Calcite cementation during bacterial manganese, iron and sulphate reduction in Jurassic shallow marine carbonates

Faunally restricted argillaceous wackestones from the Middle Jurassic of eastern England contain evidence of early diagenetic skeletal aragonite dissolution and stabilization of the carbonate matrix, closely followed by precipitation of zoned calcite cements, and precipitation of pyrite. Distinctive cathodoluminescence and trace element trends through the authigenic calcites, their negative δ¹³C compositions and the location of pyrite in the paragenetic sequence indicate that calcite precipitation took place during sequential bacterial Mn, Fe and sulphate reduction. Calcite δ¹⁸O values are compatible with cementation from essentially marine pore fluids, although compositions vary owing to minor contamination with ¹⁸O-depleted ‘late’cements. Mg and Sr concentrations in the calcites are lower than those in recent marine calcite cements. This may be a result of kinetic factors associated with the shallow burial cementation microenvironments. Bicarbonate for sustained precipitation of the authigenic calcites was derived largely from aragonite remobilization, augmented by that produced through anaerobic organic matter oxidation in the metal and sulphate reduction environments. Aragonite dissolution is thought to have been induced by acidity generated during aerobic bacterial oxidation of organic matter. Distinction of post-oxic metal reduction and anoxic sulphate reduction diagenetic environments in modern carbonate sediments is uncommon outside pelagic settings, and early bacterially mediated diagenesis in modern platform carbonates is associated with extensive carbonate dissolution. High detrital Fe contents of the Jurassic sediments, and their restricted depositional environment, were probably the critical factors promoting early cementation. These precipitates constitute a unique example of calcite authigenesis in shallow water limestones during bacterial Mn and Fe reduction.     

Evaluation of elemental enrichments in surface sediments off southwestern Taiwan

Surface slices of 20 sediment cores, off southwestern Taiwan, and bed sediment of River Kaoping were measured for major and trace elements (Al, As, Ca, Cd, Cl, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P, Pb, S, Si, Ti, V, and Zn) to evaluate the geochemical processes responsible for their distribution, including elemental contamination. Major element/Al ratio and mean grain size indicate quartz-dominated, coarse grained sediments that likely derived from sedimentary rocks of Taiwan and upper crust of Yangtze Craton. Bi-plot of SiO₂ versus Fe₂O₃^T suggests the possible iron enrichment in sediments of slag dumping sites. Highest concentrations of Cr, Mn, P, S, and Zn found in sediments of dumping sites support this. Correlation analysis shows dual associations, detrital and organic carbon, for Cr, P, S, and V with the latter association typical for sediments in dumping sites. Normalization of trace elements to Al indicates high enrichment factors (>2) for As, Cd, Pb, and Zn, revealing contamination. Factor analysis extracted four geochemical associations with the principal factor accounted for 25.1% of the total variance and identifies the combined effects of dumped iron and steel slag-induced C–S–Fe relationship owing to authigenic precipitation of Fe–Mn oxyhydroxides and/or metal sulfides, and organic matter complexation of Fe, Mn, Ca, Cr, P, and V. Factors 2, 3, and 4 reveal detrital association (Ti, Al, Ni, Pb, Cu, and V), effect of sea salt (Cl, Mg, Na, and K) and anthropogenic component (As and Zn)-carbonate link, respectively, in the investigated sediments.     

Early diagenetic vivianite [Fe3(PO4)2 · 8H2O] in a contaminated freshwater sediment and insights into zinc uptake: A μ-EXAFS, μ-XANES and Raman study

