Geochemical prospecting for groundwater in the granitic terrain around Ghatkesar,A.P. (India)

Soil samples collected from a depth of 8 cm near open wells were studied. Finer (minus 80-mesh) fractions of soil from the A-horizon contain more Mn and Fe compared to coarser fractions and these elements show higher concentrations in soils around wells with a deeper water-table. Greater weathering due to percolation of larger volumes of water through soil results in thorough decomposition of all the minerals, liberating the elements. During this process iron hydroxides with very little Mn form large fragile fragments. Higher Fe/Mn ratios in the minus 44 plus 60-mesh fractions of these soils are characteristic of deeper, high-yielding wells and have a positive correlation with depth of water table.     

Continental-scale patterns in soil geochemistry and mineralogy: Results from two transects across the United States and Canada

In 2004, the US Geological Survey (USGS) and the Geological Survey of Canada (GSC) initiated a pilot study that involved collection of more than 1500 soil samples from 221 sites along two continental transects across Canada and the United States. The pilot study was designed to test and refine protocols for a soil geochemical survey of North America. The two transects crossed a wide array of soil parent materials, soil ages, climatic conditions, landforms, land covers and land uses. Sample sites were selected randomly at approximately 40-km intervals from a population defined as all soils of the continent. At each site, soils representing 0 to 5 cm depth, and the O, A, and C horizons, if present, were collected and analyzed for their near-total content of over 40 major and trace elements. Soils from 0–5 cm depth were also collected for analysis of organic compounds. Results from the transects confirm that soil samples collected at a 40-km spacing reveal coherent, continental- to subcontinental-scale geochemical and mineralogical patterns that can be correlated to aspects of underlying soil parent material, soil age and climate influence. The geochemical data also demonstrate that at the continental-scale the dominance of any of these major factors that control soil geochemistry can change across the landscape. Along both transects, soil mineralogy and geochemistry change abruptly with changes in soil parent materials. However, the chemical influence of a soil’s parent material can be obscured by changing climatic conditions. For the transects, increasing precipitation from west to east and increasing temperature from north to south affect both soil mineralogy and geochemistry because of climate effects on soil weathering and leaching, and plant productivity. Regional anomalous metal concentrations can be linked to natural variations in soil parent materials, such as high Ni and Cr in soils developed on ultramafic rocks in California or high P in soils formed on weathered Ordovician limestones in central Kentucky. On local scales, anomalous metal concentrations recognized in soil profiles, such as high P in soils from animal confinement sites, are consistent with local anthropogenic disturbances. At a larger scale, the distribution of Hg across the west to east transect demonstrates that it can be difficult to distinguish between natural or anthropogenic contributions and that many factors can contribute to an element’s spatial distribution.Only three samples in a subset of seventy-three 0–5 cm depth soil samples from the north to south transect had organochlorine pesticides values above the method detection limit, apparently related to historic usage of the pesticides DDT and dieldrin.     

Trend-surface analysis of distribution of some heavy minerals in shelf sediments off Mangalore, India

The mineralogy of the 0.062–0.125 and 0.125–0.25 mm fractions of 58 selected samples from a set of 78 samples collected at a spacing of 1–2 km in the inner shelf of Mangalore were studied. Trend-surface analysis of distribution of the heavy minerals, hornblende, muscovite, garnet, and sillimanite, were made to determine the various factors controlling the mineral-distribution patterns in the area. Parts of the area showing contrasting environments were analyzed separately to determine the relationship of the regional and local trends and the various factors controlling the trends. The linear, quadratic and cubic trends for hornblende, garnet, and sillimanite were controlled by the source, westerly river flow and southerly currents; for mica, the response to processes has been the main factor. The mineral distribution in this area is mainly the result of dynamic interaction of process and response elements and a process-response model is suggested.Published with permission of the Director General, Geological Survey of India.     

