Chemical partitioning of trace and major elements in soils contaminated by mining and smelting activities

Soils from historical Pb mining and smelting areas in Derbyshire, England have been analysed by a 5-step sequential extraction procedure, with multielement determination on extraction solutions at each step by ICP-AES. Each of the chemical fractions is operationally defined as: (i) exchangeable; (ii) bound to carbonates or specifically adsorbed; (iii) bound to Fe–Mn oxides; (iv) bound to organic matter and sulphides; (v) residual. The precision was estimated to be about 5%, and the overall recovery rates were between 85 and 110%. The carbonate/specifically adsorbed and Fe–Mn oxide phases are the largest fractions for Pb in soils contaminated by both mining and smelting. Most of the Zn is associated with Fe–Mn oxide and the residual fractions. Cadmium is concentrated in the first 3 extraction steps, particularly in the exchangeable phase. The most marked difference found between soils from the mining and smelting sites is the much higher concentrations and proportions of metals in the exchangeable fraction at the latter sites. This indicates greater mobility and potential bioavailability of Pb, Zn and Cd in soils at the smelting sites than in those in the mining area. The most important fraction for Fe and Al is the residual phase, followed by the Fe–Mn oxide forms. In contrast, the Fe–Mn oxide fraction is the dominant phase for Mn in these soils. In the mining area, most of the Ca is in the carbonate fraction (CaCO₃), while the exchangeable and residual phases are the main fractions for Ca at the smelting sites. Phosphorus is mainly in the residual and organic fractions in both areas. The exchangeable fractions of Pb, Zn and Cd in soils were found to be significantly related to the concentrations of these metals in pasture herbage.     

Laser ablation of stream-sediment pebble coatings for simultaneous multi-element analysis in geochemical exploration

Laser ablation of the Fe and Mn oxide coatings on stream sediments has been tested as a means of rapidly introducing this highly sorptive geochemical exploration medium into an inductively coupled plasma emission spectrometer (ICP) for simultaneous multielement analysis.Training data were obtained by selectively leaching coatings on about ten 1-cm diameter pebbles from 50 sites in the Allen drainage system, Southwest England. The Pb, Zn, Fe and Mn concentrations of the resulting leachates were determined by atomic absorption spectrophotometry. This procedure is relatively rapid and economical, but the leachate is suitable only for the determination of a restricted range of elements (mainly heavy metals). The laser-microprobe testing data were obtained by vaporizing approximately 1 μg of coating from one pebble from each sample site with a laser pulse, producing a crater in the coating 150–200 μm in diameter and 30–50 μm deep. The ablation was effected within a cell which the laser beam penetrates via a quartz window and the vaporized material quickly condenses into an aerosol which is carried in a flow of argon passing through the cell to the ICP, for simultaneous determination of up to 36 elements.Training and testing data for the elements determined were normalized by ratioing to Fe or Mn following a preliminary statistical inspection of the data to ascertain predominant correlations. In the Allen drainage basin, where a narrow and impersistent galena vein with subordinate sphalerite occupies a north-south-trending fracture, Pb determinations on coatings correlate well with the Fe content of coatings, while Zn correlates with Mn. The Pb/Fe dispersion patterns produced by the training and testing procedures are essentially similar, as are the Zn/Mn patterns from each of the procedures, demonstrating the potential of the novel laser microprobe technique.Anomalous Pb/Fe and Zn/Mn ratios in pebble coatings occur in the vicinity of the mineralized fracture. These compare favourably in terms of anomaly contrast and length of dispersion trains (especially their extension beyond major confluences) with the Pb and Zn anomalies detected by the more conventional analysis of the minus 200 μm fraction of the stream sediment. The low levels of potential pathfinder elements associated with mineralization do not lend themselves readily to determination in leachates derived from pebble coatings. Laser microprobe data, however, revealed a low-order but punctual As/Fe anomaly in a tributary, where this cuts the mineralized vein.     

