Calcium isotope evidence for suppression of carbonate dissolution in carbonate-bearing organic-rich sediments

Pore fluid calcium isotope, calcium concentration and strontium concentration data are used to measure the rates of diagenetic dissolution and precipitation of calcite in deep-sea sediments containing abundant clay and organic material. This type of study of deep-sea sediment diagenesis provides unique information about the ultra-slow chemical reactions that occur in natural marine sediments that affect global geochemical cycles and the preservation of paleo-environmental information in carbonate fossils. For this study, calcium isotope ratios (δ^44/40Ca) of pore fluid calcium from Ocean Drilling Program (ODP) Sites 984 (North Atlantic) and 1082 (off the coast of West Africa) were measured to augment available pore fluid measurements of calcium and strontium concentration. Both study sites have high sedimentation rates and support quantitative sulfate reduction, methanogenesis and anaerobic methane oxidation. The pattern of change of δ^44/40Ca of pore fluid calcium versus depth at Sites 984 and 1082 differs markedly from that of previously studied deep-sea Sites like 590B and 807, which are composed of nearly pure carbonate sediment. In the 984 and 1082 pore fluids, δ^44/40Ca remains elevated near seawater values deep in the sediments, rather than shifting rapidly toward the δ^44/40Ca of carbonate solids. This observation indicates that the rate of calcite dissolution is far lower than at previously studied carbonate-rich sites. The data are fit using a numerical model, as well as more approximate analytical models, to estimate the rates of carbonate dissolution and precipitation and the relationship of these rates to the abundance of clay and organic material. Our models give mutually consistent results and indicate that calcite dissolution rates at Sites 984 and 1082 are roughly two orders of magnitude lower than at previously studied carbonate-rich sites, and the rate correlates with the abundance of clay. Our calculated rates are conservative for these sites (the actual rates could be significantly slower) because other processes that impact the calcium isotope composition of sedimentary pore fluid have not been included. The results provide direct geochemical evidence for the anecdotal observation that the best-preserved carbonate fossils are often found in clay or organic-rich sedimentary horizons. The results also suggest that the presence of clay minerals has a strong passivating effect on the surfaces of biogenic carbonate minerals, slowing dissolution dramatically even in relation to the already-slow rates typical of carbonate-rich sediments.     

Selective extraction of organically bound gold in soils, lake sediments and stream sediments

The extraction of organically bound gold from surficial materials is accomplished by using a solution of 5% sodium hypochlorite. A 10-g sample is digested at least twice with 50 mL of hypochlorite solution. The recovery of gold from the organic phase is nearly quantitative for lake sediments and stream sediments high in organic content. For stream sediments and soils low in organics, the recovery of gold is complicated by the sorption of released gold onto inorganic sample components. For these materials, recoveries as low as 70% of the organically bound gold are possible. For a stream sediment sample containing 53.4 ppb gold, the precision of the method is approximately 6% for a 10-g sample and 14% when a 5-g sample of stream sediment is used. The results obtained for all materials tested indicate that a substantial fraction of the gold found in sediments and soils exists as organically bound gold.     

An investigation into the selective dissolution of sulphide phases from stream sediments and soils

A leaching technique was investigated for the dissolution of sulphide and other mineral phases in geochemical exploration samples. Samples were leached with a mixture of H₂O₁ and ascorbic acid at room temperature and the insoluble residues were leached a second time with a warm solution of ammonium acetate. Sample solutions were analysed by atomic absorption spectrophotometry. Results obtained provide useful information for assessing the significance of anomalous geochemical exploration data.     