Soil properties and moisture characteristics and their relationship with crop mid-day stress in the Sudan Gezira

This study is mainly about the relationship of the moisture holding and release capacity of soils with their texture, particularly the clay fraction. Soil samples collected from various sites in the Sudan Gezira were analysed for physical and chemical properties and moisture characteristics. Generally the soils were clayey except the recent alluvium which was loamy. The pH was alkaline and the electric conductivity < 1.0 dS m^–1. The studied soils were calcareous and very poor in organic matter, their intermediate to high water holding capacity being due mainly to the presence of large quantities of clay. Matric potentials of –0.4 to –1.5 MPa reduced soil moisture for all types of soils but the effects were not necessarily quantitatively equal. Permanent wilting point — moisture content at – 1.5 MPa — varied widely (10.5 – 22.0%) amongst the different soils and this was mainly attributed to texture and mineralogy of the soil clays. Bulk density decreased with increase in clay content. Calcium carbonate content was found to have no apparent relationship with the moisture content of these soils. The amount of silt fraction seems to have an overriding effect on the relationship between soil moisture availability in the recent alluvium soil and its subsequent release to growing plants. The results are discussed in relation to the phenomenon of mid-day stress observed in all grown crops of the Sudan Gezira.     

Process recognition in multi-element soil and stream-sediment geochemical data

Stream-sediment and soil geochemical data from the Upper and Lower Coastal Plains of South Carolina (USA) were studied to determine relationships between soils and stream sediments. From multi-element associations, characteristic compositions were determined for both media. Primary associations of elements reflect mineralogy, including heavy minerals, carbonates and clays, and the effects of groundwater. The effects of groundwater on element concentrations are more evident in soils than stream sediments. A “winnowing index” was created using ratios of Th to Al that revealed differing erosional and depositional environments. Both soils and stream sediments from the Upper and Lower Coastal Plains show derivation from similar materials and subsequent similar multi-element relationships, but have some distinct differences. In the Lower Coastal Plain, soils have high values of elements concentrated in heavy minerals (Ce, Y, Th) that grade into high values of elements concentrated into finer-grain-size, lower-density materials, primarily comprised of carbonates and feldspar minerals (Mg, Ca, Na, K, Al). These gradational trends in mineralogy and geochemistry are inferred to reflect reworking of materials during marine transgressions and regressions. Upper Coastal Plain stream-sediment geochemistry shows a higher winnowing index relative to soil geochemistry. A comparison of the 4 media (Upper Coastal Plain soils and stream sediments and Lower Coastal Plain soils and stream sediments) shows that Upper Coastal Plain stream sediments have a higher winnowing index and a higher concentration of elements contained within heavy minerals, whereas Lower Coastal Plain stream sediments show a strong correlation between elements typically contained within clays. It is not possible to calculate a functional relationship between stream sediment–soil compositions for all elements due to the complex history of weathering, deposition, reworking and re-deposition. However, depending on the spatial separation of the stream-sediment and soil samples, some elements are more highly correlated than others.     

Relative spatial soil geochemical variability along two transects across the United States and Canada

To support the development of protocols for the proposed North American Soil Geochemical Landscapes project, whose objective is to establish baselines for the geochemistry of North American soils, two continental-scale transects across the United States and Canada were sampled in 2004. The sampling employed a spatially stratified random sampling design in order to estimate the variability between 40-km linear sampling units, within them, at sample sites, and due to sample preparation and analytical chemical procedures. The 40-km scale was chosen to be consistent with the density proposed for the continental-scale project. The two transects, north–south (N–S) from northern Manitoba to the USA–Mexico border near El Paso, Texas, and east–west (E–W) from the Virginia shore north of Washington, DC, to north of San Francisco, California, closely following the 38th parallel, have been studied individually. The purpose of this study was to determine if statistically significant systematic spatial variation occurred along the transects. Data for 38 major, minor and trace elements in A- and C-horizon soils where less than 5% of the data were below the detection limit were investigated by Analysis of Variance (ANOVA). A total of 15 elements (K, Na, As, Ba, Be, Ce, La, Mn, Nb, P, Rb, Sb, Th, Tl and W) demonstrated statistically significant (p < 0.05) variability at the between-40-km scale for both horizons along both transects. Only Cu failed to demonstrate significant variability at the between-40-km scale for both soil horizons along both transects.The patterns of relative variability differ by transect and horizon. The N–S transect A-horizon soils show significant between-40-km scale variability for 29 elements, with only 4 elements (Ca, Mg, Pb and Sr) showing in excess of 50% of their variability at the within-40-km and ‘at-site’ scales. In contrast, the C-horizon data demonstrate significant between-40-km scale variability for 26 elements, with 21 having in excess of 50% of their variability at the within-40-km and ‘at-site’ scales. In 36 instances, the ‘at-site’ variability is statistically significant in terms of the sample preparation and analysis variability. It is postulated that this contrast between the A- and C- horizons along the N–S transect, that is dominated by agricultural land uses, is due to the local homogenization of Ap-horizon soils by tillage reducing the ‘at-site’ variability. The spatial variability is distributed similarly between scales for the A- and C-horizon soils of the E–W transect. For all elements, there is significant variability at the within-40-km scale. Notwithstanding this, there is significant between-40-km variability for 28 and 20 of the elements in the A- and C-horizon data, respectively. The differences between the two transects are attributed to (1) geology, the N–S transect runs generally parallel to regional strikes, whereas the E–W transect runs across regional structures and lithologies; and (2) land use, with agricultural tillage dominating along the N–S transect. The spatial analysis of the transect data indicates that continental-scale maps demonstrating statistically significant patterns of geochemical variability may be prepared for many elements from data on soil samples collected on a 40 × 40 km grid or similar sampling designs resulting in a sample density of 1 site per 1600 km².     