Fe-Mn oxide coatings in stream sediment geochemical surveys

Downstream dispersion curves for certain trace metals were obtained from two mineralized areas in the southeastern United States. Fe-Mn oxide coating on lithic fragments and quartz pebbles, as well as the minus 80-mesh fraction of the coexisting stream sediment were analyzed for a variety of metals. In Lincoln County, Georgia, 8 sample sets were collected along a stream draining the Magruder mine, a polymetallic sulfide deposit (Zn-Cu-Pb-Ag-Au) in metavolcanic rocks. Five sample sets were collected along Joe Mill Creek in Grainger County, Tennessee, downstream from a zone of zinc mineralization in carbonate rocks (Mississippi Valley-type). In addition, 5 sample sets were collected from an unmineralized area near Athens, Georgia.The results indicate the following: (1) the anomaly/background ratio for zinc and copper is markedly higher in the Fe-Mn oxide coatings in the mineralized drainages; (2) in drainages containing lead mineralization, the anomaly/background ratio is markedly higher in the minus 80-mesh fraction for lead which is not concentrated in the coatings; and (3) the ratios Zn/Mn and Cu/Mn, as well as Zn/Co and Cu/Co, in the Fe-Mn oxide coatings enhance downstream detectability of mineralization.There are several potential advantages of using coatings versus the conventional minus 80-mesh fraction in stream sediment geochemical surveys. Because soluble metal is brought into the stream mainly in groundwater, deeper anomaly sources may be detectable from the oxide coatings than from clastic fractions of alluvium where much of the metal is derived from surficial erosion. Variability due to sampling may also be reduced, providing better discrimination of anomalies. In areas of glacial or alluvial cover, coating surveys may be particularly applicable.     

Enzyme leach anomalies associated with deep Mississippi Valley-type zinc ore bodies at the Elmwood Mine, Tennessee

Deeply buried Mississippi Valley-type deposits that have been or are currently being mined in North America were initially discovered by drilling. Conventional geochemical methods are ineffective for detecting these ‘blind' deposits when they occur deep within sequences of stable-platform carbonates and shales. The ‘enzyme' leach is a selective analytical technique for determining trace elements associated with amorphous Mn oxide coatings in soils. In many areas of the world, the enzyme leach method is useful for detecting low-level geochemical anomalies in soils, which are associated with blind mineral deposits. Enzyme leach analysis of soils, collected at the Elmwood Mine, Tennessee, revealed high-contrast anomalies over ore bodies 370 m below the surface. In areas where the soils are in chemical equilibrium, ‘combination' anomalies occur over Zn ore bodies. These are characterized by asymmetrical halogen halos which occur around a halogen ‘central low'. Commodity metals (Zn and Pb) and trace elements associated with the ore (Cd, Ba, and Mn) form apical anomalies, which occur over the ore bodies and within the halogen halo. Under most circumstances, agricultural practices do not affect enzyme leach results. However, agricultural activity in central Tennessee appears to have altered the proportion of amorphous Mn oxides in the soils in some locations. Where the MnO₂-form equilibrium of the soil has been disturbed, enzyme leach data are erratic. In the one instance where this was encountered, ratioing the data to Mn reveals anomalies which bracket the blind ore bodies.     

Chemistry of rainwaters in the south Pacific area of Russia

On the south-eastern edge of Russia, the chemical composition of rainwater is controlled by sea salts, terrestrial material, as well as volcanic (Kuril islands volcanic area) and anthropogenic emissions, mostly in the southern part of the area. The predominant major ions of the Primorye, Sakhalin and the Kuril Islands rainwaters were respectively HCO₃⁻–SO₄²⁻, Ca–Na, and of Cl–Na. Concentration of trace elements changes within 1–2 orders of magnitude but some difference in the distribution of the elements between continental and island rainwater is found. The concentration of the chemical elements in the particulate fraction varies from < 10% to 90% of the total concentration (dissolved + particulate) with the following distribution: Tl, Na, Ca, Sr, Zn, Cd (< 10%)–Be, Th, Bi, Rb, U, K, Sc (10–20%)–Cu, Mn, Mg, Mo, Se, Ba, Ni, As, Ag, Cs, Co, Y, Ga, V (20–50%)–Sb, Pb, Ge, Cr, Fe, Al (50–90%).The concentration of elements of the particulate fraction of the rainwater usually is significantly different from concentrations in the crust, including both higher and lower concentrations. The terrestrial contribution to dissolved elements was evaluated and follows the decreasing order: Fe > K, Mg, Ca > Ba, Sr > Na (65–1%). Close order was found for total (dissolved and solid) concentrations. Sea salt contribution to dissolved element concentration in the rainwater decrease in the following order: Cl, Mg > K, SO₄ > Ca > HCO₃⁻, Ba, Fe (78–0.1%). Calculation of anthropogenic and volcanic inputs for two ions (Cl⁻ and SO₄²⁻) shows that anthropogenic inputs for the Vladivostok and Yuzno-Sakhalinsk cities can be evaluated as 15–20% of Cl⁻ and up to 80–90% of SO₄²⁻. Volcanic components in the Kuril Islands, where anthropogenic inputs are absent, can reach up to 76% of SO₄²⁻ and 36% of Cl⁻.     