The sediments in the Salford Quays, a heavily-modified urban water body, contain high levels of organic matter, Fe, Zn and nutrients as a result of past contaminant inputs. Vivianite [Fe₃(PO₄)₂ · 8H₂O] has been observed to have precipitated within these sediments during early diagenesis as a result of the release of Fe and P to porewaters. These mineral grains are small (<100 μm) and micron-scale analysis techniques (SEM, electron microprobe, μ-EXAFS, μ-XANES and Raman) have been applied in this study to obtain information upon the structure of this vivianite and the nature of Zn uptake in the mineral. Petrographic observations, and elemental, X-ray diffraction and Raman spectroscopic analysis confirms the presence of vivianite. EXAFS model fitting of the FeK-edge spectra for individual vivianite grains produces Fe–O and Fe–P co-ordination numbers and bond lengths consistent with previous structural studies of vivianite (4O atoms at 1.99–2.05 Å; 2P atoms at 3.17–3.25 Å). One analysed grain displays evidence of a significant Fe³⁺ component, which is interpreted to have resulted from oxidation during sample handling and/or analysis. EXAFS modelling of the Zn K-edge data, together with linear combination XANES fitting of model compounds, indicates that Zn may be incorporated into the crystal structure of vivianite (4O atoms at 1.97 Å; 2P atoms at 3.17 Å). Low levels of Zn sulphate or Zn-sorbed goethite are also indicated from linear combination XANES fitting and to a limited extent, the EXAFS fitting, the origin of which may either be an oxidation artifact or the inclusion of Zn sulphate into the vivianite grains during precipitation. This study confirms that early diagenetic vivianite may act as a sink for Zn, and potentially other contaminants (e.g. As) during its formation and, therefore, forms an important component of metal cycling in contaminated sediments and waters. Furthermore, for the case of Zn, the EXAFS fits for Zn phosphate suggest this uptake is structural and not via surface adsorption.     

Geochemical and mineral magnetic characterisation of urban sediment particulates,Manchester, UK

Urban sediments are part of a complex system in which particulates accumulate potentially toxic pollutants, ultimately posing a threat to urban water-bodies and public health. It is therefore important to recognise sources, signatures and pathways of urban particulates. Urban sediment samples were analysed from both inner and outer city road surfaces of Manchester, UK. High metal concentrations, coupled with the largely ferrimagnetic multi-domain (MD) mineral magnetic composition of the particulates, indicate inputs of anthropogenic origin, primarily particulates derived from automobiles, as being the dominant source to the urban sediment system. Iron and Pb concentrations show a clear spatial trend, whereby concentrations are enhanced in the inner city samples. Lead concentrations for inner and outer city samples average 354 and 185 μg g⁻¹, respectively. Iron concentrations for inner and outer city samples average 11302 and 6486 μg g⁻¹, respectively. Sequential extraction analysis shows the metals Mn, Fe, Zn and Pb are largely associated with the reducible fraction, whereas Cu is largely associated with the oxidisable fraction. Zinc is the only metal showing significant association with the exchangeable fraction (up to 33%), suggesting that it may be the most susceptible metal to mobilisation during runoff. Metal fractions identified as showing larger associations with the reducible and oxidisable fractions will continue to be vulnerable to mobilisation as a result of changes in ambient pH and/or redox conditions. Mineral magnetic concentration parameters, such as the saturation isothermal remanent magnetisation (SIRM), together with hysteresis parameters such as the coercive force and interparametric ratios (such as (B_o)_cr/H_c and IRM_-100mT/SIRM) show that ferrimagnetic MD minerals dominate the Manchester urban sediments. Average results for frequency-dependent susceptibility as a percentage (2%) suggest that the composition of these Manchester sediments is not dominated by soil-derived material, and therefore magnetically coarser, anthropogenically-derived material is dominant. Unlike Pb and Fe concentrations, mineral magnetic characteristics of the Manchester urban sediment samples exhibit no significant spatial variation.     

Major ion chemistry and metal distribution in coal mine pit lake contaminated with industrial effluents: constraints of weathering and anthropogenic inputs

