Ra/Ra and Ra/Ba ratios to track barite formation and transport in the water column

We measured ²²⁸Ra_ex/²²⁶Ra_ex and ²²⁶Ra_ex/Ba_ex ratios in suspended and sinking particles collected at the Oceanic Flux Program (OFP) time-series site in the western Sargasso Sea and compared them to seawater ratios to provide information on the origin and transport of barite (BaSO₄) in the water column. The ²²⁸Ra_ex/²²⁶Ra_ex ratios of the suspended particles down to 2000 m are nearly identical to those of seawater at the same water depth. These ratios are much lower than expected if suspended barite was produced in surface waters and indicate that barite is produced throughout the mesopelagic layer. The ²²⁸Ra_ex/²²⁶Ra_ex activity ratios of sinking particles collected at 1500 and 3200 m varied mostly between 0.1 and 0.2, which is intermediate between the seawater ratio at these depths (<0.03) and the seawater ratios found in the upper 250 m (0.31-0.42). This suggests that excess Ba (i.e., Ba_ex = Ba_total − Ba_lithogenic), considered to be mainly barite, present in the sinking flux is a mixture of crystals formed recently in the upper water column, formed several years earlier in the upper water column, or formed recently in deeper waters. We observe a sizeable temporal variability in the ²²⁸Ra_ex/²²⁶Ra_ex ratios of sinking particles, which indicates temporal variability in the relative proportion of barite crystals originating from surface (with a high ²²⁸Ra_ex/²²⁶Ra_ex ratio) and mesopelagic (with a low ²²⁸Ra_ex/²²⁶Ra_ex ratio) sources. However, we could not discern a clear pattern that would elucidate the factors that control this variability. The ²²⁶Ra/Ba ratios measured in seawater are consistent with the value reported from the GEOSECS expeditions (2.3 dpm μmol⁻¹) below 500 m depth, but are significantly lower in the upper 500 m. High ²²⁶Ra_ex/Ba_ex ratios and elevated Sr concentrations in suspended particles from the upper water column suggest preferential uptake of ²²⁶Ra over Ba during formation of SrSO₄ skeletons by acantharians, which must contribute to barite formation in shallow waters. Deeper in the water column the ²²⁶Ra_ex/Ba_ex ratios of suspended particles are lower than those of seawater. Since ²²⁸Ra_ex/²²⁶Ra_ex ratios demonstrate that suspended barite at these depths has been produced recently and in situ, their low ²²⁶Ra_ex/Ba_ex ratios indicate preferential uptake of Ba over Ra in barite formed in mesopelagic water.     

Ra/Ra and Ra/Ba ratios in the Western Mediterranean Sea: Barite formation and transport in the water column

²²⁶Ra, ²²⁸Ra and Ba distributions as well as ²²⁸Ra/²²⁶Ra and ²²⁶Ra/Ba ratios were measured in seawater, suspended and sinking particles at the DYFAMED station in the Western Mediterranean Sea at different seasons of year 2003 in order to track the build-up and fate of barite through time. The study of the ²²⁸Ra_ex/²²⁶Ra_ex ratios (Ra_ex = Ra activities corrected for the lithogenic Ra) of suspended particles suggests that Ba_ex (Ba_ex = Ba concentrations corrected for the lithogenic Ba, mostly barite) formation takes place not only in the upper 500 m of the water column but also deeper (i.e. throughout the mesopelagic layer). Temporal changes in the ²²⁸Ra_ex/²²⁶Ra_ex ratios of sinking particles collected at 1000 m depth likely reflect changes in the relative proportion of barite originating from the upper water column (with a high ²²⁸Ra/²²⁶Ra ratio) and formed in the mesopelagic layer (with a low ²²⁸Ra/²²⁶Ra ratio). ²²⁸Ra_ex/²²⁶Ra_ex ratios measured in sinking particles collected in the 1000 m-trap in April and May suggest that barite predominantly formed in the upper water column during that period, while barite found outside the phytoplankton bloom period (February and June) appears to form deeper in the water column. Combining ratios of both the suspended and sinking particles provides information on aggregation/disaggregation processes. High ²²⁶Ra_ex/Ba_ex ratios were also found in suspended particles collected in the upper 500 m of the water column. Because celestite is expected to be enriched in Ra [Bernstein R. E., Byrne R. H. and Schijf J. (1998) Acantharians: a missing link in the oceanic biogeochemistry of barium. Deep-Sea Res. II45, 491-505], acantharian skeletons may contribute to these high ratios in shallow waters. The formation of both acantharian skeletons and barite enriched in ²²⁶Ra may thus contribute to the decrease in the dissolved ²²⁶Ra activity and ²²⁶Ra/Ba ratios of surface waters observed between February and June 2003 at the DYFAMED station.     