Biogeochemistry of manganese oxide coatings on pebble surfaces in the Kikukawa River System,Shizuoka, Japan

The biogeochemistry of Mn-oxide coatings formed over submerged pebble surfaces on the streambed of the Kikukawa river system has been investigated. Located in central Shizuoka, Japan, this system drains strongly acidified soils under tea plantations. Besides containing high amounts of Mn (up to 450 μg/cm²), the coatings are capable of scavenging and accumulating other elements including Ba, Zn, Ni, Co, W, Mo and Sb. When suspensions of the coating material were incubated with 0.2 mM Mn²⁺, the Mn(II) ion was microbially transformed into Mn-oxides. When the same suspensions were spread on agar plates containing acetate, yeast-extract, and 1.0 mM Mn²⁺ (AY agar medium) both Mn-oxidizing bacteria and fungi appeared, indicating the existence of a diversity of Mn-oxidizing microorganisms in the system. Plate counts using two agar culture media with varied nutrient levels indicated that the ability of these microorganisms to oxidize Mn(II) was strongly dependent on nutrient supply. The relatively nutrient-poor AY agar medium was more conducive to microbial growth than the K₁ agar medium with a higher organic nutrient content. Concentrations of Mn dissolved in the stream waters did not correlate well with the amounts of solid Mn on submerged pebbles. Thus, factors other than dissolved Mn concentration (e.g., organic nutrient supply and pH) determined the ability of microorganisms to oxidize Mn in the streambeds. A survey of dissolved Mn in streams and water draining tea plantations combined with chemical analysis of Mn in the underlying soils indicate that the soils have been strongly acidified through excessive applications of N-fertilizers. As a result, Mn was leached from the soil column into the Kikukawa river system. Biogenic Mn-oxide coatings on streambeds can therefore serve as an indicator of soil acidification and metal leaching from soils of the corresponding watershed.     

Experimental study of liquid evolution in an Fe-rich,layered mafic intrusion: constraints of Fe-Ti oxide precipitation on the T-fO 2 and T-ϱ paths of tholeiitic magmas

The Newark Island layered intrusion, a composite intrusion displaying a similar fractionation sequence to the Skaergaard, has both dikes which preserved liquids fed into the intrusion and chilled pillows of liquids resident in the chamber. This study reports experimentally determined one atmosphere liquid lines of descent of these compositions as a function of oxygen fugacity which varies from QFM (quartz-fayalite-magnetite) to 0.5 log₁₀ units above IW (iron-wustite). These experiments reveal a strong oxygen fugacity dependence on the order of appearance and relative abundances of the Fe–Ti oxide minerals. Titanomagnetite saturates prior to ilmenite at QFM, but the order is reversed at lower oxygen fugacities. In the layered series of the Newark Island intrusion, ilmenite arrives shortly before titanomagnetite and the titanomagnetite/ilmenite ratio decreases monotonically after the cumulus appearance of titanomagnetite. Comparison of the crystallization sequence in the intrusion with that of the experiments requires that the oxygen fugacity in the intrusion increased relative to QFM before titanomagnetite saturation and decreased afterward, but always remained between the QFM and IW buffers. Similar trends in the modes of the Fe–Ti oxides (ilmenite and titanomagnetite) in the Skaergaard, Kiglapait, and Somerset Dam intrusions along with Fe₂O₃/FeO ratios in MORBs suggest that such a temperature-oxygen fugacity path may be typical of tholeiitic magma differentiation. Calculations of the temperature-density paths of the experimental liquids indicate that, at all possible oxygen fugacities, the density must have decreased abruptly after Fe–Ti oxide saturation. Accordingly, liquids replenishing the intrusion after Fe–Ti oxide saturation should pond at the bottom of the chamber, quenching against older cumulates. Field observation at the Newark Island intrusion confirm this prediction. The similarities in the fractionation paths of several other layered intrusions to that of the Newark Island intrusion suggest that the density of the liquids in these intrusions also decreased after Fe–Ti oxide saturation. Experiments on a suggested initial Skaergaard liquid are consistent with this model.     

