Distribution and behavior of gold in soils and tills at the Nickel Plate Mine, southern British Columbia, Canada

The Nickel Plate deposit, in which gold occurs as <25 μm blebs associated with arsenopyrite in garnet-pyroxene skarns, is in the subalpine zone near the southern limit of the Thompson Plateau. During the last glaciation the Cordilleran ice sheet moved south-southwest across the deposit and deposited a stony basal till. A dispersion train with anomalous concentrations of gold in tills and soils now extends 2 km down ice from the deposit.Gold contents of samples of humus (LFH horizon) and the −212 μm fraction of mineral soils (A, B and C horizons) was determined by instrumental neutron activation and fire assay-atomic absorption, respectively. Selected samples were examined in detail to determine distribution of gold between different size and density fractions.Despite erratic variability, Au contents of the −212 μm fraction generally decrease from 200–400 ppb close to the mine site to <50 ppb at distal sites. At most sites there is also a twofold increase of gold values down the soil profile. Within samples concentrations of Au in the −420 + 212 μm, −212 + 106 μm, −106 + 53 μm and −53 μm fractions are usually roughly constant. However, because of its abundance, the −53 μm fraction contains more than 70% of the gold. Amenability of gold in this fraction to cyanidation suggests that it is largely free gold. For size fractions > 53 μm the contribution of the heavy mineral (SG > 3.3) fraction to total gold content increases with decreasing grain size.Distribution of gold between size and density fractions is consistent with its release from the bedrock or pre-glacial regolith by glacial abrasion. The bulk of the gold was incorporated into the fine fractions of the till at or close to the source. However, differences between down ice dilution ratios for gold in different heavy mineral size fractions suggest that comminution of host minerals continued to transfer gold to the finer size fractions during glacial transport.For exploration purposes, B and C horizon samples provide the best anomaly contrast. Estimates of the abundance of gold particles in different size fractions indicate that the nugget effect, which causes erratic gold values in the −212 μm fraction, can be avoided by analysis of 30 g of −53 μm material.     

Visible gold in arsenian pyrite at the Shuiyindong Carlin-type gold deposit, Guizhou, China: Implications for the environment and processes of ore formation

Carlin-type gold deposits are best known for the scarcity of visible gold in their ores. It has long been recognized that the majority of gold is “invisible”, such that it cannot be resolved by conventional microscopy, and resides in arsenian pyrite. Shuiyindong differs in that sub-μm to μm-sized native gold is present in arsenian pyrite veinlets and disseminations. It is also the largest (55 tonnes) and highest grade (7 to 18 ppm), stratabound, Carlin-type gold deposit in Guizhou, China and has produced 5 tonnes of gold from sulfide refractory ores extracted by underground mining methods. In this study, an electron microprobe analyzer (EMPA) was used to map the spatial distribution of “invisible” gold and sub-μm to μm-size visible gold particles in arsenian pyrite in high-grade ore samples from the Shuiyindong. The samples studied are hosted in Permian bioclastic ferroan limestone of the Longtan Formation and exhibit evidence of decarbonation, silicification and sulfidation. Arsenian pyrite with detectable Au (> 400 to 3800 ppm) is disseminated in altered limestone and was deposited in two stages separated by an episode of corrosion in a veinlet.The results show that there are two populations of native gold in arsenian pyrite. One is comprised of sub-μm size gold particles (0.1 to 0.2 μm) that are occasionally present in the gold-bearing arsenian pyrite disseminated in the host rocks. This arsenian pyrite is interpreted to have been formed by sulfidation of ferroan calcite and dolomite. Another is comprised of coarser (1 to 6 μm) native gold grains present in the arsenian pyrite veinlet, either on the first stage where it has been corroded or on the second stage. The lack of fluid inclusion or other evidence of boiling and the low iron content of fluid inclusions in quartz, suggest the veinlet formed by sulfidation of another fluid containing Fe. The Fe-bearing fluid may be a depleted ore fluid that gained Fe by dissolution of ferroan limestone after H₂S had been consumed. The association of the largest visible gold grains with an episode of corrosion suggests that fluids episodically became undersaturated with arsenian pyrite while remaining saturated with gold (e.g., pH decrease or an increase in the oxidation state). This may have resulted from incursion of relatively acidic or oxidized fluids that were able to dissolve arsenian pyrite and remain saturated with gold. In this case, sulfidation of iron from the host rock, was the most important depositional mechanism for Au-bearing arsenian pyrite with, or without, grains of native gold.     

