, and during the first half of the Holocene, the river discharge decreased irregularly with decreasing age of sediments. The observed maxima are in fairly good agreement with the data for the Yenisei. We proposed a hypothesis on the influence of glacioisostatic movements in the marginal region of the former Kara ice sheet of late Valdai age on the cessation of marine-fluvial glaciation in the paleochannels of Ob and Yenisei in the periphery of the Ob-Yenisei shoal.     

Scenario of particulate trace metal and metalloid transport during a major flood event inferred from transient geochemical signals

High-resolution sampling (every 3 h) of SPM was performed during a major flood event in a heterogeneous, medium scale watershed of the Garonne-Gironde fluvial-estuarine system (the Lot River; A = 10,700 km²; Q = 151 m³/s). Particulate metal and metalloid (Cd, Zn, Pb, Co, Cr, Ni, Mo, V, U, As, Sb, Th) concentrations were compared with monthly data of the same site (Temple site) obtained during 1999–2002. During the flood event, suspended particulate matter (SPM) concentrations closely followed river discharge with a maximum value (1530 mg/L) coinciding with the discharge peak (2970 m³/s). Trace metal/metalloid concentrations showed significant temporal variations and very contrasted responses. Particulate concentrations were similar to baseline values at the beginning of the flood and mostly increased during the event, showing anticlockwise and complex shape hystereses. Comparison of SPM yield (440,000 t) and particulate metal/metalloid fluxes during the flood with annual fluxes (1999–2002) highlights the great importance of major flood events in fluvial transport. Adequate sampling frequency during floods is necessary for reliable annual flux estimates and provides geochemical signals that may greatly improve our understanding of fluvial transport processes. The scenario of SPM and metal and metalloid transport during the flood are reconstructed by combining variations of Zn, Cd and Sb concentrations, concentration ratios (e.g. Zn/Cd, As/Th, Cd/Th) and hysteresis loops. Changes in SPM and metal/metalloid transport during distinct key stages of the flood were attributed to successive dominance of different water masses transporting material from different sources (e.g. industrial point source, bed sediment from reservoirs, plain erosion). Flood management (dam flushing) clearly enhanced the remobilization of up to 30-a old polluted sediment from reservoir lakes. Sediment remobilization accounted for ∼185,000 t of SPM (i.e. 42% of the total SPM fluxes during the flood) and strongly contributed to particulate metal/metalloid transport for Cd (90%), Zn (83%) and Pb (61%). Therefore, flood management needs to be taken into consideration in future models for erosion and pollutant transport.     

居隆庵铀矿床蚀变分带及其地球化学特征

以产于碎斑流纹岩中的铀矿化蚀变为例,对居隆庵铀矿床蚀变分带及其地球化学特征进行了系统研究,将该区蚀变分成5个带。地球化学研究表明,围岩蚀变过程中元素迁移、富集有明显的规律;常量元素（Ca、Mg、K、S）、微量元素（Cu、Pb、Zn、As、Sb、Th、Mo、W、F）和稀土元素（REE）有明显富集;亲硫元素是铀成矿作用的指示元素;成矿过程至少经历了两次热液活动;成矿流体具有还原性和深源性。     

中酸性岩浆体系成矿流体及微量元素地球化学特征

从流体成矿作用角度出发，与酸性岩浆体系有关的成矿流体可以分为：酸性岩浆硅酸盐熔融体，岩浆一热液过渡阶段硅酸盐熔融体及其分异的流体，酸性岩浆熔体分异形成的热水成矿溶液。酸性岩浆体系主要提供热源和部分矿质，其提供的热源驱动地下水淋滤、萃取围岩中的成矿物质形成地下水热液成矿流体。变质岩混合岩化形成花岗质岩浆过程中所形成的混合岩化成矿流体。在此基础上，讨论了上述不同成矿流体的微量元素地球化学特征及其对成矿的控制作用。     

Particulate trace metal and major element distributions over consecutive tidal cycles in Port Jackson Estuary,Australia