Ion chemistry of mine pit lake water reveals dominance of alkaline earths (Ca²⁺ and Mg²⁺) over total cation strength, while SO₄ ^2? and Cl^? constitute the majority of total anion load. Higher value of Ca²⁺?+?Mg²⁺/Na⁺?+?K⁺ (pre-monsoon 5.986, monsoon 8.866, post-monsoon 7.09) and Ca²⁺?+?Mg²⁺/HCO₃ ^??+?SO ₄ ² (pre-monsoon 7.14, monsoon 9.57, post-monsoon 8.29) is explained by weathering of Ca?CMg silicates and dissolution of Ca²⁺-bearing minerals present in parent rocks and overburden materials. Silicate weathering supposed to be the major geological contributor, in contrast to bicarbonate weathering does a little. Distribution coefficient for dissolved metals and sorbed to surface sediments is in the order of Cd?>?Pb?>?Fe?>?Zn?>?Cu?>?Cr?>?Mn. Speciation study of monitored metals in surface sediments shows that Fe and Mn are dominantly fractionated in exchangeable-acid reducible form, whereas rest of the metals (Cr, Pb, Cd, Zn, and Cu) mostly in residual form. Cd, Pb, and Zn show relatively higher recalcitrant factor that indicates their higher retention in lake sediments. Factor loading of monitored physico-chemical parameters resembles contribution/influences from geological weathering, anthropogenic inputs as well as natural temporal factors. Ionic load/strength of lake water accounted for geochemical process and natural factors, while pollutant load (viz BOD, COD and metals, etc.) is associated with anthropogenic inputs through industrial discharge.     

Geochemical fractionation of heavy metals in Chilka Lake (east coast of India)—a tropical coastal lagoon

Chilka lake, the largest coastal lagoon of Asia is one of the most dynamic ecosystems along the Indian coast. Historically the lagoon has undergone a considerable reduction in surface area due, in part, to input from natural processes but mostly due to human activities. The purpose of this investigation is to document the heavy metals' affinity for specific geochemical phases in the recently deposited sediments in the lagoon. Thirty-three samples were collected and analyzed for different geochemical phases of Fe, Mn, Cu, Cr, Ni, Pb, and Zn utilizing a sequential extraction scheme. In the nonlithogenous fraction, the exchangeable fraction was not geochemically significant, having <2% of the total metal concentration for all the elements. However, the carbonate fraction contained the following percentages of the total concentration: <1% Fe, 13% Mn, 6% Cu, 4% Cr, 8% Ni, 13% Pb, and 12% Zn, suggesting the detrital origin of the sediments. Reducible and organic matter-bound fractions were the significant phases in the nonlithogenous fraction, containing 9% Fe, 16% Mn, 15% Cu, 16% Cr, 16% Ni, 14% Pb, and 14% Zn in the former and 4% Fe, 3% Mn, 17% Cu, 3% Cr, 14% Ni, 15% Pb, and 14% Zn in the latter. The phenomenon has been attributed to the scavenging affinity of Fe-Mn oxides and affinity for sorption into organic matter of the lagoon sediments. The lithogenous, residual fraction generally considered as a guide for natural background values was determined to contain 87% Fe, 67% Mn, 61% Cu, 77% Cr, 61.3% Ni, 56% Pb, and 60% Zn of the total concentrations.     

Geochemical features of heavy metals in core sediments of northwestern Taihu Lake, China

Sequential core sediments from northwestern Taihu Lake in China were analyzed for grain size, organic carbon and heavy metal content. The sediments are composed of organic-poor clayey-fine silts. The chemical speciations of Cu, Fe, Mn, Ni, Pb, and Zn were also analyzed using the BCR sequential extraction procedure. Cu, Fe, Ni, and Zn are mainly associated with the residue fraction; Mn is concentrated mainly in exchangeable/carbonate fraction and residue fraction; and Pb mainly in Fe/Mn oxide fraction and organic/sulfide fraction. The exchangeable/carbonate fractions of Cu, Fe, Ni, Zn and Pb are lower. The fractions of Ni, Pb and Zn bound to the Fe/Mn oxide have significant correlations with reducible Mn; the organic/sulfide fractions of Cu, Mn, Ni, Pb, and Zn have significant correlations with TOC. The extractable fractions of Cu, Mn, Ni, Pb, and Zn are high at the top 4 cm of the core sediments as compared to those in the deeper layers, showing the anthropogenic input of heavy metals is due to rapid industrial development. The heavy metal pollution history of the sediments has been recorded since the late 1970s, determined by the result of ^137Cs dating.     

