Simultaneous Determination of Fluorine,Chlorine, Bromine and Iodine in Six Geochemical Reference Materials Using Pyrohydrolysis,Ion Chromatography and Inductively Coupled Plasma‐Mass Spectrometry

Concentrations of halogens (fluorine, chlorine, bromine and iodine) were determined in six geochemical reference materials (BHVO‐2, GS‐N, JG‐1, JR‐1, JB‐1b, JB‐2). Halogens were first extracted from powdered samples using a pyrohydrolysis technique, then hydrolysis solutions were analysed by ion chromatography for F and Cl and inductively coupled plasma‐mass spectrometry for Br and I. The detection limits in solutions were 100 μg l^?1 for both F and Cl and 10 ng l^?1 for Br and I. Considering the extraction procedure, performed on a maximum of 500 mg of sample and producing 100 ml of pyrohydrolysis solution, detection limits in rock samples were 20 mg kg^?1 for F and Cl and 2 μg kg^?1 for Br and I. The mean analytical errors on the studied composition ranges were estimated at 10 mg kg^?1 for F and Cl, 100 μg kg^?1 for Br and 25 μg kg^?1 for I. The concentration values, based on repeated (generally > 10) sample analysis, were in good agreement generally with published values and narrowed the mean dispersion around mean values. Large dispersions are discussed in terms of samples heterogeneity and contaminations during sample preparation. Basaltic RMs were found to be more suitable for studies of halogen compositions than differentiated rock material, especially granites – the powders of which were heterogeneous in halogens at the 500 mg level.     

Selenium mobilization during a flood experiment in a contaminated wetland: Stewart Lake Waterfowl Management Area,Utah

Constructed and natural wetlands can accumulate elevated levels of Se; however, few data are available on cost-effective methods for remobilization and removal of Se from these areas. A field experiment was conducted to assess the effectiveness of flooding on the removal of Se from dry surface sediments. The 83-m² flood-experiment plot contained 10 monitoring wells, a water-quality minimonitor (continuous measurement of pH, specific conductance, water temperature, and dissolved O₂), a down-hole Br electrode, and 2 pressure transducers. Flooding was initiated on August 27, 2002, and a Br tracer was added to water delivered through a pipeline to the flood plot during the first 1.2 h. Standing water depth in the flood plot was maintained at 0.3 m through September 1, 2002. The Br tracer data indicate a dual porosity system that includes fracture (mud cracks) and matrix flow components. Mean vertical water velocities for the matrix flow component were estimated to range from 0.002 to 0.012 m/h. Dissolved (less than 0.45 μm) Se increased from pre-flood concentrations of less than 10 μg/L to greater than 800 μg/L during flooding in samples from deep (2.0 m below land surface) ground water. Selenium concentrations exceeded 5500 μg/L in samples from shallow (0.8 m below land surface) ground water. Ratios of Se to Br in water samples indicate that Se moved conservatively during the experiment and was derived from leaching of near-surface sediments. Cumulative Se flux to the deep ground water during the experiment ranged from 9.0 to 170 mg/m². Pre- and post-flood surface soil sampling indicated a mean Se flux of 720 mg/m² through the top 15 cm of soil. Ground-water samples collected 8 months after termination of the flood experiment contained Se concentrations of less than 20 μg/L. The minimonitor data indicate a rapid return to chemically reducing conditions in the deep ground water, limiting the mobility of the Se dissolved in the water pulse introduced during the flood experiment. Ratios of Se to Br in deep ground-water samples collected 8 months after the experiment confirmed the removal of Se from the aqueous phase. Based on the median Se flux rate estimated during the experiment of 0.65 mg/h/m² (n = 52), 7 flooding cycles would be required to meet the 4 μg/g remediation goal in surface soils from the SLWMA wetland.     