Sulphur cycling in organic-rich marine sediments from a Scottish fjord

In this study, the biogeochemical transformations of sulphur in organic‐rich marine sediments in a Scottish fjord are investigated by a combination of pore water and sediment geochemistry with sulphide diffusive gradient thin‐film probes and sulphate isotopic data (δ³⁴S and δ¹⁸O). Particular attention is paid to sulphur cycling in the upper sediment profile where sulphate reduction occurs but free sulphide is below the detection limits of conventional pore water geochemical analysis but quantifiable by sulphide diffusive gradient thin film. In the uppermost part of the sediment core, δ¹⁸O sulphate decreased from near‐sea water values to +7‰, indicating that anoxic sulphide oxidation dominated during this interval. Sulphate δ³⁴S remained unchanged as there was no net sulphate reduction (i.e. reduction was balanced by re‐oxidation). Below 4 cm depth, there was a slight increase in sulphate δ³⁴S from 20‰ to 23‰ associated with minor accumulation of iron sulphide. The δ¹⁸O of the sulphate also increased, to around +10‰ at 10 cm depth, as a result of the isotopic exchange of sulphate–oxygen with pore water and/or sulphur disproportionation reactions mediated during sulphur cycling. These processes continued to increase the δ¹⁸O of the sulphate to 14‰ at 20 cm depth with no further change in the δ³⁴S of the sulphate. Below 20 cm depth, free sulphide is detectable in pore waters and both the δ³⁴S of the sulphate and sulphide increase with depth with an offset controlled by kinetic fractionation during bacterial sulphate reduction. The δ³⁴S of the sedimentary organic fraction shifted towards lower, more bacteriogenic, values with depth in the profile, without any increase in the size of this sulphur pool. Thus, the organic sulphur fraction was open to interaction with bacteriogenic sulphide without the occurrence of net addition. Therefore, caution should be exercised when using sulphur isotopic compositions to infer simple net addition of bacteriogenic sulphide to the organic sulphur fraction.     

Thermoluminescence dating of sediments from Oulainen and Vimpeli, Ostrobothnia, Finland

Mean ages of 94 ka and 121 ka were obtained at Oulainen for two sand layers situated above and below an organic deposit previously correlated with the Brörup interstadial. At Vimpeli, TL dates obtained for sand layers embedded in an organic deposit suggest an age for this deposit of 107 ka. The uncertainty in this result is considerable, however. Problems encountered in dating these sediments and the reliability of the results are discussed.     

Geochemistry of stream water in a catchment in Finland affected by sulphidic fine sediments

The impact of sediment type on stream water geochemistry was studied in a catchment in Finland affected by sulphidic fine-grained sediments. Stream water samples for general characterisation of water quality (pH, electrical conductivity) were taken at the basin outlet during various hydrological conditions, while samples for detailed geochemical analysis were collected at 119 sites in the catchment on one single occasion during high-water flow in autumn. The occurrence of sulphidic fine sediments was estimated based on data from an airborne electromagnetic survey carried out by the Geological Survey of Finland.Growing-symbol maps, which were prepared for each of the studied variables in water, and statistical calculations including factor analysis and Spearman correlations show that the concentrations of Al, Ga, U and Tl, all the lanthanides and several alkali and alkaline earth metals (K, Mg, Na, Li, Ca, Rb, Sr), transition metals (Cd, Co, Cu, Zn, Sc, Mn, Ni, Y, Hf) and non-metals (S, Br, I, Si) increase in water when the proportion of the catchment cover of sulphidic fine sediments increases. It is therefore argued that these elements are released and mobilised in considerable amounts by the oxidation and subsequent acidification and weathering of this type of sediment. Other elements are either slightly depleted in streams in areas of sulphidic fine sediments (V, Nb, Pb, Zr), have a distribution unrelated to sediment type (Fe, Cr, Cs, Mo), or are only weakly impacted by the occurrence of sulphidic sediments in the catchment (As, Ti, Ba). It is argued that these elements are not leached extensively from the oxidising sulphidic sediments, and that their distributions at least partly may be controlled by the contents of dissolved humic material and/or suspended organic and inorganic phases in the water.     

Diagenesis of dissolved aluminum in organic-rich estuarine sediments

The sedimentary geochemistry of dissolved Al is complicated by a number of different reactions. In this study we show that complexation by organic matter, adsorption to Fe-oxyhydroxides, and reaction with Si in solution have important effects on the distribution of dissolved Al in sediments. In the absence of physical resuspension of sediment into overlying waters, dissolved Al is rapidly consumed at the sediment-water interface and is subsequently released upon reduction of Fe-oxyhydroxides. This release does not cause noticeable perturbations in dissolved Al concentrations in sediments because of rapid consumption reactions which mask the true mobility of Al. Results suggest that one of the consumption reactions may be due to formation of an Fe-Al-silicate. The amount of authigenic aluminosilicate formed in estuarine sediments must be very small relative to the detrital component. In the deep-sea, however, the long residence time of Fe-oxyhydroxides at the sediment-water interface, with resulting greater accumulation of adsorbed Al may explain the abundance of Al in Fe-smectites reported from many different areas.     