The post-depositional reactivity of iron and managanese in the sediments of a macrotidal estuarine system

Four cores of anoxic sediments were collected from the Seine estuary to assess the early diagenesis pathways leading to the formation of previously reactive phase. Pore waters were analyzed for dissolved iron (Fe) and manganese (Mn) and different ligands (e.g., sulfate, chloride, total inorganic carbon). The anoxic zone is present up to the first centimeter depth, in these conditions the reduction of Mn and Fe oxides and SO₄ ²⁻ was verified. The sulfate reduction was well established with a subsequent carbon mineralization in the NORMAI94 core. The chemical speciation of Mn and Fe in the dissolved and solid phases was determined. For the dissolved phase, thermodynamic calculations were used to characterize and illustrate the importance of carbonate and phosphate phases as sinks for Fe and Mn. The ion activity product (IAP) of Fe and Mn species was compared to the solubility products (Ks) of these species. In the solid phase, the presence of higher concentration of calcium carbonate in the Seine sediments is an important factor controlling Mn cycle. The carbonate-bound Mn can reach more than 75% of the total concentration. This result is confirmed by the use of electron spin resonance (ESR) spectroscopy. The reduction of Fe is closely coupled to the sulfate reduction by the formation of new solid phases such as FeS and FeS₂, which can be regarded as temporal sinks for sulfides. These forms were quantified in all cores as acid volatile sulfide (AVS: FeS+ free sulfide) and chromium reducible sulfide (CRS: FeS₂+elemental sulfur S⁰).     

The effect of early diagenesis on the Fe isotope compositions of porewaters and authigenic minerals in continental margin sediments

Iron isotope compositions in marine pore fluids and sedimentary solid phases were measured at two sites along the California continental margin, where isotope compositions range from δ⁵⁶Fe = −3.0‰ to +0.4‰. At one site near Monterey Canyon off central California, organic matter oxidation likely proceeds through a number of diagenetic pathways that include significant dissimilatory iron reduction (DIR) and bacterial sulfate reduction, whereas at our other site in the Santa Barbara basin DIR appears to be comparatively small, and production of sulfides (FeS and pyrite) was extensive. The largest range in Fe isotope compositions is observed for Fe(II)_aq in porewaters, which generally have the lowest δ⁵⁶Fe values (minimum: −3.0‰) near the sediment surface, and increase with burial depth. δ⁵⁶Fe values for FeS inferred from HCl extractions vary between ∼−0.4‰ and +0.4‰, but pyrite is similar at both stations, where an average δ⁵⁶Fe value of −0.8 ± 0.2‰ was measured. We interpret variations in dissolved Fe isotope compositions to be best explained by open-system behavior that involves extensive recycling of Feflux. This study is the first to examine Fe isotope variations in modern marine sediments, and the results show that Fe isotopes in the various reactive Fe pools undergo isotopic fractionation during early diagenesis. Importantly, processes dominated by sulfide formation produce high-δ⁵⁶Fe values for porewaters, whereas the opposite occurs when Fe(III)-oxides are present and DIR is a major pathway of organic carbon respiration. Because shelf pore fluids may carry a negative δ⁵⁶Fe signature it is possible that the Fe isotope composition of ocean water reflects a significant contribution of shelf-derived iron to the open ocean. Such a signature would be an important means for tracing iron sources to the ocean and water mass circulation.     

Environmental pollution impact on water and sediments of Kumaun lakes, Lesser Himalaya, India: a comparative study