Geochemical characteristics of selected elements in iron–manganese cutans and matrices of Alfisols in central China

The elemental geochemistry of major, minor and trace elements in iron–manganese cutans and the corresponding matrix soils, collected from three Alfisols in central China, are studied using their chemical compositions as well as correlation and factor analyses. Fe–Mn cutans accumulate high concentrations of MnO₂ and Fe₂O₃. Mean values of these two elements in cutans are about 13.7 and 1.4 times higher than those in the matrix soils. pH, clay contents, extractable X-ray noncrystalline Fe (Feo) and the ratio of Feo to free Fe-oxide (Fed) in cutans are notably higher than those in the corresponding matrices. Cutans are also enriched in some bases and heavy metals. Averages of K, Na, Co and Pb concentrations are about 2.0, 1.4, 15.4 and 6.0 times higher than those in the matrices. Statistical analysis indicates that Co, Ni, Li, Cu and Zn are abundant in Mn minerals of cutans, while Pb exists mainly in iron minerals. Fe–Mn cutans constitute an active microzone of solid–solution–plant–air interaction, element movement and exchange in soils, which cause the contents of Fe- and Mn-oxides, elemental concentrations, and geochemical behavior of cutan to show marked differences in matrix soils.     

Intercrystalline cation partitioning between minerals of the triplite-zwieselite-magniotriplite and the triphylite-lithiophilite series in granitic pegmatites

Minerals of the triphylite-lithiophilite, Li(Fe, Mn)PO₄, and the triplite-zwieselite-magniotriplite series, (Mn, Fe, Mg)₂PO₄F, occur in the late stage period of pegmatite evolution. Unfortunately, neither are the genetic relationships between these phosphates fully understood nor are thermodynamic data known. Consequently, phosphate associations and assemblages from 8 granitic pegmatites — Clementine II, Rubicon II and III, and Tsaobismund (Namibia); Hagendorf-Süd and Rabenstein (Germany); Valmy (France); Viitaniemi (Finland) — have been tested for compositional zoning and intercrystalline partitioning of main elements by electron microprobe techniques. Although the selected pegmatites display varying degrees of fractionation, and the intergrowth textures indicate different genetic relationships between the phosphates, the plots of mole fractions X _Fe=Fe/(Fe+Mn+Mg+Ca), X _Mn=Mn/(Fe+Mn+Mg+Ca), and X _Mg=Mg/(Fe+Mn+Mg+Ca) can be fitted relatively well with smooth curves in Roozeboom diagrams. Their deviations from symmetrical distribution curves are mainly dependent upon X _Mg or X _Ca, and upon non-ideal solutions. Surprisingly small differences between the partition coefficients were detected for intergrowths of different origin. However, the partitioning of shared components among coexisting phases is clearly dependent upon the conditions of formation. Compositional zoning is observed only when both Fe–Mn phosphates are intergrown mutually or with other Fe–Mn–Mg mineral solid-solutios. Thus, the zoning does not seem to be due to continuous crystallization, but to later diffusion processes. The triplite structure has preference for Mn, Mg, and Ca, while Fe prefers minerals of the triphylite series. A quantification of main element fractionation between minerals of the triphylite and the triplite series is possible in the cases where diffusion can be excluded. For the Fe/(Fe+Mn) ratios of core compositions an equation with a high correlation coefficient (R=0.988) was determined: Fe/(Fe+Mn)_Tr=[Fe/(Fe+Mn)_Li]/{2.737-(1.737)[Fe/(Fe+Mn)_Li]} (Tr=triplite series, Li=triphylite series). Consequently, the Fe/(Fe+Mn) ratio of the triplite series can now also be used in the interpretation of pegmatite evolution, just like that of the triphylite series which has been successfully applied in the past.     

