Simultaneous production of magnesium carbonate and calcium carbonate from dolomites and dolomitic limestones

By use of a recarbonation process, it is possible to separate magnesium carbonate and calcium carbonate from dolomites/dolomitic limestones. Magnesium carbonate can be used for manufacturing basic refractories and magnesium chemicals; the portion rich in calcium carbonate can be used for cement manufacture if the MgO content is below 3%. In this paper the process developed for the purpose and the results of bench scale tests are reported. The results indicate that, under optimum conditions, both objectives can be fulfilled by the recarbonation process.     

Major and trace element anomalies in stream sediments of the Teign Valley Orefield

A detailed geochemical and sedimentological study of twenty-two bulk stream sediments in the Teign Valley of southwest Devon shows the influence of lithology, mineralization and contamination on such cumulative samples. K, Cu and Ni in stream sediments emerge as potential indicators of lithology. Ba and S values, as well as barytes concentrations, demonstrate the contribution of Ba, Zn and Pb mineral lodes, whilst Fe, S and heavy-mineral percentages emphasize that of Fe lodes and contamination. As, Pb and Zn anomalies are observed within Fe-oxide crusts giving evidence of Fe in the role of scavenger. High Mn values are attributed to precipitations of the metal derived largely from impregnations of the Culm.     

Major and trace element geochemistry in upper Ganga river in the Himalayas, India

Chemical weathering and resulting water compositions in the upper Ganga river in the Himalayas were studied. For the first time, temporal and spatial sampling for a 1 year period (monthly intervals) was carried out and analyzed for dissolved major elements, trace elements, Rare Earth Elements (REE), and strontium isotopic compositions. Amounts of physical and chemical loads show large seasonal variations and the overall physical load dominates over chemical load by a factor of more than three. The dominant physical weathering is also reflected in high quartz and illite/mica contents in suspended sediments. Large seasonal variations also occur in major elemental concentrations. The water type is categorized as HCO₃^––SO₄^2––Ca²⁺ dominant, which constitute >60% of the total water composition. On an average, only about 5–12% of HCO₃^– is derived from silicate lithology, indicating the predominance of carbonate lithology in water chemistry in the head waters of the Ganga river. More than 80% Na⁺ and K⁺ are derived from silicate lithology. The silicate lithology is responsible for the release of low Sr with extremely radiogenic Sr (⁸⁷Sr/⁸⁶ Sr>0.75) in Bhagirathi at Devprayag. However, there is evidence for other end-member lithologies for Sr other than carbonate and silicate lithology. Trace elements concentrations do not indicate any pollution, although presence of arsenic could be a cause for concern. High uranium mobilization from silicate rocks is also observed. The REE is much less compared to other major world rivers such as the Amazon, perhaps because in the present study, only samples filtered through <0.2 m were analysed. Negative Eu anomalies in suspended sediments is due to the excess carbonate rock weathering in the source area.     

Crack damage stress as a composite function of porosity and elastic matrix stiffness in dolomites and limestones

Twenty-five uniaxial compression tests were performed to determine stress at onset of dilation, referred to herein as “the crack damage stress,” in heterogeneous dolomites and limestones. A simplified model for crack damage stress (σ_cd) is developed here using porosity, elastic modulus, Poisson's ratio and three empirical coefficients. The model shows that when porosity decreases and elastic modulus increases, σ_cd rapidly increases and approaches its maximum value. On the other hand, when porosity increases and elastic modulus decreases, σ_cd rapidly decreases and approaches its minimum value. The proposed model is validated for six heterogeneous limestone and dolomite formations which are widely distributed in Israel.     

Major and trace element variation in ilmenite in the Skaergaard Intrusion: petrologic implications

