Distribution and speciation of gold in biogenic and abiogenic calcium carbonates - Implications for the formation of gold anomalous calcrete

Calcrete (pedogenic Ca carbonate) is an important sampling medium for geochemical gold (Au) exploration in semi-arid and arid regions of Australia, because it is widespread, easy to sample and calcium (Ca) shows a strong positive correlation with Au, but not with base metals, in calcrete overlying buried Au mineralization. In this study we show that the formation of Au-anomalous calcrete can be biomediated through the activity of resident microorganisms, and may not simply be the result of passive nucleation on inactive cells or evapotransporative processes. Calcified microfossils are highly abundant in calcrete from the Barns Au-prospect in South Australia. These microfossils are morphological analogues of calcified cells and biofilms formed in laboratory experiments conducted with active bacterial cultures enriched from Au-anomalous calcareous sand from the Barns prospect. Calcium carbonates precipitated by these cultures consisted mostly of calcite, which is the main carbonate mineral in calcrete. Synchrotron micro-X-ray fluorescence (S-μXRF) mapping was used to assess the distribution of Au, Zn, Ca and other metals in Ca carbonates precipitated by active bacterial cultures. On a μm-scale the distribution of Au was heterogeneous in these Ca carbonates and differed from base metal distribution, thus mimicking the spatial separation of these metals observed in calcrete. The speciation of Au in Ca carbonates precipitated by active bacteria was measured using micro-X-ray absorption near edge structure spectroscopy (μ-XANES) and resembled that observed in Au-anomalous calcrete closely. While metallic Au was observed in Au ‘hotpots’, ionic Au was detected in the halo surrounding the ‘hotspot’. In contrast, the precipitates produced in the presence of dead bacterial cells or by raising solution pH or pCO₂, i.e., hydroxylapatite, portlandite and vaterite, respectively, did not reflect the mineralogy of calcrete. Gold distribution and speciation in vaterite, formed by raising pCO₂, were homogenous and did not reproduce the variation observed in calcrete and Ca carbonates precipitated by active cells. Increasing the supersaturation with respect to Ca in solution by incremental drying of the medium produced only X-ray amorphous precipitates, or hydroxylapatite in the presence heat-killed cells. In conclusion, this study shows that active microbial processes that combine biogenic Ca carbonatogenesis with Au precipitation are likely to drive the formation of Au-anomalous calcrete.     

Mechanism of calcrete formation in the Lower Cretaceous (Neocomian) fluvial deposits,northeastern Iran based on petrographic,geochemical data

The Kopet-Dagh basin of northeastern Iran was formed during the Middle Triassic orogeny. From Jurassic through Miocene time, sedimentation was relatively continuous in this basin. The Shurijeh Formation (Neocomian), which consists of red bed siliciclastic sediments that were deposited in fluvial depositional settings, crops out in the southeastern part of the Kopet-Dagh basin. In addition to clastic lithofacies, non-clastic facies in the form of calcrete paleosols, were identified in this formation. The calcrete host rocks are mainly sandstone, pebbly sandstone. The calcrete in middle unit in the Shurijeh Formation consists of, from bottom to top: incipient calcrete, nodular calcrete, massive calcrete horizons. The maturity pattern of these calcrete gradationally increases from bottom to top in this unit. Lack of organo-sedimentary structure (mainly plant roots), diversity of calcite fabric, suggest that the studied calcretes have a multi-phase development: a short vadose phase followed by a long phreatic phase. These calcretes are neither pedogenic nor groundwater calcretes. Petrographic studies show that they are composed of micritic textures with a variety of calcite fabrics, microsparitic/sparitic veins, displacive, replacive fabrics, quartz, hematite grains. Cathodoluminescence images, trace elemental analysis (Fe, Mn increased, Na, Sr decreased) of calcrete samples show the effects of meteoric waters during the calcrete formation when water tables were variable. In this study, we conclude that evaporation, degassing of carbon dioxide are the two main factors in the formation of non-pedogenic or groundwater calcrete. The sources of carbonate were probably parent materials, surface waters, ground waters, eolian dusts, numerous outcrops of limestones that have been exposed in the source area during Neocomian time.     