Seasonal variability of deep ocean particle fluxes and particle composition in the north open sea of Prydz Bay

Time-series Mark VII sediment trap was deployed at 72°58.55′E, 62°28.63°S (north of the Prydz Bay, Antarctica) during the cruise of CHINARE-15 in cooperation with University of Marine of America. Seasonal variability of deep ocean particle fluxes and biogenic components were investigated in order to reveal the fluxes and biogeochemistry of sinking particles in the deep ocean. The results show that the total mass flux of sinking particles at a water depth of 1000 m ranges from 13.00 to 334.59 mg⋅d⁻¹⋅m⁻²). A marked seasonal variability exists in the fluxes of all particle components reflecting the seasonal changes in upper water productivity. Biogenic material was a significant component and biogenic silica represented more than 80% of the biogenic matter, reflecting a diatom dominated system, but a lithogenic fraction is always present. The fact that the POC dominated over particulate inorganic carbon (as CaCO₃) and C_inorg/C_org was always greater than 1, indicate a net removal of CO₂ from surface water by biological activity. __________ Translated from Acta Oceanologica Sinica, 2006, 5: 49–55 [译自:海洋 学报]     

Particulate sulfur species in the water column of the Cariaco Basin

The biogeochemistry of iron sulfide minerals in the water column of the Cariaco Basin was investigated in November 2007 (non-upwelling season) and May 2008 (upwelling season) as part of the on-going CARIACO (CArbon Retention In A Colored Ocean) time series project. The concentrations of particulate sulfur species, specifically acid volatile sulfur (AVS), greigite, pyrite, and particulate elemental sulfur, were determined at high resolution near the O₂/H₂S interface. In November 2007, AVS was low throughout the water column, with the highest concentration at the depth where sulfide was first detected (260 m) and with a second peak at 500 m. Greigite, pyrite, and particulate elemental sulfur showed distinct concentration maxima near the interface. In May 2008, AVS was not detected in the water column. Maxima for greigite, pyrite, and particulate elemental sulfur were again observed near the interface. We also studied the iron sulfide flux using sediment trap materials collected at the Cariaco station. Pyrite comprised 0.2-0.4% of the total particulate flux in the anoxic water column, with a flux of 0.5-1.6 mg S m⁻² d⁻¹.Consistent with the water column concentration profiles for iron sulfide minerals, the sulfur isotope composition of particulate sulfur found in deep anoxic traps was similar to that of dissolved sulfide near the O₂/H₂S interface. We conclude that pyrite is formed mainly within the redoxcline where sulfur cycling imparts a distinct isotopic signature compared to dissolved sulfide in the deep anoxic water. This conclusion is consistent with our previous study of sulfur species and chemoautotrophic production, which suggests that reaction of sulfide with reactive iron is an important pathway for sulfide oxidation and sulfur intermediate formation near the interface. Pyrite and elemental sulfur distributions favor a pathway of pyrite formation via the reaction of FeS with polysulfides or particulate elemental sulfur near the interface. A comparison of thermodynamic predictions with actual concentration profiles for iron sulfides leads us to argue that microbes may mediate this precipitation.     

Barite in the ocean – occurrence,geochemistry and palaeoceanographic applications

The mineral barite (BaSO₄) can precipitate in a variety of oceanic settings: in the water column, on the sea floor and within marine sediments. The geological setting where barite forms ultimately determines the geochemistry of the precipitated mineral and its usefulness for various applications. Specifically, the isotopic and elemental composition of major and trace elements in barite carry information about the solution(s) from which it precipitated. Barite precipitated in the water column (marine or pelagic barite) can be used as a recorder of changes in sea water chemistry through time. Barite formed within sediments or at the sea floor from pore water fluids (diagenetic or cold seeps barite) can aid in understanding fluid flow and sedimentary redox processes, and barite formed in association with hydrothermal activity (hydrothermal barite) provides information about conditions of crust alteration around hydrothermal vents. The accumulation rate of marine barite in oxic‐pelagic sediments can also be used to reconstruct past changes in ocean productivity. Some key areas for future work on the occurrence and origin of barite include: fully characterizing the mechanisms of precipitation of marine barite in the water column; understanding the role and potential significance of bacteria in barite precipitation; quantifying parameters controlling barite preservation in sediments; determining the influence of diagenesis on barite geochemistry; and investigating the utility of additional trace components in barite.     