Ilmenite separates from the floor (LS), roof (UBS), and wall (MBS) sequences of the Skaergaard Intrusion were analyzed for major and trace elements using DCP-AES and ICP-MS techniques. In all three sequences, FeO progressively increases, and MgO and Al₂O₃ progressively decrease with differentiation. Although trace element abundances are, in general, higher in UBS ilmenite than in MBS and LS ilmenite, all three sequences have similar trends for trace element abundance vs. crystallization. Ba, Cs, Rb, Sr, Th, U, Y, and the REEs are excluded elements in ilmenite, and remained at low abundances during differentiation. Cr, Ni, Sc, and V are included elements in ilmenite and other mafic phases, and decreased during differentiation. V contents in ilmenite, however, do not decrease significantly until the upper part of the middle zone, suggesting that magnetite did not begin to affect the magma differentiation trend until much later than when it first appears in the intrusion. Hf, Nb, Ta, and Zr, which are strongly excluded elements in silicates, are included elements in ilmenite. The element ratios Zr/Hf, Y/Ho, Nb/Ta, and U/Th are relatively constant in Skaergaard ilmenite from different parts of the intrusion, suggesting that fluid transport did not significantly effect these elements during differentiation or post-solidification cooling. Calculated partition coefficients for ilmenite in the Skaergaard Intrusion are similar to those reported from previous studies of lunar and terrestrial basalts and kimberlites, and for most elements are significantly lower than those reported for ilmenite in rhyolitic magma. Similar D_i's for Zr, Hf, Nb, and Ta suggest that ilmenite crystallization did not significantly affect Zr/Nb or Hf/Ta in the Skaergaard magma, but the ratios of Zr, Hf, Nb, or Ta to other high field strength elements, such as Th, U, Y, or the REEs, may have been altered by ilmenite fractionation.     

The determination of minor and trace element associations in coal using a sequential microwave digestion procedure

A sequential extraction procedure, using acid digestion in a CEM MDS-81D® microwave system, is reported for the investigation of trace and minor element associations in coal in (1) mineral phases other than pyrite, (2) pyrite and (3) the organic matrix. The concentrations of sulphate, pyrite and organic sulphur can also be determined by this method. The extract solutions from each stage are rapidly analysed by ICP-AES. The association of major, minor and trace elements with mineral and organic phases is suggested for a suite of certified reference coal samples. In stage 1, a significant percentage of the total Ba, Co, Cr, Cu, Mn, Ni, Pb and Sr was extracted suggesting an association with silicate, carbonate, sulphate and phosphate minerals for these elements. In stage 2, a proportion of the Cu, Mn, Ni, Pb and Zn was dissolved implying the occurrence of these elements in pyrite. An association with the organic matrix is suggested for Cr and also for Ba and Sr in lower rank coals.     

Improved methods for selective dissolution of Mn oxides: applications for studying trace element associations

The association of rare earth and other trace elements with Fe and Mn oxides was studied in Fe-Mn-nodules from a lateritic soil from Serra do Navio (Northern Brazil). Two improved methods of selective dissolution by hydroxylamine hydrochloride and acidified hydrogen peroxide along with a classical Na–citrate–bicarbonate–dithionite method were used. The two former reagents were used to dissolve Mn oxides without significant dissolution of Fe oxides, and the latter reagent was used to dissolve both Mn and Fe oxides. Soil nodules and matrix were separated by hand. Inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry after fusion with lithium metaborate, and X-ray diffraction were used to determine the elemental and mineralogical composition of the nodules and soil matrix. The latter was composed of kaolinite, gibbsite, goethite, hematite, and quartz. In the nodules, lithiophorite LiAl₂(Mn^IV₂Mn^III)O₆(OH)₆ was detected in addition to the above-mentioned minerals. The presence of hollandite (BaMn₈O₁₆) and/or coronadite (PbMn₈O₁₆) in the nodules is also possible. In comparison to the matrix, the nodules were enriched in Mn, Fe, K, and P, and relatively poor in Si, Al, and Ti. The nodules were also enriched in all trace elements determined. Phosphorus, As and Cr were associated mainly with Fe oxides; Cu, Ni, and V were associated with both Fe and Mn oxides; and Ba, Co, and Pb were associated mainly with Mn oxides. Distribution of rare earth elements indicated a strong positive Ce-anomaly in the nodules, compared to the absence of any anomaly in the matrix. Some of Ce was associated with Mn oxides. The improved methods achieved almost complete release of Mn from the sample without decreasing the selectivity of dissolution, i.e., without dissolving significant amounts of Fe oxides and other minerals, and provided reliable information on associations of trace elements with Mn oxides. These methods are thus proposed to be included in sequential extraction schemes for fractionation of trace elements in soils and sediments.     

Major and trace element patterns established during retrogressive metamorphism of granulite-facies gneisses,NW Scotland

