Surface oxidation of pyrite under ambient atmospheric and aqueous (pH = 2 to 10) conditions: electronic structure and mineralogy from X-ray absorption spectroscopy

The nature of the surface oxidation phase on pyrite, FeS₂, reacted in aqueous electrolytes at pH = 2 to 10 and with air under ambient atmospheric conditions was studied using synchrotron-based oxygen K edge, sulfur L_III edge, and iron L_II,III edge X-ray absorption spectroscopy. We demonstrate that O K edge X-ray absorption spectra provide a sensitive probe of sulfide surface oxidation that is complementary to X-ray photoelectron spectroscopy. Using total electron yield detection, the top 20 to 50 Å of the pyrite surface is characterized. In air, pyrite oxidizes to form predominantly ferric sulfate. In aqueous air-saturated solutions, the surface oxidation products of pyrite vary with pH, with a marked transition occurring around pH 4. Below pH = 4, a ferric (hydroxy)sulfate is the main oxidation product on the pyrite surface. At higher pH, we find iron(III) oxyhydroxide in addition to ferric (hydroxy)sulfate on the surface. Under the most alkaline conditions, the O K edge spectrum closely resembles that of goethite, FeOOH, and the surface is oxidized to the extent that no FeS₂ can be detected in the X-ray absorption spectra. In a 1.667 × 10⁻³ mol/L Fe³⁺ solution with ferric iron present as FeCl₃ in NaCl, the oxidation of pyrite is autocatalyzed, and formation of the surface iron(III) oxyhydroxide phase is promoted at low pH.     

Strontium as a tracer of weathering processes in a silicate catchment polluted by acid atmospheric inputs, Strengbach, France

This paper determines the weathering and atmospheric contributions of Ca in surface water from a small spruce forested silicate catchment (N–E France) receiving acid atmospheric inputs. The bedrock is a granite with K-feldspar and albite as dominant phases. The calcium content in plagioclase is low and the Ca/Na ratio in surface water is high, reflecting other sources of calcium from those expected from the weathering of major mineral phases. The biotite content is low. Only traces of apatite were detected while no calcite was found in spite of a major hydrothermal event having affected the granite. The strontium isotopic ratio ⁸⁷Sr/⁸⁶Sr and Sr content was used as a tracer of weathering and was determined in minerals and bulk bedrock, open field precipitation, throughfall, soil solution, spring and stream water. The Sr isotopic ratio of the reacting weathering end-member was predicted by simulating the alteration of the granite minerals by incorporating strontium into the water–rock interaction kinetic code KINDIS. In the early stages of water–rock interaction, K-feldspar and biotite strongly influence the isotopic composition of the weathering solution whereas, the Na-rich plagioclase appears to be the main long-term reactive weathering end-member. Approximately 50% of dissolved Sr in streamwater are atmospherically derived. The ⁸⁷Sr/⁸⁶Sr ratios of exchangeable Sr in the fine fraction at 1-m depth from a soil profile indicate that the amount of exchangeable Sr seems essentially controlled by atmospheric inputs. The exception is the deep saprolite where weathering processes could supply the Sr (and Ca). Na-Plagioclase weathering obviously control the chemistry and the isotopic composition of surface waters. The weathering of trace mineral plays a secondary role, the exception is for apatite when plagioclase is absent. Our hydrochemical, mineralogical and isotopic investigations show that a major part of the strong Ca losses detected in catchment hydrochemical budgets that result from the neutralization of acid precipitation has an atmospheric origin. Consequently, in the long term, in such areas, the availability of such an exchangeable base cation might be strongly limited and surface waters consequently acidified.     

Correction: Impact of excessive groundwater pumping on rejuvenation processes in the Bandung basin (Indonesia) as determined by hydrogeochemistry and modeling

In the Bandung basin, Indonesia, excessive groundwater pumping caused by rapid increases in industrialization and population growth has caused subsurface environmental problems, such as excessive groundwater drawdown and land subsidence. In this study, multiple hydrogeochemical techniques and numerical modeling have been applied to evaluate the recharge processes and groundwater age (rejuvenation). Although all the groundwater in the Bandung basin is recharged at the same elevation at the periphery of the basin, the water type and residence time of the shallow and deep groundwater could be clearly differentiated. However, there was significant groundwater drawdown in all the depression areas and there is evidence of groundwater mixing between the shallow and deep groundwater. The groundwater mixing was traced from the high dichlorodifluoromethane (CFC-12) concentrations in some deep groundwater samples and by estimating the rejuvenation ratio (R) in some representative observation wells. The magnitude of CFC-12 concentration, as an indicator of young groundwater, showed a good correlation with R, determined using ¹⁴C activity in samples taken between 2008 and 2012. These correlations were confirmed with the estimation of vertical downward flux from shallower to deeper aquifers using numerical modeling. Furthermore, the change in vertical flux is affected by the change in groundwater pumping. Since the 1970s, the vertical flux increased significantly and reached approximately 15% of the total pumping amount during the 2000s, as it compensated the groundwater pumping. This study clearly revealed the processes of groundwater impact caused by excessive groundwater pumping using a combination of hydrogeochemical methods and modeling.