Radiocaesium dispersion and fixation in the lagoon systems of “Ria de Aveiro”, Portugal

Radiocaesium (¹³⁷Cs) dispersion and Cs⁺ fixation were studied in the sediments collected from the lagoon systems of “Ria de Aveiro”. The Cs⁺ sorption was tested for the fine mica grains and for the < 2 μm clay fractions extracted from silty clays. The Cs⁺ exchange is found strongly onto mica-rich fractions than smectite-rich fractions. The distribution coefficient increases if the silty material is constituted by rich-mica clay fractions or if the non-clay minerals are removed from the silty-clay material. The samples studied behave as multisite ion exchange, where Cs⁺ engages in ion-exchange reactions with hydrated cations on planar sites on expansible layer silicates. Higher concentrations of the ¹³⁷Cs were found associated with mica-rich silty clays. The ¹³⁷Cs ranges from 3.2 to 3.9 Bq kg^− 1 in the < 38 μm fractions and from 2.9 to 3.3 Bq kg^− 1 in the < 64 μm fractions.     

Dissolved air flotation (DAF) of fine quartz particles using an amine as collector

Experimental studies concerning the dissolved air flotation (DAF) of fine (d_p < 100 μm) quartz particles, using two different flotation cells (setups), are presented. Pure and well characterised quartz samples were treated with a commercial amine as collector prior to flotation and bubbles were characterised by the LTM-BSizer technique. Bubble size distribution showed 71% (by volume) and 94% (by number) of the bubbles having sizes (d_b) lower than 100 μm (i.e. microbubbles). The Sauter and arithmetic mean diameters were 79 μm and 56 μm, respectively, for the bubbles generated at 300 kPa (gauge) saturation pressure (after 30 minute saturation time). Quartz particle size distribution (obtained by laser diffraction) showed a volume-moment diameter of 13 μm. The Rosin–Rammler–Bennett, Gates–Gaudin–Schumann and log-normal distribution functions were well fitted (R² > 0.96) to the bubble size distribution and quartz particle size distribution data. Values of total quartz recovery ranging from 6% to 53% (by mass) were obtained for the DAF experiments under different collector concentrations (up to 2 mg g^− 1), with an optimal collector concentration found at 1 mg g^− 1. These results are significant considering that 27% (by volume) of the quartz particles are ultrafine (d_p < 5 μm), demonstrating the widely-known efficiency of DAF to remove small particles when applied in the field of water and wastewater treatment. The true flotation behaviour, as a function of particle diameter (d_p), exhibits a local minimum when particles are approximately 3–5 μm in size. The results contribute to the discussion in the literature about the existence of such a minimum, which is generally interpreted as a change in the mechanism of particle collection from convection (collision) to diffusion at lower particle sizes.     

Orientation studies for gold in the central pediplain of the Saudi Arabian shield

Orientation studies were carried out by the BRGM mission in Saudi Arabia between 1982–1986 to investigate the dispersion of gold in soils and wadi sediments and to define the optimum sample medium around eight prospects in the central Arabian pediplain. A comparison of gold distribution in several sieved fractions with various pedologic horizons shows that the distribution of gold changes abruptly from the coarser sizes near the source to the finest sizes 150 m downstream.The coarse fraction recommended by previous workers is not representative and yields erratic results in the specific environment of the pediplain. Gold is enriched and more homogeneously distributed in the minus 80 μm fraction of the skeletal soils and wadi sediments.Regional geochemical survey can be effective using a sensitive analytical method for gold and the minus 80 μm fraction of the brown gravelly sediment with a minimum density of 2 samples per km². Geochemical halos in the 30–50 ppb range indicate gold mineralization 500 to 1000 m upstream, depending on relief.In a first follow-up stage, continued use of the same size of the upper argillaceous layer with a regular reg sampling grid gives more contrasted and more extensive anomalies than using a coarse material. These anomalies may be slightly offset by the present arid erosion. A second follow-up stage is then recommended at a closer grid and sampling the brown blocky layer below the surficial reg pavement. Again, the use of the finest fraction at this exploration stage has given the best probability of finding a blind gold target.Optical determination of gold on a nonmagnetic fraction of heavy panconcentrate is not recommended, because nugget growth is practically absent in the present arid conditions and flour-sized gold particles are lost in desliming samples.     