Quantifying the seasonal variations in fluvial and eolian sources of terrigenous material to Cariaco Basin,Venezuela

The varved sediments that accumulate in the Cariaco Basin provide a detailed archive of the region’s climatic history, including a record of the quantity of fluvial and wind-transported material. In this study, we examine the sedimentological characteristics (clay mineralogy and grain size) of both surface sediments and sinking lithogenic material collected from sediment trap samples over a three-year period from 1997 to 2000. Data from biweekly sediment trap samples show a tri-modal particle size distribution, with prominent peaks at 2, 22 and 80 μm, indicating sediment contributions from both eolian and fluvial sources. The clay mineralogy of the water column samples collected from 1997 to 1999 also shows distinctive characteristics of eolian and fluvial material. An examination of surface sediment samples from the Cariaco Basin indicates that the Unare River is the main source of riverine sediments to the eastern sub-basin. By combining these sedimentological proxies, we estimate that ～10% of the terrigenous material delivered to the Cariaco Basin is eolian, while ～90% is fluvial. This represents an annual dust accumulation rate of ～0.59 mg/cm²/yr. Since aerosols are closely linked to climate variability, the ability to quantify paleo-dust fluxes using sedimentological characteristics will be a useful tool for future paleoclimate studies looking at sub-Saharan aridity and latitudinal migration of the Intertropical Convergence Zone.     

Seasonal cycle of suspended barite in the mediterranean sea

Biogenic barium (Ba_xs) was measured in suspended particles at the DYFAMED site in the northwestern Mediterranean Sea, on a monthly basis between February and June 2003. The barium content of barite (BaSO₄) micro-crystals was investigated using Scanning Electron Microscopy (SEM). Suspended particles were collected by filtration of small volumes of seawater (∼10 L), as well as large volumes up to 2400 L in March and in May. The Ba_xs profiles obtained from small-volume filtration display the typical mesopelagic maximum reported by earlier studies at ∼200 m depth, with concentrations up to 595 pmol L⁻¹. In addition, suspended Ba_xs was found almost exclusively in the form of micro-crystalline barite, except in February. The Ba_xs profiles obtained from large-volume filtration are consistent with the small-volume filtration findings, but reveal a significant Ba_xs peak of 1698 pmol L⁻¹ in the surface waters in May. Seasonal sampling at the DYFAMED site shows a net increase in barite concentration during phytoplanktonic blooms, confirming the involvement of biological systems in barite formation, as well as the potential role of barite as a primary productivity tracer. In addition, the coincidence between the mesopelagic barite maximum and the oxygen minimum layer suggests that barite is primarily found at depths of intense remineralization, in agreement with the hypothesis that barite forms within microenvironments of decaying organic matter.     

Calcite dissolution in two deep eutrophic lakes

The calcium cycle, in particular carbonate dissolution, was analyzed in two deep eutrophic lakes, Lago di Lugano (288 m maximum depth) and Sempachersee (87 m) located in Switzerland. A box model approach was used to calculate calcite dissolution in the water column and at the sediment-water interface based on various lake monitoring data such as sediment traps, sediment cores, water and pore-water analysis. A model for stationary conditions allowing the calculation of calcite dissolution in the water column for a given particle size distribution was developed. The relative values of the simulated flux were consistent with sediment trap observations. The best fit of the dissolution rate constant of sinking calcite in Lago di Lugano was on the same order of magnitude (3 · 10⁻¹⁰ kg^1/3 s⁻¹) as published laboratory values for this surface controlled process.Both lakes show a similar specific calcite precipitation rate of 170 g Ca m⁻² a⁻¹. The diffusive flux across the sediment-water interface amounts to about 15 and 10% of total calcite precipitation in Sempachersee and Lago di Lugano, respectively. However, 61% of the precipitated calcite is dissolved in the water column of Lago di Lugano compared to only 13% in Sempachersee. These results point towards the importance of grain size distributions and settling times in stratified deep waters as the two most important factors determining calcite retention in sediments of hard water lakes.     