A detailed study of geochemical changes associated with the retrogressive metamorphism of granulite-facies gneisses of the Lewisian Complex of NW Scotland has been made, using nearly 250 gneisses analysed for 24 major, minor and trace elements. The gneiss samples have been divided into 3 groups: (1) granulite facies, (2) granulite facies retrogressed to amphibolite facies but remaining undeformed, and (3) retrogressed (amphibolite-facies) gneisses deformed in shear zones. Element distributions within these groups have been examined using correlation coefficients, and have been compared and tested for significance using Student's t and Fisher z statistics. It is shown that the process of retrogression involved considerable large-scale chemical equilibration. Major-element pairs show marked increases in correlation during retrogression, reflecting considerable reordering of elements into one or other of the main amphibolite-facies minerals: hornblende, plagioclase and (minor) biotite. These correlations are enhanced, but otherwise unchanged, in the deformed gneisses. The retrogressed gneisses have a much more constant Fe/Mg ratio and a more uniform plagioclase composition, while there is a strong correlation between Fe³⁺ and Fe²⁺ throughout the area studied. Trace elements, by contrast, mostly show a significant loss of correlation during retrogression, although Cr and Ni are exceptions. Retrogression occurred as a result of widespread introduction of hydrous fluids up vertical structures in the gneiss complex during the Early Proterozoic. These fluids allowed considerable metasomatic redistribution of elements within the complex as the whole-rock compositions adjusted to the new mineralogy. Throughout the North Atlantic Archaean Craton there is a close association between retrogression of high-grade gneisses and basic magmatism in the form of dyke swarms. It is suggested that the two may be connected, and that the fluids causing retrogression are mantle-derived.     

Major and trace element geochemistry of Lake Bogoria and Lake Nakuru,Kenya, during extreme draught

The physico-chemical properties of water samples from the two athalassic endorheic lakes Bogoria and Nakuru in Kenya were analysed. Surface water samples were taken between July 2008 and October 2009 in weekly intervals from each lake. The following parameters were determined: pH, salinity, electric conductivity, dissolved organic carbon (DOC), the major cations (FAAS and ICP-OES) and the major anions (IC), as well as certain trace elements (ICP-OES). Samples of superficial sediments were taken in October 2009 and examined using Instrumental Neutron Activation Analysis (INAA) for their major and trace element content including rare earth elements (REE). Both lakes are highly alkaline with a dominance of Na > K > Si > Ca in cations and HCO₃ > CO₃ > Cl > F > SO₄ in anions. Both lakes also exhibited high concentrations of Mo, As and fluoride. Due to an extreme draught from March to October 2009, the water level of Lake Nakuru dropped significantly. This created drastic evapoconcentration, with the total salinity rising from about 20‰ up to 63‰. Most parameters (DOC, Na, K, Ca, F, Mo and As) increased with falling water levels. A clear change in the quality of DOC was observed, followed by an almost complete depletion of dissolved Fe from the water phase. In Lake Bogoria the evapoconcentration effects were less pronounced (total salinity changed from about 40‰ to 48‰). The distributions of REE in the superficial sediments of Lake Nakuru and Lake Bogoria are presented here for the first time. The results show a high abundance of the REE and a very distinct Eu depletion of Eu/Eu* = 0.33–0.45.     

Major and trace element geochemistry of superficial sediments and suspended particulate matter of shallow saline lakes in Eastern Austria

General geochemical parameters of water, superficial sediments, and suspended particulate matter (SPM) were determined from small shallow saline lakes (soda ponds) as well as from lake Neusiedlersee in eastern Austria. Additionally, instrumental neutron activation analysis (INAA) was used to determine the distribution of major, rare earth and other trace elements in superficial sediments and SPM. Chemical results show remarkable differences in salinity and ionic strength between the investigated ponds. Anthropogenic effects, such as drawdown of ground water level and a loss of lake water due to drainage, are clearly reflected in obtained chemical and geological data. Due to a strong dependence of the complexation and scavenging behavior of the rare earth elements (REE) on ionic strength, a significant difference between REE concentrations in soda ponds with different anthropogenic impact was found. The content and composition of authigenic evaporitic minerals in superficial sediments and SPM clearly differ with a fluctuating water level and salt concentration. Furthermore, we determined the distribution of major and trace elements in superficial sediments of a nearby fluvial system. Our results show a clear correlation between REE superficial sediment concentrations in anthropogenically degraded soda ponds and fluvial system. Therefore, we assume that REE concentrations of sediments and SPM are suitable for the study of geochemical changes of inland saline lakes due to anthropogenic impacts on water balance.     