Lignin is preserved in the fine silt fraction of an arable Luvisol

Knowledge about the fate of individual biomolecules during the decomposition process in soil is limited. We used the natural isotopic label introduced by 23 years of continuous maize cropping, together with compound specific ¹³C isotope analysis, to study lignin monomers in particle size fractions of a Luvisol. Isotope data indicated apparent decadal turnover times for lignin. A kinetic model suggests the existence of a fast and a slow decomposing lignin pool in the soil, reconciling a low stock-to-input ratio with decadal turnover times. We found new, maize-derived lignin primarily in the 63–2000 μm fraction, whereas old, C₃-derived lignin from the pre-maize vegetation had accumulated mainly in the silt (2–20 μm) fraction. This distribution of lignin differed from that of total organic carbon, which was concentrated in the <2 μm fraction. Old, C₃-derived carbon in all the soil fractions was depleted in lignin compared to new, maize-derived carbon. The observation that the 2–20 μm fraction was less depleted than the others indicates that lignin preservation is particle size specific, but the underlying mechanism controlling its preservation is not clear.     

Mineralogy and petrology of Al-rich objects and amoeboid olivine aggregates in the CH carbonaceous chondrite North West Africa 739

The aluminum-rich (>10 wt% Al₂O₃) objects in the CH carbonaceous chondrite North West Africa (NWA) 739 include Ca,Al-rich inclusions (CAIs), Al-rich chondrules, and isolated mineral grains (spinel, plagioclase, glass). Based on the major mineralogy, 54 refractory inclusions found in about 1 cm² polished section of NWA 739 can be divided into hibonite-rich (16%), grossite-rich (26%), melilite-rich (28%), spinel-pyroxene-rich (16%) CAIs, and amoeboid olivine aggregates, (AOA's, 17%). Most CAIs are rounded, 25–185 μm (average=70 μm) in apparent diameter, contain abundant, tiny perovskite grains, and typically surrounded by a single- or double-layered rim composed of melilite and/or Al-diopside; occasionally, layers of spinel+hibonite and forsterite are observed. The AOAs are irregularly shaped, 100–250 μm (average=175 μm) in size, and consist of forsterite, Fe,Ni-metal, and CAIs composed of Al-diopside, anorthite, and minor spinel. One AOA contains compact, rounded melilite-spinel-perovskite CAIs and low-Ca pyroxene replacing forsterite. The Al-rich (>10 wt% bulk Al₂O₃) chondrules are divided into Al-diopside-rich and plagioclase-rich. The Al-diopside-rich chondrules, 50–310 μm (average=165 μm) in apparent diameter, consist of Al-diopside, skeletal forsterite, spinel, ±Al-rich low-Ca pyroxene, and ±mesostasis. The plagioclase-rich chondrules, 120–455 μm (average=285 μm) in apparent diameter, are composed of low-Ca and high-Ca pyroxenes, forsterite, anorthitic plagioclase, Fe,Ni-metal nodules, and mesostasis. The isolated spinel occurs as coarse, 50–125 μm in size, subhedral grains, which are probably the fragments of Al-diopside chondrules. The isolated plagioclase grains are too coarse (60–120 μm) to have been produced by disintegration of chondrules or CAIs; they range in composition from nearly pure anorthite to nearly pure albite; their origin is unclear. The Al-rich objects show no evidence for Fe-alkali metasomatic or aqueous alteration; the only exception is an Al-rich chondrule fragment with anorthite replaced by nepheline. They are texturally and mineralogically similar to those in other CH chondrites studied (Acfer 182, ALH85085, PAT91467, NWA 770), but are distinct from the Al-rich objects in other chondrite groups (CM, CO, CR, CV). The CH CAIs are dominated by very refractory minerals, such as hibonite, grossite, perovskite and gehlenitic melilite, and appear to have experienced very low degrees of high-temperature alteration reactions. These include replacement of grossite by melilite, of melilite by anorthite, diopside, and spinel, and of forsterite by low-Ca pyroxene. Only a few CAIs show evidence for melting and multilayered Wark-Lovering rims. These observations may suggest that CH CAIs experienced rather simple formation history and escaped extensive recycling. In order to preserve the high-temperature mineral assemblages, they must have been efficiently isolated from the hot nebular region, like some chondrules and the zoned Fe,Ni-metal grains in CH chondrites.     