A refined garnet - biotite Fe−Mg exchange geothermometer and its application in amphibolites and granulites

A new formulation of garnet-biotite Fe–Mg exchange thermometer has been developed through statistical regression of the reversed experimental data of Ferry and Spear. Input parameters include available thermo-chemical data for quaternary Fe–Mg–Ca–Mn garnet solid solution and for excess free energy terms, associated with mixing of Al and Ti, in octahedral sites, in biotite solid solution. The regression indicates that Fe–Mg mixing in biotite approximates a symmetrical regular solution model showing positive deviation from ideality withW _FeMg ^bi =1073±490 cal/mol. H _r and S _r for the garnet-biotite exchange equilibrium were derived to be 4301 cal and 1.85 cal respectively. The resultant thermometer gives consistent results for rocks with a much wider compositional range than can be accommodated by earlier formulations.     

Elemental distribution of coastal sea and stream sediments in the island-arc region of Japan and mass transfer processes from terrestrial to marine environments

A total of 49 elements have been identified in 338 coastal sea sediment samples collected from an area situated off the Ise-Tokai region of Japan for a nationwide marine geochemical mapping project. The spatial distribution patterns of the elemental concentrations in coastal seas along with the existing geochemical maps in terrestrial areas were used to define the natural geochemical background variation, mass transport, and contamination processes. The elemental concentrations of coastal sea sediments are determined primarily by particle size and regional differences. Most elemental concentrations increase with a decrease in particle size. Some elements such as Ca, Mn, and Yb are found to exist in large quantities in coarse particles containing calcareous shells, Fe–Mn oxides, and felsic volcanic sediments. Regional differences reflect the mass transfer process from terrestrial areas to coastal seas and the influence of the local marine geology. An analysis of variance (ANOVA) reveals that for many elements, the particle size effect is predominant over regional difference. The mean chemical compositions of coastal sea sediments are similar to those of stream sediments in adjacent terrestrial areas and in the upper crust of Japan. This observation supports the fact that coastal sea sediments have certainly originated from terrestrial materials. However, the spatial distributions of elemental concentrations are not always continuous between the land and coastal seas. The scale of mass movement observed in marine geochemical maps occurs at a distance of 20 km from the river mouth. A detailed examination of the spatial distribution patterns of K (K₂O) and Cr concentrations suggests that terrestrial materials supplied through rivers are deposited near the shore initially, and then gravity-driven processes shift the sediments deeper into the basin. Contamination with heavy metals such as Zn, Cd and Pb was observed in coastal bays surrounded by urban and industrial areas. It is noteworthy that the areas with the highest concentration of these elements usually do not occur near the shore (not near the contamination source) but at the center of the bay. Unexpected low concentrations of Zn, Cd and Pb near shore may either be due to a decreased anthropogenic load in the most recent sediments or to dilution by unpolluted flood sediments.     

New calibration data for the Fe–Ti oxide thermo-oxybarometers from experiments in the Fe–Ti–O system at 1 bar, 1,000–1,300°C and a large range of oxygen fugacities

The current formulations of the Fe–Ti oxide thermobarometer (titanomagnetite–ilmenite_ss) fail to reproduce experimental results, in particular at the high temperatures that are relevant for basaltic assemblages. With the aim of improving the experimental basis of the calibration in the Fe–Ti–O system, we have synthesised assemblages of titanomagnetite–ilmenite_ss (Tmt–Ilm_ss), ilmenite_ss–pseudobrookite_ss (Ilm_ss–Psb_ss) and single-phase samples under a wide range of fO₂ (fixed with CO/CO₂ mixtures or by solid oxygen buffers) in sub-solidus conditions (1,000–1,300°C) at 1 bar. Runs lasted 24 h at 1,300°C and up to 240 h at 1,000°C and were terminated by quenching in water. All run products are polycrystalline, roughly equigranular aggregates, with grain sizes of 10–50 m. They were examined and analysed with the SEM and EMP. Tmt compositions are broadly in accordance with the current models at moderate fO₂, but significantly richer in Ti at low fO₂ and high T, due to cationic vacancies. Ilm_ss compositions depart from the predicted values practically at all fO₂ and T conditions, which is related to unsatisfactory thermodynamic models for the rhombohedral oxide. For Ilm_ss–Psb_ss assemblages the best agreement between our data and current calculations is at 1,000°C and moderately high fO₂. Otherwise, experimental and calculated data strongly disagree. The experimental data set on the three Fe–Ti oxide solid solutions presented here is intended to support new versions of both the titanomagnetite–ilmenite_ss thermo-oxybarometer and the ilmenite_ss–pseudobrookite_ss oxybarometer.     