The influence of humic substances on the geochemistry of iodine in nearshore and hemipelagic marine sediments

Iodine is characteristically enriched at the surface of hemipelagic and nearshore sediments deposited under oxygenated conditions. In such sediments, bulk I/C_org ratios usually decrease with depth to values which are characteristic of anoxic sediments, reflecting a preferential release of I during early diagenesis. There is some debate as to whether sedimentary I is associated with the iron oxyhydroxide phase or with the organic fraction, and whether the decrease in I/C_org with depth is due to the dissolution of the iron oxyhydroxides or the decomposition of labile organic matter.It is shown that in a surficial hemipelagic sediment sample and in a nearshore sediment core I is mainly associated with the organic fraction and, moreover, that humic substances are involved in the surficial iodine enrichment. Laboratory experiments on the uptake and release of I by and from sedimentary humic substances also suggest a mechanism whereby humic materials reduce iodate at the sediment/water interface to an electrophilic I species which further reacts with the organic matter to produce iodinated organic molecules. During burial, this excess I could be displaced from the organic matrix by nucleophiles such as sulphide ions or thiosulphate, thus providing a possible explanation for the decrease in I/C_org ratio with depth observed in many nearshore and hemipelagic sediments.     

Halogens and noble gases in sedimentary formation waters and Zn–Pb deposits: A case study from the Lennard Shelf,Australia

Halogen ratios (Br/Cl and I/Cl) and concentrations provide important information about how sedimentary formation waters acquire their salinity, but the possible influence of organic Br derived from sedimentary wall-rocks is rarely quantified. Here, it is demonstrated that Br/Cl versus I/Cl mixing diagrams can be used to deconvolve organic Br contributions; that organic matter has a limited range of Br/I ratios; and that organic Br is a more significant component in Zn–Pb deposit ore fluids than previously recognised. The significance of these findings is illustrated for the Lennard Shelf Zn–Pb deposits of Western Australia.Fluid inclusions related to Lennard Shelf Zn–Pb mineralisation have variable salinity and hydrocarbon contents. The halogen data from these fluid inclusions require mixing of three fluid end-members: (1) an evaporated seawater bittern brine (30 wt.% NaCl equiv.) with greater than seawater Br/Cl ratio; (2) a lower salinity pore fluid (?5 wt.% NaCl equiv.) with moderately elevated Br/Cl and I/Cl; and (3) fluids with Br/Cl ratios of ～5 times seawater and extremely elevated I/Cl ratios of ～11,500 times seawater. The first two fluids have ⁴⁰Ar/³⁶Ar of 300–400 and greater than air saturated water ³⁶Ar concentrations that are typical of fluid inclusions related to Zn–Pb mineralisation. The third ‘organic-rich’ fluid has the highest ⁴⁰Ar/³⁶Ar ratio of up to 1500 and a depleted ³⁶Ar concentration.Mineralisation is interpreted to have resulted from mixing of Zn-rich evaporitic brines and H₂S present in hydrocarbons. It is suggested that aqueous fluids acquired organic Br and I from hydrocarbons, and that hydrocarbons exsolving from the aqueous fluid removed noble gases from solution. Interaction of variably saline brines and hydrocarbons could account for the variable Br/Cl and I/Cl composition, and ³⁶Ar concentrations, recorded by Lennard Shelf fluid inclusions. The distinct ⁴⁰Ar/³⁶Ar signature of the fluid with the highest I/Cl ratio suggests the hydrocarbons and brines were sourced independently from different parts of the sedimentary basin. These data indicate the complementary nature of halogen and noble gas analysis and provide new constraints on important mixing processes during sediment-hosted Zn–Pb mineralisation.     