Distribution of copper, zinc, lead and cadmium concentrations in stream sediments from the Mapocho River in Santiago, Chile

The Mapocho river, which crosses downtown Santiago, is one of the most important rivers in contact with a population of about six million inhabitants. Anthropogenic activities, industrialization, farming activities, transport, urbanization, animal and human excretions, domestic wastes and copper mining have affected the river, contaminating it and its sediments with heavy metals. Concentration and distribution of Cu, Zn, Pb and Cd were studied with the purpose of determining their bioavailability and their relation with the characteristics of the sediments. Freshly deposited seasonal sediments were collected from 0–8 cm depths from 6 locations (S₁ to S₆) along the 30-km long channel length, in the four seasons of year on the following dates: May 2001 (D₁, autumn); August 2001 (D₂, winter); October 2001 (D₃, spring) and January 2002 (D₄, summer). The dried samples were sifted to obtain the < 63-μm sediment fraction, since it has been shown that large amounts of heavy metals are bound in the fine-grained fraction of the sediment. Cu and Zn were analyzed by atomic absorption spectrophotometry and Pb and Cd by square wave anodic stripping voltammetry. The highest concentrations of Cu (2850 μg g^− 1) were found in the northern part of the river (S₁, average D₁–D₄), near the mountains and a copper mine, and then decreased downstream to 209 μg g^− 1 (S₆). Total Zn showed an irregular variation, with higher values at S₁ (1290 μg g^− 1) and high values in some winter sampling (1384 μg g^− 1 S₄, S₅–D₂). Pb showed different trends, increasing from S₁ to S₆ (17 to 61 μg g^− 1), with the highest values in the summer samples (83 μg g^− 1, S₄–S₆, D₄), and total Cd increased slightly from mean values of 0.2 and 0.5 μg g^− 1. Partition into five fractions was made using Tessier's analytical sequential extraction technique; the residue was treated with aqua regia for recovery studies, although this step is not part of the Tessier procedure. The results show that Cu, Zn and Pb in the sediments were dependent on the sampling places along the river, and variation in two years was low (D₁–D₄). The highest values of total organic matter, carbonate and conductivity were found in S₆, which has the smallest size particles, while at S₁ the sediments were predominantly sand and contain larger amounts of silica. Cu associated with carbonate decreased gradually from 58% (1771 μg g^− 1, S₁) to 16% (32 μg g^− 1, S₆); Cu bonded to reducible fraction was almost constant (33% to 37%), and Cu associated with oxidizable fraction increased from 7% (S₁) to 34% (S₆), but copper content was lower (214 to 68 μg g^− 1). Zn had a similar fractionation profile. However, Pb bound to oxidizable fraction did not show significant percent variation along the river (20% to 19%), but the amount bounded was 4 to 12 μg g^− 1. The residual fraction increased from 24% to 41% (5 to 25 μg g^− 1, S₁ to S₆). The distribution of Cd in the sediment was almost independent of the sampling stations and was bound to carbonate, reducible and residual fraction in similar proportion. Cu and Zn at S₁ were mainly bound to carbonates and reducible phases with 91% and 73% (2779 and 965 μg g^− 1, respectively), and with a change in the pH and/or the redox potential of the sediment–water system, these contaminants could easily enter the food chain. In S₆ the amount of Cu and Zn in these phases was 50% and 53% (100 to 313 μg g^− 1, respectively).     

Distribution and dispersion of gold in point bar and pavement sediments of the Huai Hin Laep, Loei, northeastern Thailand

Gold anomalies in drainage sediments are often erratic, reflecting both the nugget effect and hydraulic effects whereby gold is concentrated at favorable sites along a stream. This study investigates these factors in a stream in northeastern Thailand.Bulk sediment samples, consisting of approximately 40 kg of −12 mm material, were collected from bar and pavement sites along an 8 km study reach. Samples were wet sieved into eight size fractions. The five fractions between 425 μm and 53 μm were then processed to obtain heavy mineral concentrates (SG > 3.3). Gold content of all size and density fractions finer than 425 μm was determined by fire assay-atomic absorption.Concentrations of Au in the heavy mineral concentrates typically range from 10,000 to 50,000 ppb (maximum 198,000 ppb), whereas the corresponding light mineral fractions and the −53 μm fraction generally contain <5 ppb gold. Within the heavy mineral fractions concentrations of Au generally increase downstream away from their supposed source and are higher at pavement than at point bar sites. Variations in abundance of gold between point bar sites can be related to stream characteristics (such as width, velocity and bed roughness) that are indicative of changing energy conditions and of the ability of the stream to winnow light minerals from its bed.The estimated median number of gold particles in the heavy mineral concentrates increase from less than one in the 212–425 μm fraction to about three in the 53–106 μm size range. However, because of dilution by the light mineral and −53 μm fractions, the probability of a 30 g analytical sub-sample containing a particle of gold is so low that in thirteen out of sixteen −149 μm sediment samples no gold was detected. Insofar as this results from dilution by large quantities of −53 μm sediment, failure of conventional sieved sediment samples to reliably detect the anomaly is probably a consequence of increased erosion caused by deforestation and land usage.Heavy mineral concentrates from pavement and other high energy sites are more reliable than conventional sediment samples for detecting gold anomalies of the Huai Hin Laep type. A low sample density is adequate but, because anomaly contrast may increase downstream, careful interpretation is required.     