Isotopic and trace-element profiles across the New Britain island arc,Papua New Guinea

New Pb-, Sr-, and Nd-isotopic data have been obtained for the rocks of volcanoes overlying a wide range of depths (100–580 km) to the Wadati-Benioff Zone (WBZ) in the New Britain island arc, Papua New Guinea. Well-defined trends consistent with two-component mixing are observed in combined Pb-isotope/trace-element plots. One of the components is believed to represent a slab contribution whose isotopic signature, unlike those noted for several other arcs, appears to be dominated by subducted, altered, oceanic crust rather than by sediment. This conclusion is consistent with the results of a recent Be–B study of New Britain rocks. The influence of the slab component is considered to decrease as depth to the WBZ increases. Higher abundances of high-field-strength elements correlate with increasing depths to the WBZ, and may be indicative of smaller degrees of partial melting of the mantle wedge as WBZ depths increase. Abundances of other incompatible elements appear to reflect a complex interplay between the slab-derived flux and melting process.     

A water-leach procedure for estimating bioaccessibility of elements in soils from transects across the United States and Canada

An objective of the North American Soil Geochemical Landscapes Project is to provide relevant data concerning bioaccessible concentrations of elements in soil to government and other institutions undertaking environmental studies. A protocol was developed that employs a 1-g soil sample agitated overnight with 40 mL of reverse-osmosis de-ionized water for 20 h, and determination of 63 elements following three steps of centrifugation by inductively coupled plasma–atomic emission spectrometry and inductively coupled plasma–mass spectrometry the following day. Statistical summaries are presented for those 48 elements (Ag, Al, As, B, Ba, Be, Br, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Ho, I, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, P, Pb, Pr, Rb, Re, S, Sb, Si, Sm, Sn, Sr, Tb, Ti, Tl, Tm, U, V, W, Y, Yb, Zn, Zr, and pH) for which <20% of their data were reported as below the detection limit. The resulting data set contains analyses for 161 A-horizon soils collected along two transects, one along the 38th parallel across the USA and the other from northern Manitoba to the USA–Mexico border. The spatial distribution of three selected elements (Ca, Cu, and Pb) along the two transects is discussed in this paper both as absolute amounts liberated by the leach and expressed as a percentage of the total, or near-total, amounts determined for the elements. The Ca data reflect broad trends in soil parent materials, their weathering, and subsequent soil development. Calcium concentrations are generally found to be lower in the older soils of the eastern USA. The Cu data are higher in the eastern half of the USA, correlating with soil organic C, with which it is sequestered. The Pb data exhibit little regional variability due to natural sources, but are influenced by anthropogenic sources. Based on the Pb results, the percentage water-extractable data demonstrate promise as a tool for identifying anthropogenic components. The soil–water partition (distribution) coefficients, K_ds (L/kg), were determined and their relevance to estimating bioaccessible amounts of elements to soil fauna and flora is discussed. Finally, a possible link between W concentrations in human urine and water-extractable W levels in Nevada soils is discussed.     