A study of the water and sediment chemistry of the Nainital, Bhimtal, Naukuchiyatal and Sattal Lakes of Kumaun, has shown that the water of these lakes are alkaline and that electrical conductivity, total dissolved solid and bicarbonate HCO ₃ ⁻ are much higher in Nainital than in the other three lakes. The weathering of limestone lithology and anthropogenic pollution, the latter due to the very high density of population in the Nainital valley, are the primary sources of enhanced parameters. The low pH of Nainital Lake water is due to low photosynthesis and enhanced respiration, increasing CO₂ in the water and the consequent enhancement of Ca²⁺ and HCO ₃ ⁻ . The dissolved oxygen in Nainital Lake is less compared to other lakes, indicating anoxic conditions developing at the mud–water interface at depth. The PO ₄ ³⁻ content in Nainital is higher (124 μg/l), showing an increasing trend over time leading to eutrophic conditions. The trace metals (Cu, Co, Zn, Ni, Mn, and Sr) are present in greater amounts in the water of Nainital Lake than in the other three lakes, though Fe and Cr are high in Bhimtal and Fe in Naukuchiyatal. The higher abundance is derived from the leaching of Fe–Mg from metavolcanic and metabasic rocks. Most of the heavy metals (Cr, Ni, Cu, Mn, Fe, Sr, and Zn) significantly enrich the suspended sediments of the lakes compared to the bed sediments which due to their adsorption on finer particles and owing to multiple hydroxide coating and organic content, except for Fe, which is enriched in the bed sediments. The high rate of sedimentation, 11.5 mm/year in Nainital, compared to Bhimtal with 4.70 mm/year, Naukuchiyatal with 3.72 mm/year, and Sattal with 2.99 mm/year, has resulted in shorter residence time, poor sorting of grains, and lesser adsorption of heavy metals, leading consequently, their depletion in the bed sediments of Nainital Lake.     

Distribution and partitioning of major and trace elements in pyrite-bearing sediments of a Mediterranean coastal lagoon

The formation of iron sulphide minerals exerts significant control on the behaviour of trace elements in sediments. In this study, three short sediment cores, retrieved from the remote Antinioti lagoon (N. Kerkyra Island, NW Greece), are investigated concerning the solid phase composition, distribution, and partitioning of major (Al, Fe) and trace elements (Cd, Cu, Mn, Pb, and Zn). According to ²¹⁰Pb, the sediments sampled correspond to depositions of the last 120 years. The high amounts of organic carbon (4.1–27.5%) result in the formation of Fe sulphides, predominantly pyrite, already at the surface sediment layers. Pyrite morphologies include monocrystals, polyframboids, and complex FeS–FeS₂ aggregates. According to synchrotron-generated micro X-ray fluorescence and X-ray absorption near-edge structure spectra, authigenically formed, Mn-containing, Fe(III) oxyhydroxides (goethite type) co-exist with pyrite in the sediments studied. Microscopic techniques evidence the formation of galena, sphalerite and CuS, whereas sequential extractions show that carbonates are important hosts for Mn, Cd, and Zn. However, significant percentages of non-lattice held elements are bound to Fe/Mn oxyhydroxides that resist reductive dissolution (on average 60% of Pb, 46% of Cd, 43% of Zn and 9% of Cu). The partitioning pattern changes drastically in the deeper part of the core that is influenced by freshwater inputs. In these sediments, the post-depositional pyritization mechanism, illustrated by overgrowths of Fe monosulphides on pre-existing pyrite grains, results in relatively high degree of pyritization that reaches 49% for Cd, 66% for Cu, 32% for Zn and 7% for Pb.     

Diagenetic cycling of trace elements in the bottom sediments of the Swan River Estuary,Western Australia

Teflon strips were used in-situ in the bottom sediments at two sites in the Swan River Estuary to collect diagenetic Fe–Mn oxyhydroxides and monitor monthly changes in their morphology and trace element geochemistry. This study demonstrates that substantial concentrations of trace elements accumulate at the redox front during the formation of diagenetic Fe–Mn oxyhydroxides. It is likely that the Fe–Mn oxyhydroxides initially nucleate and grow on the Teflon strips via bacterial activity. Trace element geochemistry of the diagenetic Fe–Mn oxyhydroxides is influenced by changes in the supply of trace elements from either the bottom sediments and/or water column or changes in the physico-chemical status of bottom and porewaters. If sufficient diagenetic Fe–Mn oxyhydroxides are preserved in the upper layer(s) of the bottom sediment it is possible that diagenetic (secondary) trace element enrichment profiles may be produced which modify the historical input of natural or anthropogenic trace element sources. Alternatively, partial or complete dissolution of the diagenetic Fe–Mn oxyhydroxides in response to temporal changes in the redox status of the bottom sediment may lead to a substantial underestimate of trace element fluxes in historical bottom sediment profiles. This study highlights that considerable care must be taken when interpreting short- to long-term geochemical profiles in bottom sediments due to the possible occurrence of rapid, seasonally mediated diagenetic processes.     