Modern pollen spectra from lake sediments in Finland and Finnmark, north Norway

Absolute (APF) and relative surface pollen spectra from 67 moderate-sized lakes in Finland and Finnmark are presented as pollen diagrams and isopoll maps and analysed by multidimensional scaling. The results are applicable to problems of regional vegetational history through comparisons of pollen spectra and the use of R-values. It is shown that relative spectra can discriminate the major vegetational regions. APFs give better resolution among northern forest regions and low APFs characterize tundra. Gradients of tree-pollen percentages in south and central Finland are related quantitatively to the major forest gradients, which are azonal, mainly related to soils, and affected but not obscured by human influence. Forest clearance is reflected in frequencies of various non-tree pollen types. Non-tree pollen and spores also provide vegetational and climatic information in the far north.     

Heavy minerals in stream sediments,Southwest Norway

As part of a regional prospecting programme, 600 panned stream sediment concentrates from 1000 km² have been examined for scheelite (CaWO₄) using ultraviolet light. The mineralogical compositions of the heavy mineral concentrates were determined and related to bedrock geology. The results of the investigation are presented on maps showing the distribution of scheelite, magnetite, and ilmenite. Follow-up work resulted in the discovery of nine new tungsten occurrences. Magnetite dominates in areas of acid rocks, and ilmenite in areas of basic rocks. The areal distribution of hornblende and hypersthene reflects the metamorphic grades.     

Selective extraction of anthropogenic lead from sediments using Tiron

A selective extraction method for anthropogenic lead is presented. Successive extractions using a 0.1 M Tiron solution (4,5-dihydroxy-1,3 benzene disulfonic acid disodium salt) at pH= 8 and 80°C for 6 h successfully extract anthropogenic lead from the sediment surface without leaching natural lead associated with the sediment matrix. This method helps acquire a more detailed knowledge of the history of lead pollution in a given river catchment. For instance, it has been found that the first lead fallout appeared in the Montreal region in the early 1920's, whereas they are detected around 1930 in the Saguenay region, province of Quebec. Information on lead availability is obtained and it is found that iron hydroxides play a significant role on the lead retention.     

Estimating specific surface area of fine stream bed sediments from geochemistry

Specific surface area (SSA) of headwater stream bed sediments is a fundamental property which determines the nature of sediment surface reactions and influences ecosystem-level, biological processes. Measurements of SSA – commonly undertaken by BET nitrogen adsorption – are relatively costly in terms of instrumentation and operator time. A novel approach is presented for estimating fine (<150 μm) stream bed sediment SSA from their geochemistry – after removal of organic matter – for agricultural headwater catchments across 15,400 km² of central England, UK. From a regional set of 1972 stream bed sediment sites with common characteristics for which geochemical data were available, 60 samples were selected – based on maximising their variation in Al concentrations – and their BET SSA measured by N₂ adsorption. After careful selection of potential regression predictors following a principal component analysis and removal of a subset of samples with the largest Mo concentrations (>2.5 mg kg⁻¹), four elements were identified as significant predictors of SSA (ordered by decreasing predictive power): V > Ca > Al > Rb. The optimum model from these four elements accounted for 73% of the variation in bed sediment SSA (range 6–46 m² g⁻¹) with a root mean squared error of prediction – based on leave-one-out cross-validation – of 6.3 m² g⁻¹. It is believed that V is the most significant predictor because its concentration is strongly correlated both with the quantity of Fe-oxides and clay minerals in the stream bed sediments, which dominate sediment SSA. Sample heterogeneity in SSA – based on triplicate measurements of sub-samples – was a substantial source of variation (standard error = 2.2 m² g⁻¹) which cannot be accounted for in the regression model.     