Paleosol profiles in the Shiohama Formation of the Lower Cretaceous Kanmon Group,Southwest Japan and implications for sediment supply frequency

This paper describes the pedogenic features of paleosols in the upper Lower Cretaceous Shiohama Formation, the lowest unit of the Shimonoseki Subgroup, in Yoshimi, Yamaguchi Prefecture, southwest Japan. The paleosol profiles in the Shiohama Formation are compound and complex, characterized by the presence of abundant calcrete horizons. An analysis of these profiles reveals that the floodplain upon which the Shiohama Formation was deposited was part of an unstable aggradation system characterized by the intermittent influx of sediments and occasional erosion. Furthermore, the mean annual range of precipitation was less than about 30 mm, suggesting only minor seasonal change between wet and dry conditions during deposition of the Shiohama Formation. The microstructures of the observed calcretes include dense microfabric, floating detrital grains, micronodules, circum-granular cracks, and complex cracks. These features formed by chemical precipitation under dry conditions, with little bioactivity. The calcrete horizons are classified into seven types (I–VII) based on their modes of occurrence. Two processes of carbonate accumulation can be identified based on the size and abundance of nodules: VI–V–III–(II)–I and VI–(V)–IV–II–I. These processes represent the development of calcrete horizons from the early to late stages of calcretization. Type I represents the most highly developed stage of calcretization. Calcretes within the Lower Member sequence of the Shiohama Formation show repetitions of type I and types II and III. Thus, it is interpreted that the frequency of sediment supply to the floodplain changed repeatedly over time.     

Biogeochemistry of a regolith: The New Caledonian Koniambo ultramafic massif

This work aims to elucidate the factors governing the mobility of metals in soils of a lateritic nickel ore deposit in New Caledonia. The transfer of nickel and associated metals is determined along a topographic sequence ranging from a plateau to a thalweg. Mining exploration borehole data and soil pit data enabled us to define the general geochemical trends of the lateritic weathering. The homogeneous topsoil, which consists mainly of iron oxy-hydroxides, exhibits various amounts of plant available metals. Two interrelated factors control the differences in metal availability: (1) the presence of nickel-rich soil horizons underlying the topsoil and formed of silicate minerals, and (2) the biological cycling of metals from these horizons to the surface. These results have major implications for topsoil management during the mining activity where it is important to minimise metal inputs to water systems and to restore endemic vegetation after mining.     

U‐Th‐Pb systematics of some granitoids from the northeastern Yilgarn Block,Western Australia and implications for uranium source rock potential

The Mount Boreas‐type granite and spatially associated syenitic granitoid of Western Australia yield Pb‐Pb ages of 2370 ± 100 Ma and 2760 ± 210 Ma, respectively. Th‐Pb ages, although less precise, are concordant with these ages, and therefore the apparent ages are interpreted to be the crystallisation ages for these two units. U‐Pb ages are variable and for the most part anomalously old, which suggests a Cainozoic uranium loss. However, this loss is generally small (< 3μg/g); therefore, neither granitoid in its fresh state provides a good source for nearby calcrete‐hosted uranium deposits. The possibility remains that the Mount Boreas‐type granite that has been completely weathered during the Tertiary could have been a source for the calcrete‐type uranium deposits in W.A. Although the Mount Boreas‐type granite is highly fractionated, it does not bear a strong geochemical imprint of a sedimentary precursor. This feature contrasts it with apparently fresh granitoids from other parts of the world that have lost large amounts of uranium (～ 20μg/g) and are associated with large roll‐type and other low temperature‐type uranium deposits.     

Occurrence of cyclic palustrine and calcrete deposits within the lower Pliocene Hagul formation, East Cairo district, Egypt

A depositional model of the lower Pliocene Hagul formation, which is exposed in the East Cairo district (Egypt), is proposed with more than 10 depositional cycles recognized. Field occurrence, detailed petrographic investigation and geochemical analysis revealed that the sediments within each cycle are the result of three sequential sedimentological processes: (1) alluvial sedimentation, (2) calcretization, and (3) precipitation of palustrine carbonate. It was concluded that Hagul formation has been deposited within the distal part of an alluvial plain during three successive climatic conditions: a humid climate during which alluvial sediments were deposited, a semi-arid climate with episodic precipitation which was favorable for pedogenic calcrete development, and a sub-humid climate during which groundwater level was gradually elevated and groundwater calcrete accumulated. Rising groundwater level continued until shallow wetlands covered the area and palustrine limestone was precipitated. Variations in the thickness and the nature of the host sediment, calcrete and palustrine limestone cycle suggest that each of the sedimentation processes varied from cycle to cycle.     