The contrasting geochemical behaviours of iodine and bromine in recent sediments from the Namibian shelf

The vertical distribution of iodine, bromine and organic carbon has been examined in sediment cores from a range of environments on the Namibian shelf. The relationship between Br and C org. is linear, and that between I and C org. is variable, for all surface sediments; I/C org. ratios show a decrease of about one order of magnitude between the outer shelf oxidising sediments ($\text{250 × 10}{}^{\mathrm{?4}}$) and the organic-rich inner shelf sediments ($\text{20 × 10}{}^{\mathrm{?4}}$). The contrasting behaviour of the halogens in surface sediments is explained by differences in the amount of halogen absorbed by living organisms within the euphotic zone and on seston on the seabed. It is suggested that sorption by seston occurs only in oxidising sediment where free O₂ is available. Hence, iodine is sorbed by seston in the outer shelf environment, but is not sorbed by the reducing sediments of the inner shelf. Here the iodine in the sediment represents only that taken up by plankton. On the outer shelf, 50–80% of the total iodine in the organic matter is sorbed by seston. The principal site of Br uptake is not known.The distribution of C org. in subsurface sediments broadly reflects that found at the surface, although there is a slight decrease with depth in the outer shelf cores due to dilution by terrigenous materials. In the inner shelf cores, there is no change in the relationship of iodine and bromine to organic carbon at depth. Those from the mid shelf, and especially the outer shelf, on the other hand, show decreases in both I/C org. and Br/C org. ratios, reaching values at about 70 cm depth that are similar to those in surface reduced sediments from the inner shelf. Over this depth interval I/C org. ratios decrease by a factor of five while Br/C org. ratios show a two fold decrease. These changes in the ratios at depth imply that diagenesis within the reducing cores is negligible compared with that of oxidised sediments. The implications of diagenesis with regard to halogen recycling in sediments are briefly discussed.     

Diagenesis of metal-organic complexes in sediments: Formation of metal sulphides from cystine complexes

Metal-cystine complexes of iron, lead, zinc, copper and nickel under mild artificial diagenesis give rise to crystalline metal sulphides and insoluble organic matter as well as gaseous and “oily” organic products. Under confined reducing conditions at 200°C for 100 h a virtual 100% conversion of metal complex to metal sulphide occurs, while < 10% of the associated organic material may remain as kerogen. Such a mechanism could account for the formation of metal sulphides and in particular pyrite from protein- or amino acid-rich material in carbonaceous sediments during diagenesis.     

Early diagenetic vivianite [Fe3(PO4)2 · 8H2O] in a contaminated freshwater sediment and insights into zinc uptake: A μ-EXAFS, μ-XANES and Raman study

The sediments in the Salford Quays, a heavily-modified urban water body, contain high levels of organic matter, Fe, Zn and nutrients as a result of past contaminant inputs. Vivianite [Fe₃(PO₄)₂ · 8H₂O] has been observed to have precipitated within these sediments during early diagenesis as a result of the release of Fe and P to porewaters. These mineral grains are small (<100 μm) and micron-scale analysis techniques (SEM, electron microprobe, μ-EXAFS, μ-XANES and Raman) have been applied in this study to obtain information upon the structure of this vivianite and the nature of Zn uptake in the mineral. Petrographic observations, and elemental, X-ray diffraction and Raman spectroscopic analysis confirms the presence of vivianite. EXAFS model fitting of the FeK-edge spectra for individual vivianite grains produces Fe–O and Fe–P co-ordination numbers and bond lengths consistent with previous structural studies of vivianite (4O atoms at 1.99–2.05 Å; 2P atoms at 3.17–3.25 Å). One analysed grain displays evidence of a significant Fe³⁺ component, which is interpreted to have resulted from oxidation during sample handling and/or analysis. EXAFS modelling of the Zn K-edge data, together with linear combination XANES fitting of model compounds, indicates that Zn may be incorporated into the crystal structure of vivianite (4O atoms at 1.97 Å; 2P atoms at 3.17 Å). Low levels of Zn sulphate or Zn-sorbed goethite are also indicated from linear combination XANES fitting and to a limited extent, the EXAFS fitting, the origin of which may either be an oxidation artifact or the inclusion of Zn sulphate into the vivianite grains during precipitation. This study confirms that early diagenetic vivianite may act as a sink for Zn, and potentially other contaminants (e.g. As) during its formation and, therefore, forms an important component of metal cycling in contaminated sediments and waters. Furthermore, for the case of Zn, the EXAFS fits for Zn phosphate suggest this uptake is structural and not via surface adsorption.     