Geochemistry of two sediment cores from the west coast of India

Copper, Pb, Zn, Ni, Co, Mn, AI, Ca, magnetic susceptibility and loss on ignition of sediments from two cores near Mangalore along the western continental shelf of India have been studied. The sediments have high Al and organic matter contents due to the high sedimentation rate and their proximity to river mouths. Down-core variations of elements indicate a decrease of lithogenous component during probably the past few centuries. While abundance of calcareous shells in some zones has lead to the dilution of most of the metals, it appears that Pb and Mn are associated with this phase. Copper, Zn and Fe are associated with organic matter and detrital particles, whereas Ni and Co are predominantly associated with the insoluble fraction. Oxides/hydroxides of Fe and Mn are absent because of the reducing conditions and the high terrigenous influx. Geochemically, Mn and Fe are present in different phases of sediments (in the insoluble fraction and organic matter respectively). The Fe content of one of the cores is positively correlated with magnetic susceptibility.     

Electron microbeam analysis of urban road-deposited sediment,Manchester, UK: Improved source discrimination and metal speciation assessment

Road-deposited sediment (RDS) is an accumulation of particulates upon street surfaces in urban centres. It is commonly highly contaminated and has major potential impacts upon surface water quality and human health, as well as becoming a waste material upon street sweeping. Although significant research has been undertaken upon the fine fraction within these systems, there is a lack of detailed, high-resolution grain-specific mineralogical and chemical data for the coarser fractions, which contain the bulk of the contamination by mass. The study reported here utilizes backscatter electron microscopic, electron microprobe and Raman spectroscopic analysis to provide novel data on RDS material from Manchester, UK, with significant implications for the improved understanding of source discrimination and contaminant metal speciation. The RDS samples studied are highly heterogeneous and the abundant nature of anthropogenic grains is particularly apparent. The RDS material has been found to be composed of a number of grain types: (i) silicate and alumino-silicate grains derived from a wide range of sources; (ii) iron oxide grains derived from the corrosion of galvanized steel; (iii) iron-rich glass grains derived as slag material from metal and waste processing activities and (iv) spherical Fe oxide and Fe-rich glass grains derived from high temperature combustion processes. Elemental metallic grains (Fe, Cu, Pb) are also present in minor amounts.     

Assessment of trace metal contents in water and bottom sediments from Eğirdir Lake,Turkey

The concentration of metals (Pb, As, Co, Cu, Ni, Zn, Fe and Mn) was investigated in water and sediment samples of E?irdir Lake. The Lake is the second largest fresh water lake of Turkey and it is used as drinking water in the region. The anthropogenic pollutants are primary sources of trace metals which are negatively affected lake water quality. These negative effects were observed in both lake water and bottom sediments. According to obtained data, Pb, Cu, Ni, Fe and Zn have significant enrichment in sediments samples. In addition, the hydrodynamic model of the lake was determined as effectively for Pb, Co, Cu, Ni, Zn, Fe and Mn accumulations. Also, the effect of anthropogenic pollutants was found to be more dominant than geogenic effect in metal accumulation of the lake bottom sediments. Therefore, anthropogenic pollutants within the lake basin should be consistently controlled for the sustainable usage of the lake.     