半干旱—干旱地区以钙积层为采样介质的隐伏金矿地球化学勘查

在隐伏金矿的地球化学勘查中,常用的采样介质包括岩石、水系沉积物、土壤、植物和地气等.近几十年,澳大利亚在半干旱—干旱地区以钙积层作为隐伏金矿床地球化学勘查的采样介质,并取得了成功.本文对以钙积层作为隐伏金矿地球化学勘查采样介质的理论和勘查进展进行总结,其勘查理论基础是土壤剖面中金-钙高度相关性,其成因机理较合理地解释为...     

Autoradiography and scanning electron microscopy combined with energy-dispersive spectrometry (SEM-EDS) in the service of geochemical exploration

The importance of the identification of the mineral phases in the heavy fractions of geochemical samples is emphasized. A knowledge of the chemical composition with information about the anomalous contents of the economically interesting metals in the samples is not sufficient, it is also essential to know the mineralogical source of the metals especially when the exploitation possibilities of the searched-for deposits are being estimated. A version of autoradiography suitable for the location and quantitative determination of radioactive minerals in the heavy fractions of geochemical samples is described. Furthermore, the use of a scanning electron microscope (SEM) equipped with an energy-dispersive spectrometer (EDS) in the identification of the heavy minerals is also described. An example of the use of SEM-EDS identification of radioactive minerals, located by the autoradiography, is described.     

Detection of concealed Cu–Zn massive sulfide mineralization below eolian sand and a calcrete cover in the eastern part of the Namaqua Metamorphic Province, South Africa

The regolith studied here is located at the defunct Areachap mine and the newly discovered Kantienpan Cu–Zn volcanic-hosted massive sulfide (VHMS) deposit, located in the Areachap Group of the eastern part of Mesoproterozoic Namaqua Metamorphic Province. This area is highly prospective for further VHMS discoveries. Paleo and recent weathering of the upper most parts of massive sulfide deposits led to the formation of a gossan zone. Due to semi-arid climatic conditions during the late Cretaceous, affecting the African Land surface, the lowermost units of the Kalahari Group and the underlying floor rocks were calcretized. An approximately 6 m thick calcrete layer formed above the gossan zone and this was later covered by eolian Kalahari sand. Samples were collected from the eolian sand cover in the study areas to determine the best analytical method that would enable recognition of the concealed ore deposits and detect the widest secondary dispersion halo.Mobile metal ions from the finest fraction of the eolian sand samples (< 75 μm) were extracted with a NH₄EDTA (EDTA) solution. The solution was analysed for Cu, Zn, Pb and Mn by inductively coupled plasma mass spectrometry (ICP-MS). The same grainsize fraction of the original samples was also analysed for comparison purposes by means of X-ray fluorescence (XRF).Results indicate that the ore zone in both areas may be recognized by both partial and total analyses of the eolian sand samples collected, although the calcrete layer, below the sand cover, acts as a partial geochemical barrier. The recognition of the ore zone depends on the regolith forming processes and the thickness of the eolian sand cover. In the Areachap area, with a relatively thick sand cover (in excess of 1 m) above the calcrete layer, the detectable geochemical halo is related to the distribution of the mobile metal ions, and partial extraction (EDTA solution) results define a larger dispersion halo than that, that could be detected by total analysis (XRF). Whereas, in the Kantienpan area with a very thin sand cover (< 50 cm) dispersion appears to be related more to the secondary redistribution of gossaniferous clasts released by recent weathering out of the calcrete, than to dispersion of mobile metal ions on the surface of sand particles. In this area, the XRF results reveal a wider dispersion of the elements of interest.     