Particulate trace metal (Cu, Cr, Ni, Pb and Zn) and major element (Fe, Mn and Al) concentrations have been determined following intensive sampling over two consecutive spring tidal cycles in the 'turbidity maximum zone' (TMZ) of the Port Jackson estuary, Australia. Salinity, temperature, pH, dissolved oxygen, suspended particulate matter (SPM) and chlorophyll a were also determined. A three-factor analysis of variance was used to test temporal variability in concentrations of particulate trace metals and major elements as a result of tidal oscillation. Estuarine master variables, such as temperature and pH, varied within a narrow range; nevertheless, the tidal signal was clear for surface and bottom waters. In surface water, no variance was detected in SPM concentrations between consecutive tidal cycles or between tidal stages (i.e. flood, ebb and slack water). In bottom water, however, SPM concentrations were significantly higher (PА.05) at flood tide than at slack high water and ebb tide. Concentrations of particulate trace metals and major elements in surface water do not display significant variability between tidal cycles or stages. Nevertheless, differences within each tidal stage were significant (PА.05) for all elements. In bottom water, only particulate Fe and Al exhibited significant differences (PА.05) between tidal cycles, whereas particulate Ni was the only trace element that presented significant differences (PА.05) between tidal stages, following the distribution of SPM, with highest concentrations at flood tide. Among the metals studied, significant variation was found at all three temporal scales examined (i.e. from hours to consecutive tidal cycles), although the patterns of variation were different for each metal. The semi-diurnal fluctuation of SPM and particulate trace metal concentrations during spring tides is interpreted as a resuspension-deposition cycle caused by cyclical oscillations of bottom currents. The results are discussed in the context of the implications of tidal cycle influence on the geochemistry and cycling of particulate trace metals in the Port Jackson estuary.     

Identification of sedimentary cycles through Fourier analysis of geochemical data

Trace elements are sensitive to slight shifts in the chemical equilibrium of a body of water, and as a result they can be expected to reflect cyclical events in the earth's history. Geochemical data from a section of Upper Jurassic (Kimmeridgian) bituminous sediments in Great Britain, 20 m thick, have been examined by single Fourier series analysis, thereby permitting an objective assessment of sedimentary cycles. Subjectivity only enters into the final interpretative stage.Assumptions made as to the rate of deposition of these sediments have indicated several superimposed periodicities with respective durations of (?) 200,000, 100,000, 40,000, 14,000, and 11,000 years.Comparison is made with long-term cyclic durations estimated by other workers. Several of these periods are coincident with the duration of astronomical phenomena which could cause climatic fluctuations.     

B,As, and F contamination of river water due to wastewater discharge of the Yangbajing geothermal power plant,Tibet, China

Thermal waters from the Yangbajing geothermal field, Tibet, contain high concentrations of B, As, and F, up to 119, 5.7 and 19.6 mg/L, respectively. In this paper, the distribution of B, As, and F in the aquatic environment at Yangbajing was surveyed. The results show that most river water samples collected downstream of the Zangbo River have comparatively higher concentrations of B, As, and F (up to 3.82, 0.27 and 1.85 mg/L, respectively), indicating that the wastewater discharge of the geothermal power plant at Yangbajing has resulted in B, As, and F contamination in the river. Although the concentrations of B, As, and F of the Zangbo river waters decline downstream of the wastewater discharge site due to dilution effect and sorption onto bottom sediments, the sample from the conjunction of the Zangbo River and the Yangbajing River has higher contents of B, As, and F as compared with their predicted values obtained using our regression analysis models. The differences between actual and calculated contents of B, As, and F can be attributed to the contribution from upstream of the Yangbajing River. Water quality deterioration of the river has induced health problems among dwellers living in and downstream of Yangbajing. Effective measures, such as decontamination of wastewater and reinjection into the geothermal field, should be taken to protect the environment at Yangbajing.     

Numerical simulation on the marine landslide due to gas hydrate dissociation

Marine landslide due to gas hydrate dissociation is a kind of potential heavy hazards. Numerical simulation was processed to investigate the deformation, landslide and effects of main factors on the critical scale of dissociation zone to induce marine landslides during/after dissociation of gas hydrate. A simple method for analyzing the critical scale was presented based on the limit equilibrium method. It is shown that the maximum settlement is located near the upper side of the dissociation zone. The soil near the lower side of the dissociation zone uplifts. There is a critical scale of dissociation zone over which landslide will occur under given conditions. Expansion modes of the dissociation zone have obvious effects on the critical scale.     

平台石墨炉原子吸收法测定地球化学样品中痕量锡

本文采用石墨炉原子吸收光谱法测定地球化学样品中痕量锡.以硝酸钯、硝酸镁和硝酸铵为基体改进剂,研究了最佳的分析测定条件.用该方法测定国家地球化学标准样品的结果与标准值相符.     