Behavior of arsenic and antimony in the surface freshwater reaches of a highly turbid estuary, the Gironde Estuary, France

This study reports on the behavior of two redox-sensitive elements, As and Sb, along the turbidity gradient in the freshwater reaches of the turbid Gironde Estuary. During a 17-month survey, surface water and suspended particulate matter (SPM) were sampled monthly at six sites representing both fluvial branches of the Gironde Estuary. Additionally, two longitudinal high resolution profiles were sampled along the fluvial estuary of the Garonne Branch during two contrasted seasons, i.e. with and without the presence of the maximum turbidity zone (MTZ). Seasonal variability and spatial distribution of dissolved (<0.2 μm; <0.02 μm) and particulate As, Sb and Fe were measured and combined with SPM data to understand metalloid behavior in the estuarine freshwater turbidity gradient.At the two main fluvial entries of the Gironde Estuary, dissolved As and Sb concentrations showed strong (by a factor of 2–4) seasonal variations, that were only partly controlled by discharge-related dilution. Seasonal addition of dissolved As and Sb was attributed to the degradation of particulate As and Sb carrier phases in bottom sediment and/or in the adjacent aquifers, rather than release from SPM. In the surface freshwater reaches of the Gironde Estuary, Sb behaved conservatively under all hydrological conditions. In contrast, As was strongly reactive in the presence of the MTZ, with opposite behaviors in the two fluvial branches of the estuary: in the Garonne Branch As was removed from the dissolved phase, whereas in the Dordogne Branch As was added. Redistribution of As between the dissolved and the particulate phases along the turbidity gradient in estuarine freshwater only affected the <0.02 μm fraction, as the 0.02–0.2 μm fraction remained constant (300 ng L⁻¹ in September 2005). Accordingly, As removal seemed to be decoupled from concomitant “colloidal” (0.02–0.2 μm) Fe flocculation in the turbidity gradient. The contrasting behavior of dissolved As in the fluvial estuaries of the Garonne and Dordogne Branches was attributed to sorption processes during equilibration of river-borne dissolved As with estuarine SPM forming the MTZ. This equilibrium, described by a distinct distribution coefficient K_d(As)  11,000 L kg⁻¹ in the MTZ, resulted in either As release (desorption; Dordogne Branch) or removal (adsorption; Garonne Branch) in the respective fluvial estuaries. A mixing experiment under controlled laboratory conditions tended to support that equilibration between the dissolved phase and MTZ particles may induce both As release and removal in the estuarine freshwater reaches, with As distribution evolving towards a distinct K_d value for increasing SPM concentrations. The long-term survey allowed estimating annual (2004) dissolved fluxes of As and, for the first time Sb, at the main fluvial entries of the Gironde Estuary at 30.7 t a⁻¹ and 3.2 t a⁻¹ (Garonne River) and at 8.0 t a⁻¹ and 2.3 t a⁻¹ (Dordogne River), respectively.     

A radiotracer study on the kinetics of gold sorption by mineral surfaces

Aqueous solutions with about 10 ppt¹⁹⁵Au and [HCl] of 10^–2.3 and 10^–1.3 m were exposed to solid minerals for several months. The gold uptake with time was observed by time-stepped sampling and radiochemical Au analysis. Sorbants were polished thick sections of quartz, pyrite, pyrrhotite and elemental gold, as well as crushed grains and sawed mineral cubes of quartz and pyrite (all randomly oriented). The kinetics of gold sorption strongly varied with the surface area of the sorbents, the type of mineral and the pH of the solution. Mineral-specific differences in reaction rates were observed only at experimental pH values around 2.3, where sorption on pyrrhotite and elemental gold was much more rapid than by quartz and pyrite. At pH around 1.3 gold sorption was rapid on all minerals. This finding is thought to reflect the gold speciation, i.e. neutral hydroxo-gold complexes above pH 1.5, for which only chemisorption is possible, versus dominantly AuCl ₄ ^– below pH 1.5, where unspecific electrostatic interaction enhances reaction rates with all protonated mineral surfaces.     