Microbial mat development and dolomite formation under pre-evaporitic conditions during the Atlantic in a temperate area: The Sarliève Lake (French Massif Central)

The Sarliève marsh in the Limagne plain, in the heart of the French Massif Central, functioned as an endorheic lake during the Late Glacial and the Early and Middle Holocene. During the Late Boreal and the Atlantic it experienced drastic lowering of the water level as a result of dry and warm climatic episodes. Then, pre-evaporitic conditions triggered the deposition of sediment rich in organic matter (OM) and in carbonates including dolomite. Fifty-one samples from a ca. 1.8 m sediment core section covering the period were analysed using Rock–Eval pyrolysis and gas chromatography–mass spectrometry (GC–MS). Throughout the interval, the OM content remained notable to high [up to 13.35% total organic carbon (TOC)] and of good quality as indicated by low oxygen index (OI) values (<200 mg CO₂ g⁻¹ TOC) and high hydrogen index (HI) values (160–660 mg HC g⁻¹) which, as a rule, increased with increasing TOC content.In contrast to the acid fractions, which sometimes contained notable proportions of n-C₁₆ or n-C₁₈ fatty acids (FAs; analysed as the methyl esters, FAMEs), the neutral fractions were almost devoid of low molecular weight compounds. The latter were probably biodegraded during early diagenesis. Conversely, high molecular weight compounds were abundant in both fractions and were dominated by n-alkanols, n-alkanes, steroids and hopanoids in the neutrals and even numbered FAs and hopanoids in the acid fractions. The hopanoids were dominated by regular bishomohopanoids, accompanied by 2-methylated bishomohopanoids, as well as by unidentified bishomohopanoids with methylation in either the D or E ring. These distributions, typical for bacteria, provide support for previous hypotheses on the contribution of microorganisms to the studied record and for providing conditions for the precipitation and growth of dolomite and other pristine carbonate minerals [Bréheret, J.G., Fourmont, A., Macaire, J.J., Négrel, Ph., 2008. Microbially mediated carbonates in the Holocene lacustrine deposits of the Marais de Sarliève (French Massif Central) testify to the evolution of a restricted environment. Sedimentology 55, 557–578]. The preservation of the compounds was probably ensured by persistent reducing conditions during diagenesis, despite variable climatic conditions and related changes in lake level and sedimentation rate. Comparable distributions of hopanoic acids and hopanols, as well as roughly parallel variation with depth in the corresponding components in both fractions, strongly suggest that all the hopanoids derive from the same microbial precursors, slight shifts in the acid/alcohol ratio being governed by limited changes in redox conditions during early diagenesis.     

湖北潜江凹陷古近系深层富钾卤水成因及演化

地下深层富钾卤水是非常重要的钾盐资源,目前很少从区域尺度系统研究沉积盆地中富钾卤水水化学特征及成因.对潜江凹陷深层富钾卤水进行了主、微量元素分析.研究区卤水矿化度为125.70～347.00 g/L,K含量为0.32～6.83 g/L;富集Li、B、I、Na、Cl,亏损Mg、Br,Ca、SO4有富集也有亏损.储层岩石矿...     