Metalliferous sediments from the H.M.S. Challenger voyage (1872-1876)

The legendary cruise of H.M.S. Challenger (1872-1876) around the globe must always occupy an eminent place in the annals of oceanography, as being the first systematic attempt made on a global scale to explore the ocean. This expedition made fundamental discoveries in biology and geology which have not been surpassed by any later scientific cruise. Sediment with high content of metals (later called “metalliferous”) was among the enigmatic findings taken onboard. Although the nature of metalliferous sediments is well known today, the very first sampled sediments of this type have not been studied to date. Motivated by the historical value of Challenger’s metalliferous sediment collection we undertook an investigation addressing two questions: (1) the composition of sediments from seafloor for which we have very limited data; (2) Sr-Nd-Pb-Fe-Zn-isotope signature of these sediments collected before the substantial human impact on the ocean during the 20th century.The SE Pacific metalliferous sediments sampled by the Challenger’s explorers are of 2 types: (1) metalliferous oozes blanketing ridge crests and flanks down to the calcite compensation depth (CCD); and (2) stripped of CaCO₃ metalliferous sediments located beneath the CCD in the deeps near the mid-ocean ridges. The abiogenic part of these sediments is composed mainly of poorly-crystalline to X-ray amorphous Fe-Mn-oxyhydroxides, and an amorphous silicate phase. These sediments have geochemical features similar to those of all the other metalliferous sediments: very high Fe and Mn content (on abiogenic basis), very low Al/(Al + Fe + Mn), and high content (on abiogenic basis) of As, Ba, Be, Bi, Cd, Co, Cu, Mo, Ni, Pb, Sb, Th, Tl, U, V, W, Y, Zn and Zr. Their REE distribution patterns are similar to that of deep seawater and show weak signs of hydrothermal imprint (weak positive or no Eu anomaly).Seawater and/or terrigenous input from South America control the Sr-Nd-Pb-isotope signature of the Challenger metalliferous sediments and have almost completely obliterated any original MORB-derived hydrothermal signal. Zn isotopes are mainly contributed from seawater although other Zn sources (hydrothermal fluid and detrital aluminosilicates, barite and volcanic glass) are necessary to fully explain Zn-isotope ratios. Fe isotopes indicate relatively slow Fe²⁺ to Fe³⁺ oxidation in the non-buoyant plume, thus producing relatively lighter Fe-isotope signature of the FeOOH particles that formed the studied metalliferous sediments.     

Transient States in Diagenesis Following the Deposition of a Gravity Layer: Dynamics of O<Subscript>2</Subscript>, Mn,Fe and N-Species in Experimental Units

Biogeochemical processes induced by the deposition of gravity layer in marine sediment were studied in a 295-day experiment. Combining voltammetric microelectrode measurements and conventional analytical techniques, the concentrations of C, O₂, N-species, Mn and Fe have been determined in porewaters and sediments of experimental units. Dynamics of the major diagenetic species following the sudden sediment deposition of few cm-thick layer was explained by alternative diagenetic pathways whose relative importance in marine sediments is still a matter of debate. Time-series results indicated that the diffusion of O₂ from overlying waters to sediments was efficient after the deposition event: anoxic conditions prevailed during the sedimentation. After a few days, a permanent oxic horizon was formed in the top few millimetres. At the same time, the oxidation of Mn²⁺ and then Fe²⁺, which diffused from anoxic sediments, contributed to the surficial enrichment of fresh Mn(III/IV)- and Fe(III)-oxides. Vertical diffusive fluxes and mass balance calculations indicated that a steady-state model described the dynamic of Mn despite the transitory nature of the system. This model was not adequate to describe Fe dynamics because of the multiple sources and phases of Fe²⁺. No significant transfer of Mn and Fe was observed between the underlying sediment and the new deposit: Mn- and Fe-oxides buried at the original interface acted as an oxidative barrier to reduced species that diffused from below. Nitrification processes led to the formation of a NO₃⁻/NO₂⁻ rich horizon at the new oxic horizon. Over the experiment period, NO₃⁻ concentrations were also measured in the anoxic sediment suggesting anaerobic nitrate production.     