Cretaceous black shales as active bioreactors: A biogeochemical model for the deep biosphere encountered during ODP Leg 207 (Demerara Rise)

A transport-reaction model was designed to identify the combination and importance of biogeochemical processes operating in four sites drilled during ODP Leg 207 (Demerara Rise, Equatorial Atlantic). Almost 100 Ma after their deposition, deeply buried Cretaceous black shales still act as active bioreactors in great sediment depths and control the biogeochemical reaction network of the whole sediment column. According to a model calibrated at the four drill sites through inverse modeling techniques, methanogenesis could be identified as a key process that dominates not only organic matter degradation but also sulfate availability through the anaerobic oxidation of methane above the black shales. A complete depletion of sulfate within the black shale sequences promotes the remobilization of biogenic barium that reprecipitates as authigenic barite at the top of the sulfate depletion zone. Temporal dynamics of degradation processes caused continuous shifts of the barite precipitation zone during burial, thus inhibiting the formation of an authigenic barite front or causing the dissolution of earlier formed fronts. Major deviations of pore water sulfate profiles from a linear gradient coincide with depths of decelerated or accelerated transport caused by local porosity minima or maxima. Model-determined reaction rates are by far lower than those found in shallower sediments due to the low metabolic activities that are characteristic for the Deep Biosphere. But even after almost 100 Ma, changing organic matter quality still influences the degradation within the black shale sequences, as it is indicated by model results.     

Suboxic trace metal geochemistry in the Eastern Tropical North Pacific

We analyzed Al, Ti, Fe, Mn, Cu, Ba, Cd, U, Mo, V, and Re in water column, settling particulate, and sediment (0 to 22 cm) samples from the intense oxygen minimum zone (OMZ) of the eastern tropical North Pacific near Mazatlán, Mexico. The goal was to determine how the geochemistry of these elements was influenced by suboxic water column conditions and whether the sediments have a unique “suboxic” geochemical signature.The water column was characterized by a Mn maximum, reaching ∼8 nmol kg⁻¹ at 400 m. Concentrations of Cu, Ba, Cd, Mo, Re, U, and V were unaffected by the low O₂ conditions and were comparable to those of the open ocean. Sinking particles were composed of lithogenic particles of detrital origin and nonlithogenic particles of biogenic origin. Al, Ti, and Fe were mostly (at least 79%) lithogenic. About 75% of the Mn was nonlithogenic. Significant amounts (at least 58%) of Cu, Ba, Cd, and Mo were nonlithogenic.Sediment geochemistry varied across the continental shelf and slope. Cadmium, U, and Re have prominent maxima centered at 310 m, with 12.3 ppm, 10.9 ppm, and 68.3 ppb, respectively, at the core top. High values of Mo (averaging 6.8 ppm) and V (averaging 90 ppm) are seen in OMZ surface sediment. Additional down-core enrichment occurs for all redox-sensitive elements in the top 10 cm. For U, Mo, V, and Re, surface sediments are a poor indicator of metal enrichment. Comparison of the nonlithogenic composition of sediments with sinking particles suggests that direct input of plankton material enriched in metals makes a significant contribution to the total composition, especially for Cd, U, and Mo.We evaluated Re/Mo and Cd/U ratios as tracers for redox environments. Rhenium and Mo concentrations and Re/Mo ratios do not lead to consistent conclusions. Concurrent enrichments of Re and Mo are an indicator of an anoxic depositional environment. In contrast, high Re/Mo ratios are an indicator of suboxic conditions. Cadmium is enriched in surface sediments, while U has considerable down-core enrichment. The concentrations of Cd and U and the Cd/U ratio do not follow patterns predicted from thermodynamics. Though the water column is suboxic, these four redox-sensitive elements indicate that the sediments are anoxic. The implication for paleostudies is that a trace metal sediment signature that indicates anoxic conditions is not necessarily attributable to an anoxic water column.     