Rock-magnetic characterization of early, redoxomorphic diagenesis in turbiditic sediments from the Madeira Abyssal Plain

Rock‐magnetic measurements of two sediment cores from the Madeira Abyssal Plain (MAP), north Atlantic, are used to investigate post‐depositional changes in the concentration, grain size and composition of magnetic minerals in the sediments that have occurred within organic‐rich turbidite horizons. The changes are associated with an initial stage of suboxic (reductive) diagenesis, following depletion of porewater O₂, and a later stage of oxidative diagenesis associated with the slow descent of an oxidation front through the sediment, as a result of diffusion of O₂ from the overlying sea water. The turbidites are of late Quaternary age (δ¹⁸O stages 1–3) and derive both from different sites on the NW African continental margin, and from the flanks of the Canary Islands. Thus, the turbidites are variable compositionally, especially in terms of carbonate, detrital magnetic mineral and organic carbon content. Diagenetic changes in these sediments have been identified using solid‐phase geochemical data (U, Mn, C_org and CaCO₃) reported previously in more than one study. Rock‐magnetic parameters of the sediments, when expressed on a carbonate‐free basis, reveal that significant depletion of detrital ferrimagnetic iron (Fe²⁺/Fe³⁺) oxide grains has occurred within organic‐rich turbidites during redoxomorphic diagenesis. Normalized quotients of magnetic parameters also show that reductive diagenesis is a ferrimagnetic grain size‐selective process, but it has a minimal effect on the canted‐antiferromagnetic Fe³⁺ oxides in the sediment. Such components, if present, therefore become relatively enriched in magnetic assemblages as the ferrimagnetic grains are dissolved progressively, and bulk magnetic concentration is thus depleted. There is clear evidence in both cores for the existence of ultrafine ferrimagnetic grains at depth within the suboxic zone of the organic‐rich turbidites, beneath both active and fossil oxidation fronts. These grains are most probably associated with populations of live magnetotactic bacteria, which commonly inhabit such organic‐rich horizons and play a part in the chain of bacterially mediated reactions normally associated with suboxic diagenesis. These results show that simple and rapid rock‐magnetic techniques can be used to characterize early diagenetic processes involving iron phases in deep‐sea sediments, at least as effectively as more laborious, time‐consuming and sample‐destructive geochemical measurements.     

Geochemistry and origin of rare earth elements (REEs) in the Shengli River oil shale, northern Tibet, China

The Shengli River-Changshe Mountain oil shale zone, located in the North Qiangtang depression, northern Tibet plateau, represents a potentially large marine oil shale resource in China. Twenty-eight samples including oil shale, micritic limestone and marl were collected from the Shengli River area to determine the contents and distribution patterns of rare earth elements (REEs) in marine oil shale. Oil shale samples from the Shengli River area have high ash yield (61.86–67.48%) and TOC content (8.02–13.67%) with low total sulfur (S_t,d) content (0.76–1.39%) and intermediate shale oil content (3.60–16.30%). The total rare earth element (ΣREE) content in oil shale samples is notably depleted (46.79–67.90 μg/g), approximately one third of the mean value of the North American Shale Composite (NASC), and lower than that of world-wide black shales and Chinese coals, but higher than that of world-wide coals and micritic limestone samples (29.21 μg/g) from the Shengli River area. The oil shale samples from the Shengli River area exhibit shale-like Chondrite or NASC-normalized REE patterns similar to those of micritic limestone and marl samples from this area, indicating that REEs of these different lithological samples may have been derived from a similar terrigenous source.REE contents of oil shale samples are highly positive correlated with ash yield and show a positive correlation with Fe and a weakly positive correlation with organic sulfur, and the vertical variations of REEs mainly follow those of Si, Al, K and Ti. All these facts indicate that the REE contents in oil shale seams are mainly controlled by clay minerals and, to a lesser extent, by pyrite, as well as partly associated with oil shale organic constituents. Rare earth elements in the Shengli River oil shale have originated from two sources: a felsic volcanic rock source and a clastic or/and limestone source.     