Cryogenic carbonates in cave environments: A review

Cryogenic cave carbonate (CCC) represents a specific type of speleothem. Its precipitation proceeds at the freezing point and is triggered by freezing-induced concentration of solutes. Compared to classical speleothems (stalagmites, flowstones), CCC occurs as accumulations of loose uncemented aggregates. The grain sizes range from less than 1 μm to over 1 cm in diameter. Karst groundwater chemistry and its freezing rate upon entering the cave are responsible for highly variable grain morphology. Rapid freezing of water results in the formation of CCC powders with grain size typically below 50 μm. Slow freezing of water in caves (usually in systems where the CO₂ escape is partly restricted; e.g., ice covered water pools) results in the formation of large mineral grains, with sizes from less than 1 mm to about 20 mm. The range of carbon and oxygen stable isotope compositions of CCC is larger than for a typical carbonate speleothem. Rapid freezing of water accompanied by a quick kinetic CO₂ degassing results in large ranges of δ¹³C of the CCC powders (between –10‰ and +18‰ PDB). Slow freezing of water, with a restricted CO₂ escape results in gradual increase of δ¹³C values (from −9‰ to +6‰ PDB; data ranges in individual caves are usually much more restricted), accompanied by a δ¹⁸O decrease of the precipitated carbonate (overall range from −10‰ to −24‰ PDB). These unusual trends of the carbonate δ¹⁸O evolution reflect incorporation of the heavier ¹⁸O isotope into the formed ice. New isotope data on CCC from three Romanian ice caves allow better understanding of the carbon and oxygen isotope fingerprint in carbonates precipitated from freezing of bulk water. CCCs are proposed as a new genetic group of speleothems.     

Marble mylonites in the Bancroft shear zone, Ontario, Canada: microstructures and deformation mechanisms

Mylonitization of medium-grade marbles in the Bancroft shear zone, Ontario, Canada, is characterized by decreasing grain-size of both calcite and graphite, and a variety of textures. Calcite grain-sizes vary from several millimeters in the protolith, to 50–200 μm in mylonite, to <30 μm in ultramylonite. Corresponding calcite grain shapes are equant in the protolith, elongate in protomylonite (first-developed dimensional preferred orientation), equant in coarse mylonite, elongate in fine mylonite (second-developed dimensional preferred orientation) and generally equant in ultramylonite, which suggests that external energy (applied stress) that tends to elongate grains competed with internal energy sources (e.g. distortional strain) that favor equant shapes. Graphite grain-size changes from several millimeters to centimeters in the protolith to submicroscopic in ultramylonite. In the mylonitic stages, graphite is present as dark bands, while in the ultramylonitic stage it is preserved as a fine coating on calcite grains.Based on textural evidence, twinning (exponential creep; regime I), dynamic recrystallization (power law creep; regime II) and possibly grain boundary sliding superplasticity (regime III) are considered the dominant deformation mechanisms with increasing intensity of mylonitization; their activity is largely controlled by calcite grain-size. Calcite grain-size reduction occurred predominantly by the process of rotation recrystallization during the early stages of mylonitization, as indicated by the occurrence of core and mantle or mortar structures, and by the grain-size of subgrains and recrystallized grains. Grain elongation in S-C structures indicates the activity of migration recrystallization; these structures are not the result of flattening of originally equant grains. Differential stress estimates in coarse mylonites and ultramylonites, based on recrystallized grain-size, are 2–5 and 14–38 MPa, respectively. Initial grain-size reduction of graphite occurred by progressive separation along basal planes, analogous to mica fish formation in quartzo-feldspathic mylonites.Calcite-graphite thermometry on mylonitic and ultramylonitic samples shows that the metamorphic conditions during mylonitization were 475 ± 50°C, which, combined with a differential stress value of 26 MPa, gives a strain rate of 1.2 x 10⁻¹⁰s⁻¹ based on constitutive equations; corresponding displacement rates are <38 mmyr⁻¹.     