Mineralogical and geochemical patterns of urban surface soils, the example of Pforzheim, Germany

This study presents a combined geochemical and mineralogical survey of urban surface soils. Many studies on urban soils are restricted to purely chemical surveys in order to investigate soil pollution caused by anthropogenic activities such as traffic, heating, industrial processing, waste disposal and many more. In environmental studies, chemical elements are often distinguished as lithogenic and anthropogenic elements. As a novel contribution to those studies, the authors combined the analysis of a broad set of chemical elements with the analysis of the main mineralogical phases. The semi-quantification of mineralogical phases supported the assignment of groups of chemical elements to lithogenic or anthropogenic origin. Minerals are important sinks for toxic elements. Thus, knowledge about their distribution in soils is crucial for the assessment of the environmental hazards due to pollution of urban soils. In Pforzheim, surface soils (0–5 cm depth) from various land use types (forest, agriculture, urban green space, settlement areas of various site densities) overlying different geological units (clastic and chemical sediments) were investigated. Urban surface soils of Pforzheim reflect to a considerable degree the mineral and chemical composition of parent rocks. Irrespective of the parent rocks, elevated concentrations of heavy metals (Zn, Cu, Pb, Sn, Ag) were found in soils throughout the whole inner urban settlement area of Pforzheim indicating pollution. These pollutants will tend to accumulate in inner urban surface soils according to the available adsorption capacity, which is normally higher in soils overlying limestone than in soils overlying sandstone. However, inner urban surface soils overlying sandstone show elevated concentrations of carbonates, phyllo-silicates and Fe and elevated pH values compared with forest soils overlying sandstone. Thus, in comparison to forest soils overlying sandstones, inner urban soils overlying sandstone affected by pollution concurrently possess elevated concentrations of mineral phases typically providing relatively high adsorption capacities for heavy metals.     

Arsenic release from biotite into a Holocene groundwater aquifer in Bangladesh

Continuous core sediments (to a depth of 90.1 m) taken at a transitional area of Holocene and Pleistocene deposits in Sonargaon, Bangladesh were characterized for their mineralogy and chemistry. Among the sediments of the lower part of the Holocene aquifer (depth: 18–29 m), where most domestic wells are installed, As is mostly fixed in biotite and organic phases. A positive correlation of As concentration with those of Al and Fe but not that of total organic C clearly suggests that biotite is a primary source of As. Although microbial reduction–dissolution of As-containing Fe oxyhydroxides is thought to cause As-enriched groundwater in the Ganges–Brahmaputra–Meghna delta plain, the authors conclude that chemical weathering of biotite is the primary formation mechanism and prevailing reducing conditions contribute to the expansion of As-enriched groundwater in the study area.     

Carbonatization and mobility of Ti,Y, and Zr in Ascot Formation metabasalts,SE Quebec

The middle Ordovician Ascot Formation of southeastern Quebec consists of greenschist facies metamorphosed silicic to mafic pyroclastic rocks and lava flows and associated metasediments. Chemical analyses of lavas reveal a preponderance of metarhyolites and metabasalts, together with some porphyritic rocks with intermediate SiO₂ contents. The metabasalts exhibit wide ranges in concentrations of TiO₂ (0.25–2.0 wt.°), Y (9–46 ppm), and Zr (5–135 ppm). The extent of the ranges, and unusual interelement ratios, suggest that the concentrations of these normally immobile elements have been affected by secondary processes.There is a strong correlation between trace-element concentrations and the degree of carbonatization of the metabasalts. Low carbonate rocks are severely depleted in Ti, Y, and Zr whereas high carbonate rocks are depleted in Y and Zr and enriched in Ti. The differing movement of Ti can be explained in terms of variable chemical potential due to the various carbonatization reactions affecting titaniferous phases. Overall mobility of these generally immobile/rd elements is attributed to high CO₂ levels in the fluid phase during metamorphism.Extrapolation of the two alteration trends to a common origin enables one to infer primary concentrations of the trace-elements. Primary inter-element ratios arrived at in this way are compatible with an island-arc origin for the Ascot Formation although TiO₂ concentrations are a little high (1.5 wt/%).     