Direct evidence for nitrogen isotope discrimination during sedimentation and early diagenesis in Lake Kasumigaura, Japan

Sediment core samples from the center of Lake Kasumigaura, Japan, were collected from 1979 to 2007 at intervals of 1 month to 5 yr. We evaluated the degree of modification in N isotope composition during sedimentation and diagenesis. We estimated the degree of isotope discrimination during diagenesis by comparing historical changes in N isotope composition of the surface sediment (top 2 cm) against the vertical profile of the isotope composition of sediment core samples (15 cm depth). The degree of ¹⁵N enrichment during sedimentation appeared to be significant under the preferential N decomposition that occurred in the periods with low C/N ratio values of suspended particulate organic matter. We documented ¹⁵N depletion in sediment deeper than approximately 3 cm during diagenesis. The contrasting directions of N isotope discrimination during sedimentation and diagenesis suggest changing mechanisms of isotopic shift across an oxidation-reduction boundary.     

Vertical variation of phosphorus forms in surface sediments from Wuli Bay, Taihu Lake, China

1IntroductionPhosphorus,an essential nutrient for the primaryproductivity in freshwater systems,is an important fac-tor controlling lacustrine eutrophication.Although ex-ternal input of phosphorus has been assumed as the vi-tal responsibility for the eutrophication of lakes(ZhuJun et al.,2005),the remobilization of phosphorus insediments has a distinct influence on it as well(Bostr m et al.,1982).The concentrations of totalphosphorus(Ptotal)in the sediments are often related tothe trophic st…     

Quantification of Cl,Br and I in Geological Materials by NH4F Digestion: Comparison with Rapid Acid Digestion

The lack of analytical techniques for halogens in geological materials is mainly due to the loss of analytes during sample preparation. This study describes a rapid bulk rock digestion method (NH₄F digestion) for determination of the abundances of Cl, Br and I in geological materials by SF-ICP-MS. During high temperature (200–240 °C) digestion, NH₃ released from the decomposition of molten NH₄F can effectively prevent the loss of halogens released from geological samples. Chlorine, Br and I were not lost during NH₄F digestion at 220 °C for 0.25–6 h. The limits of quantitation for NH₄F digestion were 2.8, 0.018 and 0.003 μg g^-1 Cl, Br and I, respectively. Most results for halogens in geological reference materials by NH₄F digestion were in agreement with their certified values, confirming that the high-performance rapid bulk rock NH₄F digestion has sufficient digestion capability to extract Cl, Br and I from rocks, sediments and soils. In comparison, results obtained following acid digestion showed that HNO₃ + HF digestion could effectively extract Br and I from soil and sediment samples, and that HNO₃ acid digestion is only suitable to use for the determination of Br and I in soil samples.     

Transformation of arsenic compounds in modern intertidal sediments of Iriomote Island, Japan

The arsenic accumulation process in intertidal sediments of Iriomote Island, Japan, is analyzed as a naturally balanced arsenic-fixation system. Major and minor element chemistry is analyzed by X-ray fluorescence photometry, mineralogy is investigated by X-ray diffractometry, and four arsenic compounds are characterized by hydrogen-generated atomic absorption photometry. It is found that arsenic is accumulated by iron hydroxides/oxides precipitated following the decomposition of humic acids in the shallower sediment, and is subsequently incorporated into iron sulfide minerals at depth. The arsenic is immobile during incorporation into arsenic-bearing phases, suggesting that arsenic is unlikely to be released into the porewater under natural conditions in early diagenesis. The formation and decomposition of arsenic-bearing organic compounds appear to be associated with the formation and decomposition of arsenic in oxyhydroxides/oxides, suggesting that microbial activity may play an important role in controlling the behavior of arsenic and arsenic-bearing phases in the sediment column.     

Accumulation rates and predominant atmospheric sources of natural and anthropogenic Hg and Pb on the Faroe Islands