Biogeochemistry of trace metals (Mn, Sr, Rb, Ba, Cu, Zn, Pb and Cd) in a river-wetland-lake system (Balaton Region, Hungary)

Mn, Sr, Ba, Rb, Cu, Zn, Pb and Cd concentrations have been measured seasonally in the water and deposited sediments of the system comprising: Zala river (main input) — Lakes Kis-Balaton 1 and 2 (small artificial lakes created in a former bay of Lake Balaton) — Keszthely bay (hypertrophic part of Lake Balaton). The concentrations of the trace elements together with pH, alkalinity, dissolved cations (Ca²⁺, Mg²⁺, Na⁺, and K⁺), dissolved inorganic ligands (Cl^–, SO₄ ^2–), particulate Al, Ca, inorganic and organic carbon are used to assess the contamination of the study area and biogeochemical processes controlling trace element concentrations. Thermodynamic speciation calculations have also been utilized to enhance our understanding of the system. In the sediments Rb, Ba, Cu and Zn concentrations were mainly controlled by the abundance of the aluminosilicate fraction. Strontium was mainly associated with the calcium carbonate fraction. The aluminosilicate fraction constitutes a major sink for Mn and Cd but the concentration of these elements are also strongly related to calcite precipitation. The main processes that control the dissolved distribution of trace elements in the Balaton system were: solid phase formation (carbonate) for Mn; coprecipitation with calcite for Sr, Ba, Rb and possibly Mn and Cd; adsorption/desorption processes (pH dependent) for Zn and Pb; solubilization of Mn and precipitation of Cd and Cu in reed covered wetland areas where anoxic conditions were probably existing during the warm season. A preliminary budget of atmospheric and river input to Lake Balaton has also been outlined. Although Lake Balaton, is subjected to anthropogenic inputs mainly from agricultural and domestic activities, their impact on trace element concentrations in the Balaton system is very limited due to the efficiency of removal processes (i.e. adsorption and co-precipitation) and to high sedimentation rates and strong sediment re-suspension. Anthropogenic inputs are only detected for Pb.     

Dahab stream sediments, southeastern Sinai, Egypt: a potential source of gold, magnetite and zircon

The stream sediments of Dahab area, southeastern Sinai, Egypt, were studied for their content of economic minerals. These sediments are immature as indicated by poor sorting and other mechanical parameters. They are derived from Precambrian basement rocks, which are mostly represented by granitic rocks in addition to lesser amounts of volcanics and gabbros. The mineralogical investigation revealed that these sediments contain considerable amounts of placer gold, Fe–Ti oxides and zircon.The concentrated Fe–Ti oxides comprise homogeneous magnetite and ilmenite in addition to ilmeno-magnetite, hemo-ilmenite and rutile–hematite intergrowths. Isodynamic separation of some raw samples of SIZE=1 mm revealed that up to 15.12% magnetic minerals can be recovered. Zircon shows remarkable variations in morphology, colour, chemistry and provenance. U-poor and U-rich varieties of zircon were discriminated containing UO₂ in the ranges of 0.04–1.19 and 3.05–3.68 wt.%, respectively. REE-bearing minerals comprise monazite, allanite and La-cerianite.On mineralogical basis, the present work suggests that Dahab stream sediments represent a promising target for further geochemical exploration for precious metals, especially gold. Fire assay data indicate that placer gold in the studied sediments sometimes reaches 15.34 g/t. Narrow gullies and valleys cutting the basement manifest the development and preservation of gold in this arid environment. Background concentration of gold and variation in lithology suggest multiple source of the metal in the investigated sediments.     