Geochemistry of sedimentary rocks and its relation to crustal evolution and mineralization in Southwest Yangtze Massif, China

Through a systematic study on trace elements and REE geochemistry of mudstone deposited in the basin and lower slope environments during Upper Proterozoic to Triassic in the Southwest Yangtze Mssif,three geochemical abnormal horizons of which the geochemical characteristics are quite different from those of other horizons have been established for the first time.They are the Lower Cambrian,the Upper Devonian and the Upper Permian,As compared with the crustal evolution in this area.these three geochemical abnormal horizons are corresponding to the pulling-apart periods of geotectonic cycles.which illustrates that uncommon depositional sources puring into the basin from the earth‘s interior may be one of the most important causes to originate the geochemical anomalies in these lhrizons.Thus it can be realized that the geochemistry of post-Archean sedimentary rocks has a great deal to do with the crustal evolution and it can be used as a tracer to analyze the crustal evolution.The elements in this area are mainly concentrated in these geochemical abnormal horizons,and the degree of enrichment and deficiency of trace elements in other horizons is very limited.A series of research on mineralization indicates that the main strata-bound ore deposits discovered in the Southwest Yangtze Massif occur in the Cambrian,Devonian and Permian-Trassic strata.The results of isotope tracer resarch have also proved that most of the metallogenic elements in these ore deposits came from the host strata.which illustrates that the geochemical abnormal horizons may have made great contributions to these ore-forming processes.Thus it can be concluded that it is only the particular horizons corresponding to the particular periode of earth‘s evolution that can they be the significant source beds because only in these uncommon horizons there can be highly enriched metallogeinc elements.which may be one of the most important reasons for explaining the time-bound nature of mineralization.     

Biogeochemistry and microfossils of the Upper Jurassic and Lower Cretaceous,Anabar Bay,Laptev Sea

A detailed analysis of organic matter from the Oxfordian-Lower Valanginian interval of the Nordvik section (Anabar Bay) allows the definition of three geochemical horizons (terpane, diasterene, and hopane), which are characterized by specific geochemical compounds and their ratios. These horizons are correlated with several stages in the evolution of microfossils associated with ecological and geochemical changes in sea paleobasin. Our study shows a good correlation among the variation in many geochemical parameters, the composition of microfossil assemblages, and the transgressive-regressive phases of the paleobasin evolution. Moderately shallow-water facies was reconstructed using micropaleontological, palynological, and lithological data from the upper and lower parts of the section, where the terpane and hopane horizons were identified. Both horizons are characterized by a general dominance of hopanes over other polycyclic biomarkers, the presence of compounds with the biological configuration and organic matter of mixed terrestrial-marine origin, the presence of benzohopanes and retene, an indicator of the conifer resins. This is also reflected in the composition of palynological assemblages, which are dominated by terrestrial palynomorphs, with rare conifer pollen grains. Relatively deep-water facies were identified in the middle part of the section (diasterene horizon). A distinctive geochemical feature of this interval is high relative abundances of diasterenes and 4-methyldiasterenes. The lower subhorizon is characterized by the highest values of the pristane/n-C₁₇ ratio and relatively light δ¹³C values of noncarbonate carbon. The aromatic fractions have anomalously high concentrations of methyltrimethyltridecylchromans (MTTCs), which are interpreted to be derived mostly from chlorophyll of prasinophytes. The terpenoid distribution is marked by the presence of neohop-13(18)-enes, which probably originated from the activity of methanotrophic bacteria. The above geochemical parameters indicate high photic zone productivity (which is confirmed by the composition of palynological assemblages with abundant dinocysts and prasinophytes) that favored the accumulation of organic matter in dysaerobic conditions, which periodically occurred in the bottom of paleobasin. The alternation of dysaerobic and low-oxic bottom water conditions is easily reconstructed from the analysis of microbenthic communities. The analysis of biogeochemical, micropaleontological, paleontological, and palynological data on the Upper Volgian-lowermost Berriasian organic-rich shales revealed a very good source rock potential for this part of the section, as indicated by relatively high concentrations of organic matter of mixed bacterial-algal genesis and stagnant conditions during deposition and diagenesis. However, this potential was not realized because of the extremely “mild” thermobaric conditions that existed within the Mesozoic strata of the present-day Anabar Bay. At the same time, our results and analysis of the available data allow an optimistic assessment of the hydrocarbon potential of Jurassic-Lower Cretaceous deposits on the Laptev Sea shelf.     