Comparison of soil solution chemistry sampled by centrifugation, two types of suction lysimeters and zero-tension lysimeters

The choice of sampling method for soil solution is of great importance. In this paper soil solution chemistry sampled by centrifugation, two types of suction lysimeters and zero-tension lysimeters have been studied with the purpose of investigating systematic differences between them. The samples were taken at 4 depths from an acidified forest soil as well as from adjacent lime and ash treated soils. A centrifugation drainage method was compared with two types of suction lysimeters (‘Rhizon’ and ‘Prenart’) and zero-tension lysimeters. About half of the 27 variables measured showed a significant difference between the sampling methods used. Typically the centrifuged samples had lower pH (4.0 vs. 4.4), Ca (21 μM vs. 30 μM) and Mg (25 μM vs. 34 μM) concentrations and higher Cl (330 μM vs. 230 μM) and DOC (4.4 mM vs. 3.2 mM) concentrations than the Rhizon lysimeters. Also the other lysimeters showed significant differences compared to the centrifuged samples for about half the number of analytes. Centrifuged samples had higher concentrations of all analytes except NO₃ and PO₄ compared to zero-tension lysimeters and also for all analytes except NO₃ and Al compared to Prenart lysimeters. Among the environmental factors considered depth showed an influence to some extent, while sampling occasion had a great significant impact on the difference between the centrifugation method and the Rhizon lysimeters. Factors like individual pits or soil treatment did not show any influence on the difference between the methods.     

Gold, silver and other elements in aquatic bryophytes from a mineralised area of North Wales, U.K.

Concentrations of Au, Ag, As, Cd and Sb in aquatic bryophytes collected from the Dolgellau Mineral Belt, North Wales, U.K. are reported. One aquatic liverwort, Scapania undulata (L) Dum. and two mosses, Fontinalis squamosa Hedw. and Racomitrium aciculare (Hedw.) Brid. were collected from sites upstream and downstream of the recently reopened Gwynfyndd Au mine. There was little inter-species variation in metal contents for these three bryophytes, but Scapania undulata appeared the most sensitive to changes in water concentrations of Ag, As and Sb. Gold concentrations varied little between the contaminated and control sites. Concentrations in the range < 4–18 ng Aug g⁻¹ D.W. were typical background levels, while bryophytes collected immediately below the mine contained 6–45 ng Au g⁻¹. Silver and Sb both showed more pronounced ( 5–10 fold) elevations above control concentrations in samples collected downstream of the mine. Background concentrations for these elements were 5–85 ng Ag g⁻¹ and 0.15–1.3 μg Sb g⁻¹.Arsenic concentrations downstream of the mine (160–1080 μg g⁻¹) greatly exceeded the background range of 9–32 μg g⁻¹. It is suggested, therefore, that As may be an ideal ‘pathfinder’ element when prospecting for auriferous deposits using aquatic bryophytes.     

Use of a sensitive analytical method and the silt-clay (< 53 μm) fraction of stream sediments in exploration for gold in northern Thailand

Heavy mineral concentrates (SG 3.3) from the Huai Hin Laep, a tributary of the Huai Kho Lo River in northern Thailand, contain strongly anomalous concentrations of gold. In contrast, the gold content of the associated < 149 μm and <53 μm fractions of the sediment is generally less than the 5 ppb detection limit obtained by a conventional fire assay-atomic absorption spectrometry method. To test for the presence of a gold anomaly at concentrations < 5 ppb, we have used an aqua-regia digestion followed by an Amberlite XAD-8 column preconcentration technique that, when used with a spectrometer that enables full display of the analytical spectrum to optimize baseline analysis, gives a detection limit of 0.1 ppb Au.Gold content of the < 53 μm sediment fraction ranges from 1.0 to 3.1 ppb compared to concentrations that typically range from 1000 to more than 100,000 ppb in the heavy mineral concentrates. However, despite gold concentrations in the sediment being several orders of magnitude lower than those in the heavy mineral concentrates, the downstream dispersion patterns are similar, with gold concentrations increasing at high energy sites and downstream away from the assumed source. These results identify the presence of a greatly diluted gold anomaly in the < 53 μm fraction of the sediments and suggest that transport and deposition of this fine grained gold is controlled by the same sedimentological factors that control the behavior of gold in the sand-size range, between 53 μm and 425 μm. Most important from an exploration standpoint, is that by using a sufficiently sensitive analytical method, meaningful gold dispersion patterns can be recognized at concentrations below 5 ppb.     