     

Catastrophic and dangerous inflows to salt mines in Poland as related to the origin of water determined by isotope methods

 Tritium, ¹⁴C, δ¹³C, δ¹⁸O and δD measurements indicated as early as 1973 the existence of inflows of modern meteoric water to the Wapno salt mine in a Zechstein diapir. In spite of these early warnings, the continuation of improper exploitation led, in 1977, to sudden flooding of the mine followed by catastrophic land subsidence. The lesson learned from that catastrophe, as well as the results of isotope investigations performed in the Inowrocław salt mine, led to the decision to flood the mine artificially in order to avoid a similar land subsidence. The Kłodawa mine was not regarded to be in danger of flooding due to a thick clay cap. In fact, a large number of usually short-lasting water occurrences had the isotopic composition characteristic for evaporated ocean water. However, since 1956 an inflow has existed with δ¹⁸O and δD values close to that of pre-Quaternary saline waters and brines in the Mesozoic formations adjacent to the diapir. Two other inflows have recently occurred with the initial δ¹⁸O and δD values of modern waters. As a consequence, the mine is regarded to be in danger, and the exploitation of salt in the areas of inflows has been stopped. The Wieliczka mine, southern Poland, exploits Miocene salts overthrusted together with the Carpathian flysch from the south. The most dangerous and catastrophic inflows were caused by human errors. Isotope data show the water to be of glacial or Holocene age stored in Tertiary, slightly cemented rocks of low permeability, which neighbor the mine from the north. Owing to specific geology, the mine has survived for a long time, in spite of relatively large and long-lasting inflows. However, its existence is in permanent danger. Received: 7 March 1997 · Accepted: 17 November 1998     

火成岩侵入的石灰岩地区电法找水实践与认识

太行山前的大多数石灰岩受火成岩的侵入,造成这些地区的地下水分布极不均匀,施工成井率很低。为了合理有效地开发地下水资源,在工作区进行水文地质调查的基础上,垂直于主构造线方向布置了3条电阻率法勘探剖面线,运用对称四极电阻率测深法,分别测量了视电阻率值。通过绘制视电阻率等值线断面图,定性和定量解释火成岩侵入的石灰岩地区地下富水带在视电阻率等值线图上的表现形态,准确的确定了井位。通过钻探工程验证,水井的出水量较为理想,与物探推断分析得出来的结论吻合良好。在这类地区开展电法找水,研究水文地质条件是基础,野外工作布置要灵活,深刻分析视电阻率等值线的异常形态是关键。     

山东文登金矿成矿条件及成矿过程——阴极发光技术在包裹体研究中的应用

使用阴极发光技术可取得一般岩石显微镜无法得到的地质信息,并可将包裹体的研究从原来的“群分析”统计规律研究水平提高到“单包体分析”水平,获得更小时间单位成矿流体的演化特征,因而能更准确地模拟和恢复地质作用过程。运用阴极发光对石英等矿物的研究,发现蚀变带中的石英按不同的形态特征和发光性可以分为三期,和成矿关系密切为第一、二期石英。根据阴极发光下显示的生长微形态,系统地测试三期石英不同生长时期的包裹体物相,从而获取了整个成矿过程流体的p-t-v-x参数,确定构造作用加热大气降水形成成矿流体,体系开放流体两次减压沸腾导致金矿沉淀的矿体定位机理和成矿动力学机制。     

The effect of long-range atmospheric transport of organochlorine compounds by soil studies from Mongolia to the Arctic

The results of studies on the distribution regularities are presented for polychlorinated biphenyls (PCBs) of different degrees of chlorination and for organochlorine pesticides (OCPs): hexachlorobenzene (HCB), hexachlorocyclohexane (HCCH), and DDT with its metabolites in the soils along the Lena River valley and in background areas of Eastern Siberia and Mongolia. A statistically reliable correlation is found between the PCB–OCP and C_org concentrations. The highest levels of HCB are registered in the soils between 50 and 60° N. The concentrations of αand γ-HCCH increase reliably, while those of pp′-DDT and pp′-DDE decrease from south to north. A trend of the decrease in concentrations from Mongolia to the Laptev Sea is revealed for tri-, tetra-, and penta-chlorine-substituted PCB congeners. However, the soils sampled northwards from 60° N show a reliable increase in the concentrations of tetra-, penta-, and hexachlorine-substituted congeners.     