一种新的适合富有机质沉积岩的Re-Os同位素分析方法初探

虽然富有机质沉积岩中的Re和Os主要都富集在有机质中,但其中碎屑部分中的Re和Os也会影响其Re-Os等时线的准确度和精度。目前最常用的Cr O3-H2SO4溶样法虽然能尽量避免碎屑物质中Re和Os的溶出,但该方法具有Re流程空白高和环境污染严重等问题。因此,本研究尝试在富有机质沉积岩Re-Os同位素分析中使用H2O2-HNO3溶样来代替Cr O3-H2SO4溶样。本研究利用国际油页岩标样SGR-1b(USGS)为实验研究对象,分别对HCl-HNO3溶样、Cr O3-H2SO4溶样和H2O2-HNO3溶样3种溶样方法进行了对比研究。研究表明,H2O2与HNO3的体积比约为5﹕1的H2O2-HNO3溶液,不仅能保证样品和稀释剂的Re、Os同位素达到同位素交换平衡而且尽可能地避免碎屑物质中Re和Os的溶出。本方法相比于HCl-HNO3溶样,能尽量避免碎屑物质中Re和Os的溶出;而相比于Cr O3-H2SO4溶样,该方法具有本底低、无污染的优点。最后利用H2O2-HNO3溶样方法对广西金秀地区的泥岩样品和广东大宝山地区的碳质页岩样品进行了Re-Os同位素定年分析,分别得到了(404±5)Ma(IOs=1.57±0.13,n=8,MSWD=50)和(211±11)Ma(IOs=0.67±0.09,n=5,MSWD=11.1)的等时线年龄,这一结果与HCl-HNO3溶样得到的结果((412±11)Ma,IOs=1.18±0.38,n=8,MSWD=311;(223±18)Ma,IOs=0.59±0.14,n=5,MSWD=63)在误差范围内一致,但更为精确。     

Oil-generating potential of Tertiary coals and other organic-rich sediments of the Nyalau Formation,onshore Sarawak

The oil-generating potential of coals and other organic-rich sediments from the Late Oligocene–Early Miocene Nyalau Formation, the offshore extension of which is believed to be a major source rock, is evaluated. Coals of the Nyalau Formation are typically dominated by vitrinite, with moderate and low amounts of exinite and inertinite, respectively. Significant amounts of clay minerals are present in these coals and those containing between 15 to 65% mineral matter by volume are termed carbargilite. The samples analysed range from sub-bituminous to high-volatile bituminous rank, possessing vitrinite reflectance in the range 0.42% to 0.72%. T_max values range from 425°–450°C which is in good agreement with vitrinite reflectance data. Good oil-generating potential is anticipated from these coals and carbargilites with moderate to rich exinite content (15–35%). This is supported by their high hydrogen indices of up to 400 mgHC/gTOC, Py–GC (S2) pyrograms with n-alkane/alkene doublets extending beyond nC₃₀, and their being in the early to mid-mature oil-window range. Petrographically, the most significant evidence of the oil-generating potential of these coals is the generation of petroleum-like materials (exsudatinite) visible under the microscope. Exsudatinite is a secondary maceral, commonly considered to represent the very beginning of oil generation in coal, which is shown here to also have an important role to play in hydrocarbon expulsion. The precursor of exsudatinite in these coals is the maceral bituminite which readily expels or mobilizes to hydrocarbon-like material in the form of oil smears and/or exsudatinite as observed under the microscope. The maceral bituminite is considered to play a major generative role via early exsudatinite generation, which is considered to facilitate the overall expulsion process in coaly source rocks.     

Selective chemical extraction of carbonate-associated metals from recent lacustrine sediments

Acidic ion-exchanger was applied to the selective extraction of heavy metals in carbonate phases of recent lake sediments. Cr was not detected and Fe and Cu contents were reduced by factors of three to ten, relative to non-carbonate fractions of the sediment samples. Values obtained for Mn and Zn exemplify the effects of dilution was well as enrichment, both originating from increased carbonate percentages. Determinations on grain-sized fractions from Bodensee samples suggest that elevated inputs of dissolved Zn, which partly originate from human activities, may be immobilized by authigenic carbonate precipitation.     