Heavy metals in stream sediments: Effects of human activities

The content of 11 heavy metals in the sediments of a stream system was determined by atomic absorption analysis. Geochemical phases were investigated using a sequential extraction scheme, and bulk contents were assessed with a single HNO₃ extraction. Certain heavy metals were associated with different geochemical phases. Co, Mn, and Ba concentrated primarily in the carbonate and Mn phases, while all the remaining metals concentrated in the Fe and remnant phases. Features located along the stream system influenced the content of heavy metals. Results from the geochemical phases indicated Cu, Pb, Zn, Cd and Ag were emitted by one landfill, while Cd, Ba, and Ag were emitted by a second landfill. A wastewater treatment facility appeared to emit Ni and Cu. A stream draining a reservoir and joining the study stream resulted in dilution of the heavy metals in the sediments. A populated area along the study stream appeared to emit Mn. The single HNO₃ extraction procedure is quicker to perform than the sequential extraction but does not indicate the phase associations.     

Quantifying time scales of pedogenic calcrete formation using U-series disequilibria

Time scales of pedogenic calcrete development are quantified by subsampling carbonate from within a mature (stage V) pedogenic calcrete profile from southeast Spain and dating the material by U-series disequilibria. The location of the earliest and latest cements can be estimated by comparing previous studies of calcrete morphological development with micromorphological analysis of the study profile. Carbonate was sampled and dated from three locations within the profile: (1) below the lower surface of clasts within the hardpan (representing the earliest cement present—207±11 ka), (2) from the centre of cement filled pores within the hardpan (reflecting the final plugging of the calcrete hardpan—155±9 ka) and (3) from the laminar calcrete overlying the hardpan (representing the latest cement—112±15 ka). These results show that the hardpan took between 73 and 31 ka to form, whilst the mature stage V profile took between 121 and 69 ka to form. This is the first time that rates of mature calcrete development have been established by direct radiometric dating of the authigenic carbonate. The technique is appropriate for dating mature calcretes in dryland regions worldwide and offers the opportunity of increasing our understanding of the spatial and temporal variability in rates of pedogenic calcrete development.     

Reclamation influence and background geochemistry of neutral saline soils in the Po River Delta Plain (Northern Italy)

Reclaimed neutral saline sulphate soils constitute a large part of the eastern part of Po Plain lowlands, where intensive agricultural activities take place. The knowledge of their geochemical features is essential to develop the best management practices capable to preserve this threatened environment. With this aim, three boreholes were drilled in an agricultural field and a typical reclaimed soil profile has been characterized for major and trace element, pH, electrical conductivity, redox conditions and water-soluble anions and ammonium. Statistical analysis (cluster analysis and principal component analysis) has been used to understand the relationship between elements and grain size. The soil profile is characterized by high salinity and high organic matter contents responsible for high chloride, sulphate, and ammonium concentrations. Heavy metal content is naturally high, since Po Plain sediments are the result of ultramafic rocks erosion; in addition, organic matter tends to concentrate heavy metals by adsorption, mainly in peaty horizons. As a consequence of chemical and zootechnical fertilization, high NO₃ ^? contents have been found in the top soil, thus enhancing the risk of nitrate discharge in the water system, especially in relation to extreme climatic events.     

Abundance and fractionation of Al,Fe and trace metals following tidal inundation of a tropical acid sulfate soil