Microscopic textures in rocks deformed by chemical explosion and experimental stick-slip as a guide to conditions of palaeoseismicity

Both underground chemical explosions and stick-slip fractures are high-speed deformation events that can leave particular marks in the deformed materials. We distinguish the characteristics of high-speed deformation by direct microscopic comparison of the deformation products. Our results show that typical microscopic indicators of high-speed deformation include quartz-shock lamellae, thetomorphic glass, calcite recrystallization, mineral twists and kinks, gravel-cutting microfractures, collision wedges, radial cracks, random gravel arrangement and saw-tooth shaped cracks. These results provide a basis for the identification of palaeoseisms.     

Bonding of methyl mercury to reduced sulfur groups in soil and stream organic matter as determined by x-ray absorption spectroscopy and binding affinity studies

We combined synchrotron-based X-ray absorption near edge structure (XANES) spectroscopy, extended X-ray absorption fine structure (EXAFS) spectroscopy and binding affinity studies to determine the coordination, geometry, and strength of methyl mercury, CH₃Hg (II), bonding in soil and stream organic matter. Samples of organic soil (OS), potentially soluble organic substances (PSOS) from the soil, and organic substances from a stream (SOS) draining the soil were taken along a short “hydrological transect.” We determined the sum of concentrations of highly reduced organic S groups (designated Org-S_RED), such as thiol (RSH), disulfane (RSSH), sulfide (RSR), and disulfide (RSSR), using sulfur K-edge XANES. Org-S_RED varied between 27% and 64% of total S in our samples. Hg L_III-edge EXAFS analysis were determined on samples added CH₃Hg (II) to yield CH₃Hg (II)/Org-S_RED ratios in the range 0.01-1.62. At low ratios, Hg was associated to one C atom (the methyl group) at an average distance of 2.03 ± 0.02 Å and to one S atom at an average distance of 2.34 ± 0.03 Å, in the first coordination shell. At calculated CH₃Hg(II)/Org-S_RED ratios above 0.37 in OS, 0.32 in PSOS, and 0.24 in SOS, the organic S sites were saturated by CH₃Hg⁺, and O (and/or N) atoms were found in the first coordination shell of Hg at an average distance of 2.09 ± 0.01 Å. Based on the assumption that RSH (and possibly RSSH) groups take part in the complexation of CH₃Hg⁺, whereas RSSR and RSR groups do not, approximately 17% of total organic S consisted of RSH (+ RSSH) functionalities in the organic soil. Corresponding figures for samples PSOS and SOS were 14% and 9%, respectively. Competitive complexation of CH₃Hg⁺ by halide ions was used to determine the average binding strength of native concentrations of CH₃Hg (II) in the OS sample. Using data for Org-S_RED, calculated surface complexation constants were in the range from 10^16.3 to 10^16.7 for a model RSH site having an acidity constant of mercaptoacetic acid. These values compare favorably with identically defined stability constants (log K₁) for the binding of methyl mercury to thiol groups in well-defined organic compounds.     

The dissolution rates of natural glasses as a function of their composition at pH 4 and 10.6, and temperatures from 25 to 74°C

Far-from-equilibrium dissolution rates of a suite of volcanic glasses that range from basaltic to rhyolitic in composition were measured in mixed flow reactors at pH 4 and 10.6, and temperatures from 25 to 74°C. Experiments performed on glasses of similar composition suggest that dissolution rates are more closely proportional to geometric surface areas than their BET surface areas. Measured geometric surface area normalized dissolution rates (r_+,geo) at 25°C were found to vary exponentially with the silica content of the glasses. For pH 4 solutions this relation is given by:

(A1)     

The enthalpy of transformation of Ca(OH)2-I (portlandite) to Ca(OH)2-II (EuI2 structure) by low-temperature DSC

 Thermodynamic properties of high-pressure minerals that are not recoverable from synthesis experiments by conventional quenching methods (“unquenchable” phases) usually are calculated from equation of state data and phase diagram topologies. The present study shows that, with cryogenic methods of recovery and sample treatment, phases with a suitable decomposition rate can be made accessible to direct thermodynamic measurements. A set of samples of Ca(OH)₂-II has been synthesized in a multianvil device and subsequently recovered by cooling the high-pressure assembly with liquid nitrogen. Upon heating from liquid nitrogen to room temperature, the material transformed back to Ca(OH)₂-I. The heat effect of this backtransformation was measured by differential scanning calorimetry. A commercial differential scanning calorimeter (Netzsch DSC 404), modified to allow sample loading at liquid nitrogen temperature was used to heat the material from −150 to +200 °C at rates varying between 5 and 15 °C min⁻¹. The transformation started around −50 °C very gradually, and peaked at about 0 °C. To obtain a baseline correction, each sample was scanned under exactly the same conditions after the backtransformation was complete. Because of the relative sluggishness, onset and offset temperatures were not well defined as compared to fast (e.g., melting) reactions. To aid in integration, the resulting signals were successfully fitted using a generic asymmetric peak model. The enthalpy of backtransformation was determined to be ΔH =−10.37 ± 0.50 kJ mol⁻¹. From previous in situ X-ray diffraction experiments, the location of the direct transformation in P-T space has been constrained to 5.7 ± 0.4 GPa at 500 °C (Kunz et al. 1996). With the reaction volume known from the same study, and assuming that ΔC _p of the transformation remains negligible between the conditions of our measurements and 500 °C, our result gives an estimate of the entropy of transition and the P-T slope of the reaction curve. To a first approximation, the values ΔS = −16.00 ± 0.65 J(mol · K)⁻¹ and dP/dT = 0.0040 ± 0.0002 GPa/K have been determined. These results need to be refined by equation of state data for Ca(OH)₂-II. Received: 30 December 1999 / Accepted: 10 April 2000     