Mineralogy and mineral chemistry of auriferous stream sediments from Al Wajh area, NW Saudi Arabia

A detailed ore microscopic study strengthened by fire assay data of Al Wajh stream sediments (Wadi Al Miyah, Wadi Haramil and Wadi Thalbah) in northwestern Saudi Arabia shows economic concentrations of gold in the silt fraction (40–63 μm). However, particles of extremely fine “dusty” gold (≤40 μm in size) were also identified in most stations as independent grains. The maximum gold content in the samples of Wadi Al Miyah is 13.61 wt%, which is reported for the heavy fraction (<40 μm). Maximum gold content in the heavy fractions of Wadi Haramil stream sediments amounts 6.90 g/t Au in a relatively coarse fraction (63–125 μm). It appears that the most fertile heavy fraction in gold among the analysed samples are those from Wadi Thalbah that have the highest index figure, which makes the placer gold in them more profitable from the economic point of view. The gold content in the heavy fractions of samples from Wadi Thalbah is economically high lying in the range 6.27–28.83 g/t Au, except for a sample collected at the upstream with 0.77 g/t Au. Al Wajh stream sediments (including the beach light and black sands) are also rich in Fe–Ti oxides, rutile and zircon, whereas monazite and thorite are much lesser. Mineral chemistry of magnetite indicates a distinct titanomagnetite variety (with 3.85 wt% TiO₂) which is consistent with the ore microscopic investigation. The titanomagnetite is V- and Cr-free, which indicates derivation from a more felsic source than a mafic one. No traces of U were found in zircon that sometimes bears up to 2.74 wt% Hf₂O₃. Chemical analyses of monazite show typical common contents of rare earth elements such as La, Ce, Nd and Sm. Thorite is either U-free or uranothorite varieties where the latter contains up to 31.79 wt% UO₂. One of the U-free thorite grains is Y-bearing and contains 7.13 wt% Y₂O₃.

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كيميائية المعادن من التحليل التقديري الناري لرسوبيات الوديان في منطقة الوجه- شمال غرب المملكة العربية السعودية

توضح الدراسة المجهرية للخامات المعدنية والتي تعضدها بيانات التحليل التقديري الناري لرسوبيات الوديان بمنطقة الوجه (وادي المياه، وادي حرامل، وادي ثلبة) في شمال المملكة العربية السعودية، أن هناك تركيزات اقتصادية للذهب في كسرة الغرين التي يتراوح حجمها من 40 إلى 63 ميكرومتر. في معظم الحالات المدروسة تم رصد حبيبات من الذهب الطليق متناهية الصغر (أقل أو تساوي 40 ميكروميتر). كما اتضح أيضا أن أعلى محتوى لفلز الذهب وجد في القطفات المعدنية الثقيلة دقيقة الحجم المأخوذة من وادي المياه والتي تقدر 13.61 جرام/الطن. أما المحتوى الأعلى في القطفات المعدنية الثقيلة الأكبر نسبيا في الحجم (تتراوح من 63 إلى 125 ميكروميتر) المأخوذة من الرواسب الوديانية بوادي حرامل يصل إلى 6.90 جرام/طن. ويبدو أن القطفات الثقيلة لرسوبيات وادي ثلبة الوديانية هي الأخصب من حيث محتوى الذهب وتلك العينات لها شكل مميز مما يجعل ذهب المراقد بذلك الوادي ذو ربحية مشجعة وذلك من الناحية الاقتصادية. وتتراوح التركيزات الاقتصادية للذهب في عينات وادي ثلبة بين 6.27 - 28.83 جرام/طن باستثناء عينة وحيدة تم تسجيل كمية ذهب بها لا تتعدى 0.77 جرام/طن. عينات الرواسب الوديانية بمنطقة الوجه (بما في ذلك الرمال الشاطئية السوداء والفاتحة اللون) غنية بمعادن خامات أكاسيد الحديد والتيتانيوم والروتيل والزيركون، بالإضافة إلى كميات أقل بكثير من معدني المونازيت والثوريت. وتوضح كيمياء المعادن أن معدن الماجنيتيت غني بالتيتانوماجنيتيت (ماجنيتيت تيتاني به 3.85% من ثاني أوكسيد التيتانيوم) وهو ما أثبتته أيضا الدراسة المجهرية. وهذا الماجنيتيت التيتاني لا يحتوي على عنصري الكروم والفاتيديوم مما يعطي دلالة على أن هذه الصخور فلسية أكثر منها مافية، وأن الزيركون الموجود لا يحتوي على عنصر اليورانيوم بينما يحتوي على أكسيد هافتيوم حتى 2.74%. أما التحاليل الكيميائية للمونازيت فإنها تظهر وجود كميات من العناصر الأرضية النادرة مثل اللانثاتوم والسيريوم والنيوديوم والسماريوم. أما معدن الثوريت فقد تم تسجيل نوعان منه أحدهما لا يحتوي على اليورانيوم أما الآخر فيحتوي على 31.79% من ثاني أوكسيد اليورانيوم. ولقد اكتشف في إحدى حبيبات الثوريت أنها لا تحتوي على اليورانيوم ولكنها تحتوي على عنصر أكسيد الأيتريوم تصل نسبته إلى 7.13%.