A monolith representing 5420 ¹⁴C yr of peat accumulation was collected from a blanket bog at Myrarnar, Faroe Islands. The maximum Hg concentration (498 ng/g at a depth of 4.5 cm) coincides with the maximum concentration of anthropogenic Pb (111 μg/g). Age dating of recent peat accumulation using ²¹⁰Pb (CRS model) shows that the maxima in Hg and Pb concentrations occur at AD 1954 ± 2. These results, combined with the isotopic composition of Pb in that sample (²⁰⁶Pb/²⁰⁷Pb = 1.1720 ± 0.0017), suggest that coal burning was the dominant source of both elements. From the onset of peat accumulation (ca. 4286 BC) until AD 1385, the ratios Hg/Br and Hg/Se were constant (2.2 ± 0.5 × 10^-4 and 8.5 ± 1.8 × 10^-3, respectively). Since then, Hg/Br and Hg/Se values have increased, also reaching their maxima in AD 1954. The age date of the maximum concentrations of anthropogenic Hg and Pb in the Faroe Islands is consistent with a previous study of peat cores from Greenland and Denmark (dated using the atmospheric bomb pulse curve of ¹⁴C), which showed maximum concentrations in AD 1953.The average rate of atmospheric Hg accumulation from 1520 BC to AD 1385 was 1.27 ± 0.38 μg/m²/yr. The Br and Se concentrations and the background Hg/Br and Hg/Se ratios were used to calculate the average rate of natural Hg accumulation for the same period, 1.32 ± 0.36 μg/m²/yr and 1.34 ± 0.29 μg/m²/yr, respectively. These fluxes are similar to the preanthropogenic rates obtained using peat cores from Switzerland, southern Greenland, southern Ontario, Canada, and the northeastern United States. Episodic volcanic emissions and the continual supply of marine aerosols to the Faroe Islands, therefore, have not contributed significantly to the Hg inventory or the Hg accumulation rates, relative to these other areas. The maximum rate of Hg accumulation was 34 μg/m²/yr. The greatest fluxes of anthropogenic Hg accumulation calculated using Br and Se, respectively, were 26 and 31 μg/m²/yr. The rate of atmospheric Hg accumulation in 1998 (16 μg/m²/yr) is comparable to the values recently obtained by atmospheric transport modeling for Denmark, the Faroe Islands, and Greenland.     

New constraints on fluid sources in orogenic gold deposits,Victoria, Australia

Fluid inclusion microthermometry, Raman spectroscopy and noble gas plus halogen geochemistry, complemented by published stable isotope data, have been used to assess the origin of gold-rich fluids in the Lachlan Fold Belt of central Victoria, south-eastern Australia. Victorian gold deposits vary from large turbidite-hosted ‘orogenic’ lode and disseminated-stockwork gold-only deposits, formed close to the metamorphic peak, to smaller polymetallic gold deposits, temporally associated with later post-orogenic granite intrusions. Despite the differences in relative timing, metal association and the size of these deposits, fluid inclusion microthermometry indicates that all deposits are genetically associated with similar low-salinity aqueous, CO₂-bearing fluids. The majority of these fluid inclusions also have similar ⁴⁰Ar/³⁶Ar values of less than 1500 and ³⁶Ar concentrations of 2.6–58 ppb (by mass) that are equal to or much greater than air-saturation levels (1.3–2.7 ppb). Limited amounts of nitrogen-rich fluids are present at a local scale and have the highest measured ⁴⁰Ar/³⁶Ar values of up to 5,700, suggesting an external or distinct source compared to the aqueous fluids. The predominance of low-salinity aqueous–carbonic fluids with low ⁴⁰Ar/³⁶Ar values, in both ‘orogenic’ and ‘intrusion-related’ gold deposits, is attributed to fluid production from common basement volcano-sedimentary sequences and fluid interaction with sedimentary cover rocks (turbidites). Aqueous fluid inclusions in the Stawell–Magdala deposit of western Victoria (including those associated with N₂) preserve mantle-like Br/Cl and I/Cl values. In contrast, fluid inclusions in deposits in the eastern structural zones, which contain more abundant shales, have elevated molar I/Cl ratios with maximum values of 5,170 × 10⁻⁶ in the Melbourne Zone. Br/I ratios in this zone range from 0.5 to 3.0 that are characteristic of fluid interaction with organic-rich sediments. The maximum I/Cl and characteristic Br/I ratios provide evidence for organic Br and I released during metamorphism of the shales. Therefore, the regional data provide strong evidence for the involvement of sedimentary components in gold mineralisation, but are consistent with deeper metamorphic fluid sources from basement volcano-sedimentary rocks. The overlying sediments are probably involved in gold mineralisation via fluid–rock interaction.     