南海颗粒物质的通量、组成及其与沉积物积累率的关系初探

通过大孔径时间系列沉积物捕获器的多年测量及对样品的多学科综合分析表明:南海北部与中部深海区1000m左右水深颗粒通量大约为90mg·m-2·d-1,在多数情况下,季风期间的颗粒通量有比较明显的增高。颗粒物主要组成为钙质生物来源的CaCO₃、生物硅、岩源物质及海洋生物来源的有机质。颗粒通量与组成在水柱中的垂向变化表明,生源组分中CaCO₃及有机质随深度具有较为明显的减少。颗粒物侧向运动可能是造成某些时段南海中部深层颗粒通量增加的主要原因。颗粒物质在进入深海沉积物之前,CaCO₃、生物硅均在深层水与沉积物界面之间发生大量的溶解作用。有机质在沉降过程中的减少,一方面是由于硅质与钙质壳体的溶解而使结合在壳体内部的有机质随之溶解造成;另一方面可能与生物及生物地球化学作用有关。岩源物质除水柱沉降之外,还可以通过浊流等底层搬运机制进入南海北部及中部海盆,其中在南海北部这种搬运作用更为明显。     

雅浦海沟北部深渊和超深渊沉积物的物质组成、来源和形成过程研究

为探究雅浦海沟北部深渊、超深渊沉积物的组成、来源和形成特征,以1 cm分层对采自该海域不同深度的五根柱状沉积物样品的0~8 cm沉积层进行了扫描电子显微镜(SEM)观察和X射线能谱(EDS)分析,并且分析了这些样品的含水率,锰结核含量, Al、Ca、Fe、Mn、Ti、Mg等6种常量金属和Ba、Co、Cr、Ni、Pb、Sr、V、Cu、Zn等9种微量金属元素含量,以及总有机碳(TOC)含量等参数。结果表明,研究区域沉积物主要为深海软泥沉积,是不同年代沉积物的复杂混合,包含以盘星石为代表的颗石藻、海绵骨针、放射虫和硅藻等多种微体古生物化石以及辉石、重晶石、钛铁矿、长石等多种矿物。沉积组分主要来自生物源、火山源、陆源和海底热液,其中陆源沉积出现于海沟东侧深渊区。海沟西侧崖壁的沉积物比东侧崖壁的沉积物更容易发育锰结核。研究区域沉积物含水率较高并且颗粒较大,其含水率随深度增加呈减少趋势。研究区域超深渊站位沉积物的TOC和微体古生物化石含量均高于深渊站位,存在明显的漏斗效应。整体上海沟西侧崖壁沉积物含水率和TOC含量低于东侧崖壁的沉积物。自更新世以来,雅浦海沟北部的碳酸钙补偿深度(CCD)线从4 568 m以深变为4 435 m至4 568 m之间。研究区域的沉积环境为氧化环境,其0~8 cm沉积层的古老沉积物与现代沉积物发生了混合和再沉积作用,形成年代跨度极大。研究区域沉积物的形成受到海沟坡度、水动力环境、重力滑塌、浊流沉积、火山活动、漏斗效应等多种因素的显著影响。     

The mobility of radium-226 and trace metals in pre-oxidized subaqueous uranium mill tailings

The exchange of ²²⁶Ra and trace metals across the tailings-water interface and the mechanisms governing their mobility were assessed via sub-centimetre resolution profiling of dissolved constituents across the tailings–water interface in Cell 14 of the Quirke Waste Management Area at Rio Algom's Quirke Mine, near Elliot Lake, Ontario, Canada. Shallow zones (<1.5 m water depth) are characterized by sparse filamentous vegetation, well-mixed water columns and fully oxygenated bottom waters. Profiles of dissolved O₂, Fe and Mn indicate that the tailings deposits in these areas are sub-oxic below tailings depths of ∼3 cm. These zones exhibit minor remobilization of Ra in the upper 5 cm of the tailings deposit; ²²⁶Ra fluxes at these sites are relatively small, and contribute negligibly to the water column activity of ²²⁶Ra. The shallow areas also exhibit minor remobilization of Ni, As, Mo and U. The release of these elements to the water cover is, however, limited by scavenging mechanisms in the interfacial oxic horizons. The presence of thick vegetation (Chara sp.) in the deeper areas (>2 m water depth) fosters stagnant bottom waters and permits the development of anoxia above the benthic boundary. These anoxic tailings are characterized by substantial remobilization of ²²⁶Ra, resulting in a relatively large flux of ²²⁶Ra from the tailings to the water column. The strong correlation between the porewater profiles of ²²⁶Ra and Ba (r²=0.99), as well as solubility calculations, indicate that the mobility of Ra is controlled by saturation with respect to a poorly ordered and/or impure barite phase [(Ra,Ba)SO₄]. In the anoxic zones, severe undersaturation with respect to barite is sustained by microbial SO₄ reduction. Flux calculations suggest that the increase in ²²⁶Ra activity in the water cover since 1995 (from <0.5 to 2.5 Bq l⁻¹) can be attributed to an increase in the spatial distribution of anoxic bottom waters caused by increased density of benthic flora. The anoxic, vegetated areas also exhibit minor remobilization with respect to dissolved As, Ni and Zn. The removal of trace metals in the anoxic bottom waters appears to be limited by the availability of free sulphide. Collectively, the data demonstrate that while the water cover over the U mill tailings minimizes sulphide oxidation and metal mobility, anoxic conditions which have developed in deeper areas have led to increased mobility of ²²⁶Ra.     