Chemistry versus time in the volcanic complex of Ischia (Gulf of Naples,Italy): evidence of successive magmatic cycles

An extensive petrochemical and geochronological study of the volcanic complex of the island of Ischia has been made in order to assess the variation of the magmatic characteristics through time. The major and trace element chemistry and the mineralogy of more than 40 samples, coupled with their K/Ar ages, reveal four phases of volcanic activity: (1) prior to 150000 years B.P. — alkali-trachyte pyroclastic products; (2) 150000–75000 years B.P. — alkali-trachytic to phonolitic lava domes and minor pyroclastics; (3) 55000–20000 years B.P. — great pyroclastic emissions of trachytic and alkali-trachytic composition; (4) 10000 years B.P.-1302 A.D. — mainly lava flows, ranging from alkali-trachytes to magmas between basalt and latite. In spite of a relatively monotonous major element chemistry, the trace element contents of the rocks show a large variation (up to a factor of 9). Comparison of glass compositions with the modal phases permits us to distinguish at least four clearly established supplies of new magma to a shallow chamber. After the first three events, the magmas possibly evolved in a closed system controlled by fractional crystallization with at least one single eutectic crystallization occurring afterwards (sodalite, nepheline and alkali feldspar+aegirine and salite). During the fourth event, increasing proportions of a less evolved liquid, suddenly charged with mafic xenocrysts, contaminated the residual liquid in the chamber and generated through time more and more basic products. Their high Th/Ta and Th/Hf ratios and Ta, Nb and Ti negative anomalies suggest an orogenic tendency of the recent volcanic activity on the island of Ischia.     

Petrological and source region characteristics of ophiolitic hornblende gabbros from the Aksaray and Kayseri regions, central Anatolian crystalline complex, Turkey

Many Neo-Tethyan ophiolitic bodies are well exposed as thrust-slices in Central Anatolia and are predominantly represented by massive hornblende gabbros, most of which are cut by Supra Subduction Zone (SSZ) plagiogranites. The allochthonous gabbros are distinct from their autochthonous counterparts, with their mineralogy including both igneous hornblende, relict diopside rimmed by replacement hornblende and their chemical composition corresponding mostly to gabbro rather than diorite.The results of major and trace element analyses of forty-two samples, and REE analyses of nine samples, indicate that the hornblende gabbros are SSZ-type and formed from a wet magma by high-degree partial melting of peridotite possibly coupled with contamination by predominantly neighbouring-slab derived fluids within an intra-oceanic back-arc basin. The mafic magmas then underwent high-level fractional crystallization involving titaniferous magnetite, diopside, tschermakite and possibly olivine. Emplacement was followed by extensive ocean–floor metamorphism, which has induced crystallization (or recrystallization) of chlorite, biotite, amphiboles and mobilisation of most of the major elements such as alkali and alkali earth elements, and some LREE.     

Soil chemistry in lithologically diverse datasets: The quartz dilution effect

National- and continental-scale soil geochemical datasets are likely to move our understanding of broad soil geochemistry patterns forward significantly. Patterns of chemistry and mineralogy delineated from these datasets are strongly influenced by the composition of the soil parent material, which itself is largely a function of lithology and particle size sorting. Such controls present a challenge by obscuring subtler patterns arising from subsequent pedogenic processes. Here the effect of quartz concentration is examined in moist-climate soils from a pilot dataset of the North American Soil Geochemical Landscapes Project. Due to variable and high quartz contents (6.2–81.7 wt.%), and its residual and inert nature in soil, quartz is demonstrated to influence broad patterns in soil chemistry. A dilution effect is observed whereby concentrations of various elements are significantly and strongly negatively correlated with quartz. Quartz content drives artificial positive correlations between concentrations of some elements and obscures negative correlations between others. Unadjusted soil data show the highly mobile base cations Ca, Mg, and Na to be often strongly positively correlated with intermediately mobile Al or Fe, and generally uncorrelated with the relatively immobile high-field-strength elements (HFS) Ti and Nb. Both patterns are contrary to broad expectations for soils being weathered and leached. After transforming bulk soil chemistry to a quartz-free basis, the base cations are generally uncorrelated with Al and Fe, and negative correlations generally emerge with the HFS elements. Quartz-free element data may be a useful tool for elucidating patterns of weathering or parent-material chemistry in large soil datasets.     