Major and trace element geochemistry in Zeekoevlei, South Africa: A lacustrine record of present and past processes

This study reports a multi-parameter geochemical investigation in water and sediments of a shallow hyper-eutrophic urban freshwater coastal lake, Zeekoevlei, in South Africa. Zeekoevlei receives a greater fraction of dissolved major and trace elements from natural sources (e.g., chemical weathering and sea salt). Fertilizers, agricultural wastes, raw sewage effluents and road runoff in contrast, constitute the predominant anthropogenic sources, which supply As, Cd, Cu, Pb and Zn in this lake. The overall low dissolved metal load results from negligible industrial pollution, high pH and elevated metal uptake by phytoplankton. However, the surface sediments are highly polluted with Pb, Cd and Zn. Wind-induced sediment resuspension results in increased particulate and dissolved element concentrations in bottom waters. Low C/N ratio (10) indicates primarily an algal source for the sedimentary organic matter. Variation in sedimentary organic C content with depth indicates a change in primary productivity in response to historical events (e.g., seepage from wastewater treatment plant, dredging and urbanization). Primary productivity controls the enrichment of most of the metals in sediments, and elevated productivity with higher accumulation of planktonic debris (and siltation) results in increased element concentration in surface and deeper sediments. Aluminium, Fe and/or Mn oxy-hydroxides, clay minerals and calcareous sediments also play an important role in adsorbing metals in Zeekoevlei sediments.     

Aluminum-dependent trace element partitioning in clinopyroxene

As technical advances have dramatically increased our ability to analyze trace elements, the need for more reliable data on the compositional dependence of trace element partitioning between minerals and melt has become increasingly important. The late-Cretaceous Carmacks Group of south central Yukon comprises a succession of primitive high-Mg ankaramitic lavas characterized by shoshonitic chemical affinities and containing large complexly zoned clinopyroxene phenocrysts. The compositional zonation of the clinopyroxene phenocrysts is characterized by relatively Fe-rich (Mg^# = Mg/(Mg + Fe) = 0.85), but mottled, cores surrounded by mantles of cyclically-zoned clinopyroxene whose Mg^# varies repeatedly between 0.9 and 0.80. These cyclically zoned clinopyroxene mantles appear to record the repeated influx and mixing of batches of primitive with more evolved magma in a deep sub-crustal (∼1.2 GPa) magma chamber(s). Laser ablation ICP-MS was used to analyze the trace element variation in these zoned clinopyroxenes. The results indicate more than a threefold variation in the absolute concentrations of Th, Zr, rare earth elements (REE), and Y within individual clinopyroxene phenocrysts, with no apparent change in the degree of REE or high field strength element (HFSE) fractionation. The variation in absolute abundances of trace elements correlates closely with the major element composition of the clinopyroxene, with the most enriched clinopyroxene having the lowest Mg^# and highest Al contents. The problem is that the amount of crystal fractionation required to explain the major element variation (∼20%) in these clinopyroxene phenocrysts cannot explain the increase in the abundance of the incompatible trace elements, which would require more than 70% crystal fractionation, if constant partition coefficients are assumed. The anomalous increase in incompatible trace elements appears to reflect an increase in their partition coefficients with increasing Al^IV in the clinopyroxene; with an increase in Al₂O₃ from 1.5 to 4.0 wt.% during ∼20% crystal fractionation over a temperature decrease of ∼100°C being associated with more that a threefold increase in the partition coefficients of Th, Zr, REE, and Y. The magnitude of these increases may indicate that the substitution of these trace elements into clinopyroxene is better modeled in some natural systems by a local charge balance model, rather than the distributed charge model that better replicates the results of annealed experiments. These findings indicate that the effect of Al on the partition coefficients of incompatible trace elements in clinopyroxene may be under appreciated in natural magmatic systems and that the application of experimentally determined clinopyroxene partition coefficients to natural systems must be done with caution.     

A comparative study of the Rare Earth Element (REE) distributions within the Lower Cretaceous dolomites and limestones of Central Tunisia

REE distribution, strontium content and oxygen isotopic composition have been studied in the Lower Cretaceous dolomites and their interbedded and/or parental limestones of Central Tunisia. Dolomites, as indicated by previous sedimentologic, geochemical and isotopic study, are different in origin. Environments of dolomite formation include: evaporitic sabkha, deep phreatic, karst and lacustrine. With the exception of the sabkha environment, dolomitizing fluids presumably have been essentially meteoric. The comparison between REE distributions in dolomites and limestones clearly suggests that the general shapes of the REE patterns are preserved during dolomitization. Nevertheless, the total REE amounts are somewhat lowered in dolomites comparatively to parental limestones. Moreover, within the dolomites, the total REE contents are positively correlated to the Sr and δ¹⁸O contents; thus indicating that the decrease in REE, Sr, and δ¹⁸O contents is related to a decrease in the salinity of dolomitizing fluids. In addition, dolomites associated with emergence surfaces (karst) are the most impoverished in REE. Furthermore, they are relatively enriched in light REE, indicating a more or less important fractionation with the REE distributions. This enrichment has been related to the influence of the inorganic complexes which favours the greatest solubility of the heavy REE in basic solution with respect to the lightest members of the REE group.     