Ferromanganese oxide deposits from the Central Pacific Ocean,I. Encrustations from the Line Islands Archipelago

Chemical and mineralogical analyses of a well-controlled suite of ferromanganese encrustations from the Line Islands Archipelago (Central Pacific) suggest that they represent purely hydrogenous deposits—i.e. they have formed through the slow accumulation of trace metal-enriched oxides directly from the water-column. Mineralogically they consist predominantly of δMnO₂ and amorphous FeOOHxH₂O. Compositionally, they are similar to δMnO₂ nodules from adjoining basinal areas but are enriched in both Mn (mean = 20.4%, max = 29.3%) and Co (mean = 0.55%, max = 1.57%). δMnO₂ is the most important trace metal bearing phase; strong associations are noted between it and Co, Mo, Ni, Zn, and Cd, whilst only Be is associated specifically with FeOOH. V, Sr and Pb are partitioned between the authigenic oxide phases, whilst Ti most probably occurs as TiO₂xH₂O. Cu is contained in both aluminosilicate contaminant phases and Fe oxide phases. These relations are considered to reflect the differing scavenging behaviour of Mn and Fe oxides in the water column.Crusts from ~1–2 km are enriched in Mn and the Mn-related elements and exhibit higher $\text{Mn}\text{Fe}$ ratios than deeper crusts, which are compositionally constant. The higher $\text{Mn}\text{Fe}$ ratios may result from a supply of Mn from continental borderland sediments at these depths, which is transported horizontally by advective-diffusive processes. Since manganophile elements are enriched relative to Mn in the 1–2 km crusts, it is considered that the supply of Mn is scavenged by existing oxides, is oxidised and effectively occludes them. A higher proportion of oxide particles thus exhibit Mn oxide scavenging properties in the 1–2 km depth zone. The increased vertical flux of Mn resulting from the supply at ~1–2 km is not reflected by higher $\text{Mn}\text{Fe}$ ratios in deeper crusts, so that the vertical flux of oxides is not simply related to the standing crop. The $\text{Mn}\text{Fe}$ ratios of the crusts thus reflect the composition of suspended oxides at similar depths.     

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.     

Abundance, Sources and Speciation of Trace Elements in Humus-Rich Streams Affected by Acid Sulphate Soils

The behaviour of trace elements (Al, As, Cd, Co, Cr,Cu, Fe, Mn, Ni, V, Zn) was studied in five humus-richstreams (dissolved organic carbon = 14–40 mg/L)impacted by acid sulphate soils developed in marinesulphide-bearing fine-grained sediments. During heavyrainfalls in autumn, on which the study focusses, themetals Al, Cd, Co, Cu, Mn, Ni and Zn are extensivelyleached from these acidic soils (pH = 2.5–4.5), whileAs, Cr, Fe and V are not leached more strongly fromthis soil type than from areas of till and peat. Aspeciation experiment, based on anion and cationexchange of the stream waters in the field, showedthat (1) the metals Al, Cd, Co, Mn, Ni and Zn aretransported in the streams mainly as inorganiccations, (2) Cu exists mainly in cationic form but isalso to a significant extent associated with dissolvedhumic substances, (3) Fe occurs mainly in the anionicfraction explained by organic coating on colloidal Feoxyhydoxides and (4) the hydrochemistry of As, Cr andV is complex as these elements may exist in severalunquantified anionic fractions and to a minor extentin cationic species/forms. Whereas the proportion ofacid sulphate soils in the catchments had a largeimpact on concentrations levels of several elements inthe stream waters, these soils did not have a largeaffect on the speciation of elements in water.     

Petrochemistry of the Fish Cove rhyolite,Keweenaw peninsula,Michigan, U.S.A.