The Role of Organic Matter in the Formation of Siderite from Xuanlong Area,Hebei Province

Based on the analysis of siderite distribution,occurrence,chemical compositionk,structureal characteristics,carbon-oxygen isotopic characteristics and relationship between siderite and hematite,this paper presents a systematic study of siderite in the region studied.suggesting that the siderite in the Xuanlong area genetically resulted from organically reduced primary hematite during the diagenesis.The ferric and ferrous relations directly depend on organic contents.In the presence of organic matter ferrous iron can be converted to ferric iron through or ganic reduction.The above conclusion has also been proved by organic geochemistry.data.     

Geochemistry of halogens in the Milk River aquifer,Alberta, Canada

Analytical data are presented for Cl, Br and I on a regional scale for the Milk River aquifer. The three halides show strikingly similar spatial distributions and are highly correlated. Concentrations are low in the freshwater portions of the aquifer but increase by as much as two orders of magnitude along the margins. However, halide ratios reach nearly constant values moving down-gradient, suggesting the dominance of a common subsurface source for these ions. Ratios of Cl/I and Cl/Br are less than those of seawater and fit an origin derived from the diagenesis of organic matter in the sediments. Halide ratios rule out leakage and/or diffusion from the underlying Colorado Group as a major influence on the chemistry; the favored hypothesis is altered connate seawater diffusing from low-permeability units within the Milk River Formation as the primary source of salts. This hypothesis of an internal source has important implications for solute sources in other aquifers affected by saline waters because it does not require the importation of a distant fluid.The¹²⁹I/I ratio has a meteoric value in groundwater collected near the recharge area, but ratios for downflow waters are only 8–70% of this value. Due to the 16 Ma half-life of¹²⁹I, these data indicate that most of the increase in dissolved I cannot derive from concentration of a meteoric source by ion filtration, but must have a subsurface origin. Concentrations of¹²⁹I producedin situ by spontaneous fission of²³⁸U attain measurable levels only in the oldest waters sampled (ages≥ 10⁵a), in which it may account for nearly 90% of the total dissolved¹²⁹I concentration.Water ages based upon³⁶Cl/Cl data range up to 2 Ma if uncorrected for any dilution by subsurface sources of dead Cl. If one assumes that the subsurface contributions of Cl contribute at least 90% of total Cl in the distal portion, then the³⁶Cl-based ages are reduced to ∼ 1Ma, somewhat greater than those estimated by hydrodynamic modeling.     

Cl,Br and I analyses of metamorphic and sedimentary rocks by isotope dilution mass spectrometry

Isotope dilution mass spectrometry with negative thermal ions was applied to determine Cl, Br and I in rocks which, in part, contained less than 100 ppb of Br and I. Two sets of samples have been investigated: a) a series of Al-rich metapelites of increasing metamorphic grade from the Damara Orogen, Namibia and b) fresh and hydrothermally altered greywackes from the Pb−Zn deposit Bad Grund in Germany. It was found that regional metamorphism of Al-rich metapelites causes no strong fractionation of the halides. The Br/Cl ratios in the metapelites are similar to those of sea water. The I/Cl and I/Br ratios, however, are 500 times higher. The I depleted in the ocean most probably is associated with organic matter stored in sediments. The unaltered greywackes from near the Pb−Zn vein have about the same concentrations of halides as the metamorphic Al-rich pelites. By contrast, the hydrothemally altered greywackes contain about twice as much Cl and I, and about 2–5 times as much Br as the unaltered samples. The element ratios, however, are similar for all three categories of rocks, thereby indicating that sea water played no role in the hydrothermal system.