Tidal inundation was restored to a severely degraded tropical acid sulfate soil landscape and subsequent changes in the abundance and fractionation of Al, Fe and selected trace metals were investigated. After 5 a of regular tidal inundation there were large decreases in water-soluble and exchangeable Al fractions within former sulfuric horizons. This was strongly associated with decreased soil acidity and increases in pH, suggesting pH-dependent immobilisation of Al via precipitation as poorly soluble phases. The water-soluble fractions of Fe, Zn, Ni and Mn also decreased. However, there was substantial enrichment (2–5×) of the reactive Fe fraction (Fe_R; 1 M HCl extractable) near the soil surface, plus a closely corresponding enrichment of 1 M HCl extractable Cr, Zn, Ni and Mn. Surficial accumulations of Fe(III) minerals in the inter-tidal zone were poorly crystalline (up to 38% Fe_R) and comprised mainly of schwertmannite (Fe₈O₈(OH)₆SO₄) with minor quantities of goethite (α-FeOOH) and lepidocrocite (γ-FeOOH). These Fe (III) mineral accumulations provide an effective substrate for the adsorption/co-precipitation and accumulation of trace metals. Arsenic displayed contrary behaviour to trace metals with peak concentrations (∼60 μg g⁻¹) near the redox minima. Changes in the abundance and fractionation of the various metals can be primarily explained by the shift in the geochemical regime from oxic–acidic to reducing-circumneutral conditions, combined with the enrichment of reactive Fe near the soil surface. Whilst increasing sequestration of trace metals via sulfidisation is likely to occur over the long-term, the current abundance of reactive Fe near the sediment–water interface favours a dynamic environment with respect to metals in the tidally inundated areas.     

Geochemical and C, O, Sr, and U-series isotopic evidence for the meteoric origin of calcrete at Solitario Wash, Crater Flat, Nevada, USA

Calcite-rich soils (calcrete) in alluvium and colluvium at Solitario Wash, Crater Flat, Nevada, USA, contain pedogenic calcite and opaline silica similar to soils present elsewhere in the semi-arid southwestern United States. Nevertheless, a ground-water discharge origin for the Solitario Wash soil deposits was proposed in a series of publications proposing elevation-dependent variations of carbon and oxygen isotopes in calcrete samples. Discharge of ground water in the past would raise the possibility of future flooding in the unsaturated zone at Yucca Mountain, Nevada, site of a proposed high-level nuclear waste repository. New geochemical and carbon, oxygen, strontium, and uranium-series isotopic data disprove the presence of systematic elevation-isotopic composition relations, which are the main justification given for a proposed ground-water discharge origin of the calcrete deposits at Solitario Wash. Values of δ¹³C (−4.1 to −7.8 per mil [‰]), δ¹⁸O (23.8–17.2‰), ⁸⁷Sr/⁸⁶Sr (0.71270–0.71146), and initial ²³⁴U/²³⁸U activity ratios of about 1.6 in the new calcrete samples are within ranges previously observed in pedogenic carbonate deposits at Yucca Mountain and are incompatible with a ground-water origin for the calcrete. Variations in carbon and oxygen isotopes in Solitario Wash calcrete likely are caused by pedogenic deposition from meteoric water under varying Quaternary climatic conditions over hundreds of thousands of years.     

Geochemical and mineralogical study of a site severely polluted with heavy metals (Maatheide, Lommel, Belgium)

The former zinc smelter site ‘de Maatheide’ in Lommel (Belgium) was severely polluted with heavy metals and the pollution spread into the surroundings by rain water leaching and wind transportation. This study focuses on the processes of immobilization and natural attenuation that took place on the site. Three important factors were found. Firstly, the high pH values (pH 7–8) in the topsoil influence the mobility of heavy metals. Secondly, the spodic horizons below the polluted top layer seem to accumulate heavy metals, thereby slowing down their release into the environment. Finally, the glassy phases and iron oxi/hydroxides that are present can encapsulate heavy metals during their formation/recrystallization, thereby immobilizing them. An additional shielding effect results from the reaction rims of goethite around the contaminant phases, which partially inhibit the weathering process and release of contaminants. This shielding effect is an important factor to take into account when modelling contaminant release.     