A small (360 × 180 m) rhyolitic intrusive body in the lower portion of the Portage Lake Lava Series of Michigan's Keweenaw peninsula was mapped and sampled in detail. The rhyolite is one of a number of similar bodies which make up less than 1% of the total volume of this thick Late-Precambrian plateau basalt pile. The rock is a low-calcium rhyolite with fine-grained homogeneous texture and sparse phenocrysts of plagioclase and quartz. Analyses of selected trace and major elements for 21 samples taken from the body reveal a chemical zonation consisting of a core zone enriched in K, Rb and Ba, and a border zone relatively poor in these elements. Little areal difference is found with respect to other elements tested (Mn, Sr, Zr, Ca, Ti, and Fe). This apparently primary zonation seems to result from the migration of K, Rb and Ba during crystallization of the shallow intrusive. Though zoned, the trace-element chemistry of the Fish Cove body is distinct from that of eight other rhyolites in the Portage Lake Lava Series, and suggests that fingerprinting by trace elements might be a fruitful method for identifying and correlating the sources of numerous rhyolitic pebbles in conglomerates interbedded with the basaltlava flows of the Portage Lake Series.     

Analytical perspective on trace element species of interest in exploration

Analysis of soil and sediment samples, using selective extraction methods to distinguish different phases, is of particular interest in exploration geochemistry to locate deeply buried mineral deposits. There are various mechanisms of binding labile elements in the secondary environment, including physical and chemical sorption, precipitation, chelation and complexation. Phases present in soils and sediments which are likely to scavenge ‘free' elements include amorphous Mn and Fe oxides, the humic and fulvic components of humus, and clays. This paper reviews these forms of trace elements and the methods in current use to quantify them. Examples of precision data, both for control and survey samples, are given with respect to trace elements dissolved from the ‘soluble organic' component of humus, Mn oxides and amorphous Fe oxides. The high sensitivity of inductively coupled plasma mass spectrometry (ICP–MS) is required to measure accurately and precisely a large suite of trace elements, especially where only small fractions of elements are dissolved by such leaches as the commercially available Enzyme and MMI (Mobile Metal Ion) extractions. The relative standard deviations (RSD) obtained for 33 elements (e.g. Ag, Cd, In, I) in the standard reference sample (SRM), TILL-2, are in the range 0.5–8% for the hydroxylamine hydrochloride (NH₂OH·HCl) leach designed to extract hydrous Fe and Mn oxides. The corresponding RSDs for elements in the reactive Mn oxide phase extracted by the Enzyme leach are in the range 3–19% except for some trace elements at levels close to detection limit (e.g. Cd, Bi). The RSDs obtained for field duplicates are inferior to those for analytical replicates (i.e. sample splits), probably a reflection of different concentrations of the host phase. In one soil survey, the Fe extracted by a 0.25 M NH₂OH·HCl leach ranged conservatively from 0.2 to 1.7% whereas the Mn extracted by the Enzyme leach varied extensively, from 0.3 to >999 ppm. In contrast, precision, at 1–7% RSD, for field duplicates was found to be comparable with that for both analytical duplicates and the SRM, LKSD-4, for elements associated with the humic and fulvic component of humus samples sieved to <177 μm.     

Stream water, an ideal medium for rapidly locating polymetallic mineralization in forest-swamp terrain: a case study in the Da Hinggan Mts., northern Heilongjiang, China

A forest-bog landscape is developed in an area of moderate to low topography in northeastern China. Bogs are widespread along U- and V-shaped valleys (200–2000 m wide) and in depressions. Due to the cold climate, it was initially thought that chemical weathering would be slight in the area. However, a study of the geochemistry of surface water showed that, although most elements occur in relatively low concentrations compared to average contents in world river water, a number of mobile elements are dispersed over long distances. Marked Cu, Zn, Fe, Mn, and SO²⁻₄ anomalies, and relatively weak Ni, Co, Be, Pb and F anomalies form in stream water in the vicinity of known mineralization. Concentrations of Cu, Pb, Zn, Fe, and Mn in suspensates show no marked variations between background and anomalous streams whereas Ag exhibits a marked increase in suspensates near the mineralization. The pH of stream water near the mineralization is considerably lower than the 5 to 6.5 values recorded for background water. It can be concluded that water plays an important role in transporting elements chemically and stream water is a useful medium to sample in follow-up geochemical surveys for base and precious metals (Ag) in this landscape.