Changes in the molecular-level characteristics of sinking marine particles with water column depth

Over the past decade, sinking particulate organic matter (POM) samples from depth profiles in the equatorial Pacific have been analyzed by multiple techniques to evaluate the organic matter preservation mechanisms most dominant in the oceanic water column. How the samples were analyzed strongly influenced which organic matter preservation scheme appeared to dominate. Bulk functional group analysis by solid-state ¹³C-NMR showed that organic matter composition varied very little in light of the extreme degree of remineralization (>98%) that occurred with water column depth. This indicates preservation by a physical mechanism, such as sorption to mineral grains or protection within a mineral aggregate. However, detailed lipid studies of the characterizable fraction showed that selective preservation was important, with lipid structure being correlated with preservation over depth. However, the characterizable fraction decreases greatly with depth. Therefore, in this paper, direct temperature-resolved mass spectrometry (DT-MS), was used to further characterize POM, with the assumption that this approach could “see” a substantial proportion of the “uncharacterized” organic matter. DT-MS, which provides compositional information at an intermediate level between the detailed wet chemical studies and one-dimensional solid-state C¹³-NMR, also indicates an intermediate view between the mechanistic extremes of selective preservation and physical protection.     

Steroid geochemistry in the oxygen minimum zone of the eastern tropical North Pacific Ocean

Particulate matter was collected in the eastern tropical North Pacific Ocean, an area characterized by a shallow and intense oxygen minimum zone, in order to investigate the geochemistry of particulate organic matter in the ocean. Sinking, large particles and suspended, small particles were analyzed for sterols, 3-ketosteroids, 3-methoxy-steroids and sterenes. Vertical fluxes of steroid classes in sinking particles and concentrations of steroids in suspended particles decreased rapidly below the euphotic zone consistent with upper ocean sources and deep water decomposition. Significant compositional changes were observed with increasing depth and as a function of particle size. Sinking particles were enriched in C₂₇-Sterols but deficient in C₂₈ and C₂₉-sterols compared to the suspended particles. Suspended particles, especially in the oxygen minimum zone, were enriched in steroidal ketones and sterenes compared to sinking particles. Steroid distributions suggest that the oxygen minimum zone is the site of active “diagenetic” transformations, most likely microbially-mediated, of stenols to steroidal ketones, stanols and sterenes. These transformations occur preferentially in suspended particles relative to sinking particles.     

Geochemistry of Rare Earth Elements in the Ocean

This work briefly outlines modern ideas on geochemistry of rare earth elements (REE) in the ocean. Sources of REE and chemical properties of these elements, which govern their migration ability in natural processes, are considered. The REE behavior in the river water–seawater mixing zone is analyzed. The fractionation of dissolved and suspended REE in oceanic water in both aerobic and anaerobic conditions is also considered. It is shown that the variability of REE composition in pelagic sediments reflects the fractionation of these elements in the oceanic water as a consequence of material differentiation in the ocean. The REE distribution in terrigenous, authigenic, hydrothermal, and biogenic constituents of sediments, such as clay, bone debris, barite, phillipsite, Fe–Mn oxyhydroxides (ferromanganese nodules and micronodules), Fe–Ca hydroxo-phosphate, diatoms, and foraminifers, is considered.     