The association of gold with calcrete

The discovery that Au accumulates in calcrete (pedogenic carbonate or caliche) was made in 1987 by CSIRO. Calcrete is a general term describing accumulation of alkaline earth metals in soils of arid and semi-arid terrains around the world. The principal constituent of calcrete is calcite while Au is a noble metal. Calcrete has been a significant tool in a number of Au deposit discoveries, so understanding the mechanisms by which these diametrically different components come together is valuable for enhancing future discovery. Numerous laboratory experiments, case histories and exploration models have been published (most from Australia) yet we do not fully understand the mechanisms involved. It is timely, therefore, twenty-five years on since the first publication of this phenomenon, to review this highly unusual but economically important association.Critical to any review on Au in calcrete is to first consider calcretes themselves. The nature of a particular calcrete, where it has formed and mode of formation is relevant to how, where and why Au accumulates within it. This review commences with a background, nomenclature, history, classification and some examples of calcrete types found near Au deposits. How calcretes form, their origins and the role of biota is considered. Their locations in the regolith and landscape, as well as exploration models for Au in calcrete are discussed. A section on the chemistry of Au in calcretes details what we know about possible mechanisms of formation and considers what laboratory experiments on microorganisms and abiotic experiments tell us. Following on is a summary of practical aspects of identifying, collecting and analysing samples for exploration purposes. Selected mineral exploration case histories are described and how they fit into models of exploration and different regolith settings. Concluding sections include a summary and implications of this accumulated knowledge to discovering Au deposits.     

Chemical mass balance of calcrete genesis on the Toledo granite (Spain)

The chemical mass balance of calcrete genesis is studied on a typical sequence developed in granite, in the Toledo mountains, Central Spain.

Field evidence and petrographic observations indicate that the texture and the bulk volume of the parent rock are strictly preserved all along the studied calcrete profile.

Microscopic observations indicate that the calcitization process starts within the saprolite, superimposed on the usual mechanisms of granite weathering: the fresh rock is first weathered to secondary clays, mainly smectites, which are then pseudomorphically replaced by calcite. Based on this evidence, chemical mass transfers are calculated, assuming iso-volume transformation from the parent rock to the calcrete.

The mass balance results show the increasing loss of matter due to weathering of the primary phases, from the saprolite towards the calcrete layers higher in the sequence. Zr, Ti or Th, which are classically considered as immobile during weathering, are also depleted along the profile, especially in the calcrete layer. This results from the prevailing highly alkaline conditions, which could account for the simultaneous precipitation of CaCO₃ and silicate dissolution.

The calculated budget suggests that the elements exported from the weathering profile are provided dominantly by the weathering of plagioclase and biotite. We calculate that 8–42% of the original Ca remains in granitic relics, while only 15% of the authigenic Ca released by weathering is reincorporated in the calcite. This suggests that 373 kg/m² of calcium (i.e., three times the original amount) is imported into the calcrete from allochtonous sources, probably due to aeolian transport from distant limestone formations.     

Distribution of heavy metals in soils of Port Harcourt and its environs,Niger Delta,Nigeria

Geochemical evaluation of the distribution of heavy metals in soils of Port Harcourt and its environs in the Niger Delta region is presented in respect of anthropogenic factor and index of geoaccumulation. Sixteen (16) soil samples were collected from two horizons (0-10 cm and 100 cm) from the various grids and analyzed. The geo-chemical analyses showed the vertical and horizontal distributions of heavy metals. The results showed the ranges of the metals determined as follows: Pb (6.86-2.49)×10-6, with an average of 4.63×10-6; Cd (0.05-0.00)×10-6, with an average of 0.02×10-6, As (0.01-0.00)×10-6, with an average of 0.00×10-6. Cu (15.36-10.80) ×10-6, with an average of 13.36×10-6, and V (1.36-0.20)×10-6, with an average of 0.94×10-6. Quantification of the degree of pollution was carried out using anthropogenic factor (AF) and index of geoaccumulation (Igeo). The Igeo values of 0.06, 0.02 and 0.00 for Pb, Cd and As, respectively indicate low-level contamination while Zn (1.14) and V (1.40) show me-dium-level contamination. The sources of contamination are attributed to urbanized anthropogenic activities. The majority of the samples analyzed show that the AF values are less than 1 with the exception of vanadium (V) whose AF values range from 2.73 to 13.60×10-6. Vanadium is more enriched than As, Cd, Pb, and Cu. The order of degrees of anthropogenic contamination and index of geoaccumulation in the soil is V >Zn >Pb >Cu >Cd >AS. Metals were retained near the top soil and their concentrations in the deepest horizons were lower and normal for uncontaminated soils. Metal concentrations in the top soil horizons were significantly related to distance from the industrial and hu-man activities.