A new protocol for oxygen isotope analysis of authigenic and biogenic fine silica grains using laser-extraction technique

We report here a 30 W CO₂ laser heating protocol for analyzing oxygen isotope composition (δ¹⁸O in ‰ vs. V-SMOW) of quartz and amorphous silica grains lower than 50 and 2 μm with a good external precision (1σ < 0.15‰). This technique is used to investigate δ¹⁸O composition of macro-, micro- and crypto-crystalline quartz cements of quartzite levels occurring in a sand sequence from the South of France (Apt Series), after a physical separation of the quartz cements. δ¹⁸O data obtained from this technique are compared with δ¹⁸O data obtained from in situ ion microprobe analyses. This study also presents promising results on δ¹⁸O analysis of phytoliths obtained with the laser heating protocol (1σ < 0.1‰).     

Cation distribution in pentlandites (Fe,Ni)9S8: Dependence on pressure and temperature and kinetics of the cation exchange reaction

This paper describes the distribution of Fe and Ni between the octahedral and tetrahedral sites in pentlandite (Fe,Ni)₉S₈. The dependence of the distribution on pressure and temperature and the activation energy of the cation exchange reaction were determined through annealing experiments. Synthetic crystals were annealed at 433–723 K and pressures up to 4 GPa, and natural crystals were annealed at 423, 448 and 473 K in evacuated silica capillary tubes for various durations. The cation distributions in the synthetic crystals were determined with an X-ray powder method employing the anomalous dispersion effect of CuK. and FeK radiations, while those of natural crystals were calculated from the cell dimensions. The values of U, S and V for the Fe/Ni exchange reaction are –6818 J mol^–1, 20.52 J K^–1 mol^–1, and 6.99 × 10^–6 m³ mol^–1, respectively. The dependence of the Fe/Ni distribution on pressure (Pa) and temperature (Kelvin) was determined as lnK = 2.47+8.20 × 10² T ^–1+8.41 x 10^–7 T ^–1 P, where K = (Fe/Ni)_octahedral /(Fe/Ni)_tetrahedral. The activation energy of the cation exchange reaction was 185 kJ mol^–1.     

Labile barite contents and dissolved barium concentrations on Blake Ridge: New perspectives on barium cycling above gas hydrate systems

Blake Ridge hosts an extensive gas hydrate system where escaping CH₄ is consumed through anaerobic oxidation of methane (AOM) at a sulfate–methane transition (SMT) in shallow sediment. Previous geochemical work on ridge crest sediment has documented Ba fronts above the SMT, and has suggested that these horizons can be used to constrain the evolution of the SMT and AOM over time. We expand on this concept and further test it by determining the labile Ba contents of sediment and the dissolved Ba²⁺ concentrations of pore waters at four ODP sites on Blake Ridge (on the crest at Sites 994, 995 and 997, and on the southern flank at Site 1059). Labile Ba contents are fairly low at all four sites (0.44 and 1.32 mmol/kg), except within 3 m above the SMT at Sites 994, 995 and 997, where they typically exceed 1.24 mmol/kg and can reach 11.3 mmol/kg. These Ba fronts have a diagenetic origin, and SEM analyses show them to be composed of microcrystalline barite. Site 1059 lacks a prominent Ba front. The lowest labile Ba contents generally underlie the Ba fronts and correlate to the base of the SMT. Dissolved Ba²⁺ concentrations are low (< 1–4 μM) from the seafloor to within 2 m above the main Ba front. Below this depth, they rapidly increase at Sites 994, 995, and 1059, reaching peak concentrations (to 57 μM) at the base of the SMT. By contrast, a rapid rise in dissolved Ba²⁺ is not observed at Site 997. Dissolved Ba²⁺ concentrations are only moderately high (10–25 μM) below the SMT at all four sites. Collectively, this information supports a diagenetic model where barite passing into the SMT dissolves, and some of the dissolved Ba²⁺ then migrates up to form an authigenic barite peak. The contrasting signatures at the different sites indicate non-steady-state differences in the overall process. The size of the peaks on the crest of Blake Ridge necessitates that the recycling of Ba across the SMT has been operating at the current sub-bottom depths for > 100 kyr. Thus, CH₄ escaping through the AOM has likely been fairly constant over this time. It is possible that the SMT is currently rising toward the seafloor at Site 1059.