Natural contribution of harmful elements in thermal groundwaters of Ischia Island (southern Italy)

Minor and trace element investigations have been performed on groundwaters of Ischia Island, which is located at the western edge of the bay of Naples. Ischia is formed entirely of Quaternary volcanic rocks. Intense seismicity, widespread fumaroles and thermal springs witness the persistent state of activity of its magmatic system. Groundwater samples, 58 from shallow thermal wells and 15 from thermal springs, were analysed for 72 elements by ICP-MS; temperature, pH and electrical conductivity (EC) were measured at the sampling site. Analytical data indicate clearly that the concentrations in the water of some elements, such as As, Be, Cu, Fe, Mn, Sb, Se and Tl, are often higher and sometimes much higher than the intervention limits fixed by the Italian Law DM 471 (25/10/1999) for water. Worthy of mention are the very high As values, reaching >1,000 µg/l in some wells. By means of R-mode factor analysis, 30 of 72 analysed elements were grouped as elemental associations representative of lithological type, water composition and, possibly, mineralization. Ischia thermal groundwaters are the result of mixing, in variable amounts, of deep magmatic fluids that are rich in metallic elements, with marine and/or meteoric waters. R-mode factor analysis and elemental association factor score distributions of the four-factor model confirm the existence of flux of magmatic mineralised fluids with marine and/or meteoric waters. Recharge by seawater intrusions occurs mostly in the north-western area of the island whereas the influence and control of magmatic mineralised fluids is clearly accentuated in the areas of Panza-Citara, Porto di Forio-Fango and Citara-Lido dei Maronti fracture alignments. The observed compositional variability of the analysed groundwaters, even in wells lying close to one another, is due to the local hydrodynamic conditions, controlled mostly by complex fault and fracture systems, which may represent preferential thermal water outflow routes. In general, the average minor and trace element compositions of Ischia thermal waters, when compared with the composition of sea and river water, show an enrichment in metallic elements such as As, Sc, V, Cr, Zn, Mo, U, W, Au, Hg. This paper points out that, in addition to the anthropogenic source, natural contribution also plays an important role in determining the high concentrations of toxic elements in groundwaters, which create health and acceptability problems.     

海底沉积物孔隙水钡循环对天然气渗漏的指示

冷泉流体的渗漏活动强烈地影响着海底沉积物孔隙水钡循环。冷泉流体中的Ba2+ 向上扩散与孔隙水硫酸盐反应,在硫酸盐—碳氢化合物转化带（SHT）之上沉淀重晶石。随着沉积物的埋藏,先前沉淀的重晶石被埋藏于SHT之下的硫酸盐亏损带,将发生溶解,溶解的钡向上扩散,在SHT之上再次沉淀重晶石。当体系中向上扩散的Ba2+超过埋藏的重晶石中的钡时,在剖面上形成“钡锋”。向上渗漏的碳氢化合物（甲烷为主）通量控制了SHT的深度,二者之间存在很好的地球化学耦合关系,从而,可以用“钡锋”来评价天然气渗漏活动的特征。在总结和分析国际海底冷泉渗漏活动区沉积物孔隙水的甲烷和钡循环的研究进展基础上,综述了海底沉积物孔隙水钡循环对现在和过去天然气渗漏的指示,总结了渗漏成因重晶石的地质和地球化学特征。     

Normalizing XRF-scanner data: A cautionary note on the interpretation of high-resolution records from organic-rich lakes

X-ray fluorescence (XRF) scanning of unlithified, untreated sediment cores is becoming an increasingly common method used to obtain paleoproxy data from lake records. XRF-scanning is fast and delivers high-resolution records of relative variations in the elemental composition of the sediment. However, lake sediments display extreme variations in their organic matter content, which can vary from just a few percent to well over 50%. As XRF scanners are largely insensitive to organic material in the sediment, increasing levels of organic material effectively dilute those components that can be measured, such as the lithogenic material (the closed-sum effect). Consequently, in sediments with large variations in organic material, the measured variations in an element will to a large extent mirror the changes in organic material. It is therefore necessary to normalize the elements in the lithogenic component of the sediment against a conservative element to allow changes in the input of the elements to be addressed. In this study we show that Al, which is the lightest element that can be measured using the Itrax XRF-scanner, can be used to effectively normalize the elements of the lithogenic fraction of the sediment against variations in organic content. We also show that care must be taken when choosing resolution and exposure time to ensure optimal output from the measurements.