Hydrothermal alteration of granite by meteoric fluid: an example from the Carnmenellis Granite,United Kingdom

The interaction of granitic rock with meteoric fluid is instrumental in determining the chemistry of pore fluids and alteration mineralogy in downflow portions of convective groundwater circulation cells associated with many hydrothermal systems in the continental crust. Hydrothermal experiments and a detailed mineralogical study have been carried out to investigate the hydrothermal alteration of the Carnmenellis Granite, Cornwall, UK. Samples of drill chippings from a borehole 2 km deep in the Carnmenellis Granite have been reacted with a dilute Na-HCO₃-Cl fluid in hydrothermal solution equipment at temperatures of 80°, 150° and 250° C and a pressure of 50 MPa, with a water/rock mass ratio of 10, for experiment durations up to 200 days. Fluid samples were analysed for seventeen different chemical components, and solids were examined prior to, and after reaction using SEM, electron microprobe and conventional light optic techniques. Experimental fluids were mildly alkaline (pH 7–8.5) and of low salinity (TDS <800 mgl^–1). Mineral-fluid reaction was dominated by the dissolution of plagioclase and the growth of smectite, calcite (at all temperatures), laumontite (at 150° C), wairakite and anhydrite (at 250° C). Final fluids were saturated with respect to quartz and fluorite. Certain trace elements (Li, B, Sr) were either incorporated into solids precipitated during the experiments or sorbed onto mineral surfaces and cannot be considered as conservative (partitioned into the fluid phase) elements. Concentrations of all analysed chemical components showed net increases during the experiments except for Ca (at 250° C) and Mg (at all temperatures). A comparison of the alteration mineralogy observed in the experiments with that present as natural fracture infills in drillcore from the Carnmenellis Granite reveals that the solid products from the experiments correspond closely to mineral assemblages identified as occurring during the later stages of hydrothermal circulation associated with the emplacement of the granite.     

Transport of trace elements under different seasonal conditions: Effects on the quality of river water in a Mediterranean area

Concentrations of total and dissolved elements were determined in 35 water samples collected from rivers in Sardinia, a Mediterranean island in Italy. The overall composition did not change for waters sampled in both winter and summer (i.e., January at high-flow condition and June at low-flow condition), but the salinity and concentrations of the major ions increased in summer. Concentrations of elements such as Li, B, Mn, Rb, Sr, Mo, Ba and U were higher in summer with only small differences between total and dissolved (i.e., in the fraction <0.4 μm) concentrations. The fact that these elements are mostly dissolved during low flow periods appears to be related to the intensity of water–rock interaction processes that are enhanced when the contribution of rainwater to the rivers is low, that is during low-flow conditions. In contrast, the concentrations of Al and Fe were higher in winter during high flow with total concentrations significantly higher than dissolved concentrations, indicating that the total amount depends on the amount of suspended matter. In waters filtered through 0.015 μm pore-size filters, the concentrations of Al and Fe were much lower than in waters filtered through 0.4 μm pore-size filters, indicating that the dissolved fraction comprises very fine particles or colloids. Also, Co, Ni, Cu, Zn, Cd and Pb were generally higher in waters collected during the high-flow condition, with much lower concentrations in 0.015 μm pore-size filtered waters; this suggests aqueous transport via adsorption onto very fine particles. The rare earth elements (REE) and Th dissolved in the river waters display a wide range in concentrations (∑REE: 0.1–23 μg/L; Th: <0.005–0.58 μg/L). Higher REE and Th concentrations occurred at high flow. The positive correlation between ∑REE and Fe suggests that the REE are associated with very fine particles (>0.015 and <0.4 μm); the abundance of these particles in the river controls the partitioning of REE between solution and solid phases.Twenty percent of the water samples had dissolved Pb and total Hg concentrations that exceeded the Italian guidelines for drinking water (>10 μg/L Pb and >1 μg/L Hg). The highest concentrations of these heavy metals were observed at high-flow conditions and they were likely due to the weathering of mine wastes and to uncontrolled urban wastes discharged into the rivers.     