     

A rapid field method for extracting the magnetic fraction from stream sediments

Magnetic fraction concentrates for geochemical analysis can be obtained with an automagnet directly from wet stream sediments, without prior concentration by panning.     

Geochemical evolution of the Richtersveld area, South Africa, as deduced from regional geochemical maps of stream sediments

The Richtersveld area, bounded by 16° and 18° E and 28° and 29° S, has been mapped geochemically using stream sediment samples collected from first-order streams on a one-kilometre grid. The samples have been analysed for 20 elements and geochemical maps on a scale of 1:250,000 have been prepared.The basement consists of the Orange River Group which has been intruded by the Vioolsdrift Suite between 1700 and 1900 Ma. Intrusive into the Vioolsdrift Suite is the Richtersveld Suite, consisting of alkaline granite, syenite and diorite, which intruded at 970 Ma.The basement and the Richtersveld Complex are overlain by the younger Gariep Complex and in the south the Vioolsdrift Suite is overlain by the still younger Nama basin. The last intrusive event was the emplacement of three granitic plutons at 550 Ma.Geochemical maps for Rb and Y are used to characterize the geochemistry of the basement rocks. These maps show that the northern portion of the Vioolsdrift Suite is granodioritic whereas the southern portion is granitic. The boundary between the two granitic terrains is delineated.The distribution of Rb in the sandstone of the Gariep Complex reflects the Rb variation in the Vioolsdrift Suite and the Richtersveld Complex from which it was derived. The Rb in the sandstone occurs in feldspar thus demonstrating that mechanical weathering dominated during the its formation. The distribution of Y confirms both the proposed source areas and weathering conditions. Yttrium occurs in placer deposits in the sandstones of the Gariep Complex.The deep water facies of the Gariep Complex reflects the provenance areas vaguely, but due to homogenization in the basin the distribution of Y is more homogeneous in the shale. The effect of chemical traps such as dolomitic limestone is, however, apparent.The sporadic high concentration levels of Rb and Y in the sandstone of the Nama basin indicate that the granitic portion of the Vioolsdrift batholith was the source area, that mechanical weathering dominated and that placer deposits formed during the deposition of the fluvial sandstones. The dolomitic limestones, however, show evidence of the chemical fractionation of Y, indicating that chemical leaching and concentration took place during this phase.Elements such as Sn, W, Be, B, Th, Nb and Ta, all of which occur in the southern Vioolsdrift batholith, could have concentrated as placers in the Gariep and Nama sandstones. Elements such as U, Y, P, and Cu, of which substantial deposits are known, did not concentrate in the sandstones, but formed accumulations in the limestone and carbonaceous limestone of the younger sediments. Geochemical maps for Y, P and U show examples of hitherto unknown metallogenic provinces in the deep water sediments.Geochemical maps for Ti, Zr and P can be used to define the boundaries and relative concentration of diamonds within individual deposits and to identify new exploration targets.The pegmatite metallogenic province is divided into a northern P-enriched province containing accumulations of Y, Zr, Th, U and rare-earths, and a southern Nb-enriched province. The latter contains several Ta- and Be-producing pegmatites. The extension of these two pegmatitic provinces, which are also associated with the widespread W-mineralization, to the west of the Nama basin is also suggested.