Diffusion of trace elements in FeNi metal: Application to zoned metal grains in chondrites

We have measured diffusion coefficients for P, Cr, Co, Ni, Cu, Ga, Ge, Ru, Pd, Ir, and Au in Fe metal from 1150 to 1400°C and at 1 bar and 10 kbar. Diffusion couples were prepared from high-purity Fe metal and metal from the IIA iron meteorite Coahuila (single crystal kamacite) or the pallasite Springwater (polycrystalline kamacite) and held at run conditions for 3.5 to 123 h. Diffusion profiles were measured using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) or the electron microprobe. Many elements were measured from the same experimental runs so interelemental comparisons are improved over other data sets in which data for different elements come from different experiments. Some literature diffusion coefficients (D) for Ni and Co in taenite can be up to a factor of 3 higher for Ni than Co, yet our results show no difference (e.g., D_Ni and D_Co ∼ 2.2 × 10^-15 m²/s at 1150°C). Thus, diffusion of Ni and Co in single crystal taenite will not measurably fractionate the Ni/Co ratio. On the other hand, the large difference in D_Ni and D_Ir (D_Ir is ∼5 times lower) and the similarity of D_Ni and D_Ru at all temperatures investigated indicates that Ni/Ir and Ni/Ru ratios in zoned metal grains will be useful discriminators of processes controlled by diffusion vs. volatility. In zoned metal grains in primitive chondrites, deviations of the Ni/Ru and Ni/Ir ratios from a condensation curve are opposite to a diffusion-controlled process, but consistent with a volatility-controlled process. The new multielement diffusion coefficients will also be useful in evaluating a variety of other processes in planetary science.     

Mineralogical and geochemical alteration of low-grade metamorphic black slates due to oxidative weathering

Low-grade metamorphic black slates of Silurian and Lower Devonian ages (from the Thüringisches Schiefergebirge in Germany) were investigated to identify mineralogical and geochemical alterations that occur during the oxidative weathering black slates.The slates exhibit an intense total organic carbon decrease (>90 wt%) due to oxidative weathering. The organic matter in black slate consists mainly of non-pyrolysable material with only minor portions of pyrolysable material. In contrast to the non-pyrolysable organic matter, the concentration of pyrolysable organic matter is not decreased during weathering. Heating experiments have yielded information about a potential protection of pyrolysable organic matter against weathering, which is probably caused by a structural configuration or the intergrowth of organic matter and illite.The slates consist mainly of illite. Iron oxide (goethite) and phosphate encrustations were formed on slate surfaces as a result of oxidative and acid weathering of both iron sulfide and monazite. Kaolinite often occurs as an older encrustation beneath the iron oxide encrustations. Encrustations of iron oxide and phosphate are major sinks for trace elements, released during oxidative weathering.     

Sediment budget-based estimates of trace metal inputs to a Chesapeake estuary

This article evaluates whether a sediment budget for the South River, Maryland, can be coupled with metals data from sediment cores to identify and quantify sources of historic metal inputs to marsh and subtidal sediments along the estuary. Metal inputs to estuarine marsh sediments come from fluvial runoff and atmospheric deposition. Metal inputs to subtidal sediments come from atmospheric deposition, fluvial runoff, coastal erosion, and estuarine waters. The metals budget for the estuary indicates that metal inputs from coastal erosion have remained relatively constant since 1840. Historical variations in metal contents of marsh sediments have probably resulted primarily from increasing atmospheric deposition in this century, but prior to 1900 may reflect changing fluvial sources, atmospheric inputs, or factors not quantified by the budget. Residual Pb, Cu, and Zn in the marsh sediments not accounted for by fluvial inputs was low to moderate in 1840, decreased to near zero circa 1910, and by 1987 had increased to levels that were one to ten times greater than those of 1840. Sources of variability in subtidal cores could not be clearly discerned because of geochemical fluxes, turbulent mixing, and bioturbation within the cores. The sediment-metal budgeting approach appears to be a viable method for delineating metal sources in small, relatively simple estuarine systems like the South River and in systems where recent deposition (for example, prograding marshes) prevents use of deep core analysis to identify background levels of metal. In larger systems or systems with more variable sources of sediment and metal input, however, assumptions and measurement errors in the metal budgeting approach suggest that deep core analysis and normalization techniques are probably preferable for identifying anthropogenic impacts.Field and laboratory research conducted at the Department of Geography, University of Maryland, College Park, Maryland, 20742, USAField and laboratory research conducted at the Marine and Estuarine Environmental Science Program, University of Maryland, College Park, Maryland, 20742, USA