Patterns of trace element partitioning

When a phenocryst and its lava matrix have been analysed for both major and trace elements, plots of partition coefficient (mineral/matrix) against ionic radius give a family of sub-parallel curves, one univalent, one divalent, etc. Onuma et al. (1968) demonstrated this with two analyses and concluded, from the shape of these curves, that trace element partition between phenocryst and groundmass is determined primarily by crystal structure of the phenocryst. In this study, over 50 such analyses, taken from the literature, have been plotted on modified Onuma diagrams, in order to analyse the constant and variable factors in the curves. It is demonstrated that these curves can provide important additional information in trace element studies by revealing, for example, the site or sites in a mineral which a given element is occupying, the valency state of the element and even, in some cases, the proportion of different valency states present.     

甘肃龙首山成矿带新水井铀(钍)矿床元素迁移规律及成矿作用过程研究

新水井铀(钍)矿床位于甘肃省龙首山成矿带,是碱交代型铀矿床的典型代表,其矿体完全产于钠交代蚀变花岗岩中,成矿过程可划分为钠交代蚀变、铀钍矿化和成矿后3个主要阶段。文章对该矿床花岗岩原岩、蚀变岩及矿石开展了系统主微量元素分析,采用Grant等浓度线法探讨了钠交代蚀变和铀钍矿化阶段的元素迁移规律,结果表明:钠交代蚀变阶段为富含Na、Ca、过渡族元素(Sc、V、Cr、Co、Ni)、U、Th及CO2、H2O等挥发分的复杂流体,钠交代过程中原岩中的大离子亲石元素(Rb、Ba)和部分轻稀土元素(LREE)不同程度带出;而铀钍成矿阶段成矿流体则富集重稀土元素(HREE)、U、Th、PO43-等成分,CO2等挥发分大量逸出。结合前人研究,认为新水井矿床成矿流体可能来自地幔流体和大气降水热液的混合;等挥发分CO2的逸出是新水井矿床最重要的矿质沉淀机制,导致了铀钍矿物和磷酸盐矿物(磷灰石)的共沉淀,而磷灰石的沉淀又促进了以磷酸盐形式搬运的Th元素的沉淀。     

Microstructural evolution and trace element mobility in Witwatersrand pyrite

Microstructural analysis of pyrite from a single sample of Witwatersrand conglomerate indicates a complex deformation history involving components of both plastic and brittle deformation. Internal deformation associated with dislocation creep is heterogeneously developed within grains, shows no systematic relationship to bulk rock strain or the location of grain boundaries and is interpreted to represent an episode of pyrite deformation that predates the incorporation of detrital pyrite grains into the Central Rand conglomerates. In contrast, brittle deformation, manifest by grain fragmentation that transects dislocation-related microstructures, is spatially related to grain contacts and is interpreted to represent post-depositional deformation of the Central Rand conglomerates. Analysis of the low-angle boundaries associated with the early dislocation creep phase of deformation indicates the operation of <010>{100} slip systems. However, some orientation boundaries have geometrical characteristics that are not consistent with simple <010>{100} deformation. These boundaries may represent the combination of multiple slip systems or the operation of the previously unrecognized <001>{120} slip system. These boundaries are associated with order of magnitude enrichments in As, Ni and Co that indicate a deformation control on the remobilization of trace elements within pyrite and a potential slip system control on the effectiveness of fast-diffusion pathways. The results confirm the importance of grain-scale elemental remobilization within pyrite prior to their incorporation into the Witwatersrand gold-bearing conglomerates. Since the relationship between gold and pyrite is intimately related to the trace element geochemistry of pyrite, the results have implications for the application of minor element geochemistry to ore deposit formation, suggest a reason for heterogeneous conductivity and localized gold precipitation in natural pyrite and provide a framework for improving mineral processing.     

Major,minor, and trace element compositions of peridotitic and basaltic komatiites from the precambrian crust of Southern Africa

Major and trace element compositional data are reported for nine mafic and ultramafic rock samples from the Barberton greenstone belt. Rocks from this province are among the oldest fragments of the Earth's crust (3.5 b.y.). The data are consistent with an oceanic crust related origin for these rocks. The high abundances of Ni in these samples make their origin by fractional crystallization of a primitive magma unlikely but are consistent with their generation by partial melting of an upper mantle source. The basaltic samples from the Komati formation can be related by small degrees of partial melting of a primitive upper mantle source to the peridotitic komatiite which probably derived from much more extensive partial melting of a similar source. REE and especially Ni abundances limit the proportion of olivine that is permitted in the residue.