Residence of trace elements in metasomatized spinel lherzolite xenoliths: a proton-microprobe study

Minerals occurring in dry and modally metasomatized spinel lherzolites from western Victoria have been analysed by proton microprobe for Ni, Cu, Zn, Ga, Rb, Sr, Y, Zr, Nb, Ba, Pb, Br, rare-earth elements (REE), Th and U. Mass-balance calculations demonstrate that these trace elements are contained in specific acceptor minerals and do not occur in significant concentrations at clean grain boundaries. The level of particular trace elements in the rock depends on the presence of specific phases: for example high levels of REE, Sr (and U, Th, Br) require apatite, while Ba, Nb and Ta are strongly concentrated in amphibole±mica. Mantle metasomatism in these spinel lherzolites is inferred to result from an open-system process involving infiltration of fluids released by crystallizing silicate melts. This process produces metasomatic zones with different modal mineralogy and hence greatly different trace-element signatures. The data demonstrate that large-ion-lithophile (LIL) and high-field strength (HFS) elements in metasomatized spinel lherzolites are strongly concentrated in non-refractory phases, which will break down easily in heated volumes such as the walls of magma conduits. The heterogeneity observed in trace-element patterns of intraplate alkali basaltic rocks may not reflect source heterogeneity, but may result largely from contamination by metasomatized mantle wall rock. The K_Ds for most trace elements show little temperature dependence except for K_DSr between orthopyroxene and clinopyroxene where K_D decreases with increasing temperature. The generally uniform K_Ds can be used to test for disequilibrium in such assemblages.     

Geochemical signature of provenance in sand-size material in soils and stream sediments near the Tobacco Root batholith, Montana, U.S.A.

Trace-element geochemistry of sandstones are being used to determine provenance. We have conducted preliminary and limited experiments to determine to what extent daughter sands retain the geochemical signature of parent rocks. Six sets of first-order stream sediments, soils from adjacent slopes, and a variety of parent rocks were collected from southwestern Montana, U.S.A. Sampling in a low-relief area ensured that climate and residence time of soils on slopes could be eliminated as variables. Sand-size fractions of stream sediments and soils, and the corresponding parent rocks (granodiorite, quartz monzonite, granite gneiss, biotite-tonalite gneiss and amphibolite) were analyzed for most major elements and selected trace elements. Petrologic modal analysis of the parent rocks and the 0.25–0.50-mm fraction of each sand was done to monitor major mineralogic control, if any, on chemical compositions of the samples.

Our data show that the abundances of the Si and Al in sediments do not discriminate provenance. Abundances of Ca, Mg, Fe and Ti may broadly distinguish between sands derived from metamorphic and igneous source rocks, at least in the area studied. Differences in abundances of the Ba and Th, and the ratio of La/Lu between granitic, tonalitic and amphibolitic parent rocks are preserved in the daughter sediments that we studied. However, the size of the Eu anomaly in the REE patterns of different daughter sediments is not diagnostic of parent rocks. Abundances of Co and Sc distinguish between sediments derived from felsic and mafic rocks. A better provenance discrimination is obtained if the ratios La/Sc, Th/Sc, La/Co, Ba/Sc and Ba/Co are used.

Petrologic modal data show that mineral contents and chemical compositions of parent rocks are compatible with each other. The chemical composition of the sands may be roughly correlated to the petrological modal data but the abundances of some minor and trace elements of sediments cannot be inferred from modal mineralogy. This is expected because these elements may concentrate in accessory minerals and/or may weather out into aqueous or clay mineral fractions; it is also compatible with conclusions of previous studies that some of these elements do not reside in sand-size fractions of siliciclastic sediments.     

Chemical weathering in Luzon, Philippines from clay mineralogy and major-element geochemistry of river sediments

Clay mineralogy and major-element geochemistry of 35 surface sediment samples collected in 21 major to moderate rivers of Luzon, Philippines are used to evaluate the present chemical weathering process. The clay mineral assemblage consists mainly of smectite (average 86%) with minor kaolinite (9%) and chlorite (5%) and very scarce illite (1%), and does not show strong island-wide differences. The major element results of both bulk and clay-fraction sediments indicate that the formation of clay minerals is accompanied by leaching of Ca and Na first and of Fe and Mn thereafter during the chemical weathering process. A low-moderate chemical weathering degree of bulk sediments and a moderate-intensive degree of clay-fraction sediments are obtained in Luzon rivers based on proxies of chemical index of alteration (CIA) and smectite crystallinity. It is suggested that the majority of andesitic–basaltic volcanic and sedimentary rocks along with the tectonically active geological setting and sub-tropical East Asian monsoon climate are responsible for the predominance of smectite in the clay mineral assemblage.