Chemical forms of some heavy metals in Huanghe River sediments (China) and comparison with data from Rhine River sediments (West Germany)

The chemical forms of Fe, Mn, Zn, Cu, Cr, Pb and Cd in the Huanghe River sediments have been studied by sequential extraction techniques and the comparison with data from the Rhine River sediments has been made. In the Huanghe River sediments the average contents of metals, without exception, are below their respective contents in average shales and very close to their levels in Ca-poor granites. The major portion of metals is combined with the detrital and moderately reducible phases. Both in the Huanghe River and in the Rhine River sediments the distribution ratios of metals between the moderately reducible and the easily reducible phases are generally more than unity. However, the distribution ratios of Mn, Zn and Cd are obviously lower than those of Fe, Cr, Cu and Pb. As a result of contamination, the ratios of Fe, Cr, Cu and Pb show an apparent increase, but no remarkable ratio variation is observed for Mn, Zn and Cd. Metals in the Huanghe River sediments, especially Cu and Zn, show a tendency to be associated with the organic phase. The effect of carbonate on metal association preference seems to be less important than that in the Rhine River although there is higher content of carbonate in the Huanghe River sediments. Cd has a greater percentage of the exchangeable phase, which is similar to the result from the Rhine River sediments.     

The diagenetic geochemistry and contamination assessment of iron,cadmium, and lead in the sediments from the Shuangtaizi estuary,China

Sediment and pore water samples have been collected from the coastal tidal flat in the Shuangtaizi estuary, China, in order to investigate the geochemical behavior of iron, cadmium, and lead during diagenesis and to assess the degree of contamination. The calculated enrichment factors and geoaccumulation indices for separate elements show that anthropogenic activities have had no significant influence on the distribution of Fe and Pb in the study area, whereas the distribution of Cd has been closely influenced in this way. The high percentage of exchangeable Cd (average of 56.34%) suggests that Cd represents a potential hazard to benthic organisms in the estuary. The calculated diffusive fluxes of metals show that the most mobilized metal is Fe (9.22 mg m^?2 a^?1), followed by Cd (0.54 mg m^?2 a^?1) and Pb (0.42 mg m^?2 a^?1). Low Fe²⁺ contents in surface pore water, alongside high chromium-reducible sulfur contents, and low acid-volatile sulfur, and elemental sulfur contents at 0–25 cm depth in sediments show that Fe²⁺ is formed by the reduction of Fe oxides and is transformed first to a solid phase of iron monosulfides (FeS) and eventually to pyrite (FeS₂). The release of adsorbed Pb due to reductive dissolution of Fe/Mn oxides during early diagenesis could be a source of Pb²⁺ in pore water. From the relatively low total organic carbon contents measured in sediments (0.46–1.28%, with an average of 0.94%) and the vertical variation of Cd²⁺ in pore water, sulfide or Fe/Mn oxides (instead of organic matter) are presumed to exert a significant influence on carrying or releasing Cd by the sediments.     

Partitioning of copper and zinc in the sediments and porewaters of a high-elevation alkaline lake,east-central Arizona,U.S.A.

In Pacheta Lake, a high-elevation alkaline lake proximal to the smelting region of southern Arizona-New Mexico, concentrations of transition metal ions in pore waters and co-existing sediments were compared. Copper, Fe, Mn and Zn have been partitioned among operationally defined sediment solid phases (exchangeable sites, organic complexes, amorphous oxides, crystalline oxides, sulfides and residual silicates) and their concentrations in interstitial waters were measured. Concentrations are reported as a function of depth in the sediment column. The diagenetic environment is described and cycling mechanisms postulated for the above metals.Selective, sequential extraction of metals from lake sediments showed different binding mechanisms for Cu and Zn, the former most strongly associated with organic complexes, and the latter with iron oxyhydroxides. This difference has strong implications for selective metal remobilization under variable environmental conditions, both naturally and anthropogenically induced. Copper and zinc in porewaters were estimated to diffuse to overlying waters at 12.8 and 21.9 μg/cm²/a, respectively. These fluxes are large enough to account for observed concentrations of Cu and Zn in overlying waters. No sediment metal contamination was directly attributable to smelting activity. However, this study does document a flux from sediments, which have accumulated Cu and Zn, to overlying waters no longer receiving trace metal deposition from now inactive smelters.