An experimental study of magnesite dissolution rates at neutral to alkaline conditions and 150 and 200 °C as a function of pH, total dissolved carbonate concentration, and chemical affinity

Steady-state magnesite dissolution rates were measured in mixed-flow reactors at 150 and 200 °C and 4.6 < pH < 8.4, as a function of ionic strength (0.001 M ? I ? 1 M), total dissolved carbonate concentration (10⁻⁴ M < ΣCO₂ < 0.1 M), and distance from equilibrium. Rates were found to increase with increasing ionic strength, but decrease with increasing temperature from 150 to 200 °C, pH, and aqueous CO₃²⁻ activity. Measured rates were interpreted using the surface complexation model developed by Pokrovsky et al. (1999a) in conjunction with transition state theory (Eyring, 1935). Within this formalism, magnesite dissolution rates are found to be consistent with

     

The use of water-extractable Cu,Mo, Zn,As, Pb concentrations and automated mineral analysis of flue dust particles as tools for impact studies in topsoils exposed to past emissions of a Cu-smelter

An exploratory study has been conducted to test the utility of automated mineral analysis observations to identify flue dust particles in topsoils exposed for several decades to emissions of a copper smelter. The methods used are readily available in mining countries. To identify the most impacted sites, the Cu, Zn, Pb, Mo and As levels in water and diluted sulphuric acid extractions of four topsoil size fractions (833–495 μm, 246–148 μm; 74–38 μm; <38 μm) were analysed. X-ray diffraction analyses were used to demonstrate the mineralogical degradation of smectite phases when approaching the smelter. Flue dust particles in different states of conservation in topsoils were directly observed by scanning electron microscopy (SEM) aided by energy dispersive detection of X-rays. Qemscan^® scanning of dispersed topsoil preparations (10,000 particles) pinpoints smelter particles by their density; flue dust pearls can be tracked by sorting particles according to their sphericity, clearly identifying them as pyrometallurgical products. When sorting soil particles by mineral groups (e.g. sulphides), an increase in this phase group can be observed when approaching the smelter. SEM resolution limits observations to particles larger than 2–3 μm. Smaller particles can be observed by transmission electron microscopy, although observer experience and the availability of equipment time are essential as is the case for SEM.     

The history of Cu,Pb, and Zn inputs to Narragansett Bay,Rhode Island as recorded by salt-marsh sediments

The distribution of metals with depth in sediment cores sampled from industrialized estuaries can reveal long-term trends in loadings to the waterbody. Salt marsh cores were sampled from five locations from the head to the mouth of Narragansett Bay and from one location from a marsh inside a lagoon on the coast of Block Island Sound with the intent of reconstructing historical loadings of Pb, Cu, and Zn to this estuary. Concentrations of Fe and Mn were measured as indicators of redox conditions of the sediment column. Chronologies were developed using accretion rates determined previsly from²¹⁰Pb analyses of the same cores. Excess metal inventories and enrichment over pre-industrial concentrations were greater in upper bay cores reflecting the location of sources at the head of the estuary. The bay cores were similar with respect to the distributions of Cu, Pb, and Zn. Concentrations of all metals began to increase over background levels at depths corredponding approximately to the year 1900. Most of the cores showed peak concentrations of Cu and Pb in the early 1950s and 1970s. Distributions of Zn were more variable among cores, showing peaks in the early 1920s in some cores and in the 1950s and 1970s in others. In general, the observed distributions in the bay cores are consistent with estimated long-term trends in loadings from atmospheric and sewage sources. The metal distributions in the lagoon core appear to reflect atmospheric loadings. However, there are features in some cores that are not explainable using the estimated trends in source inputs. There also is not a 1∶1 correspondence between changes in sediment metal concentrations and changes in loadings. It is likely that this method of reconstruction would benefit from a more detailed characterization of sources, but comparison of sediment and historical records do show that attempts to reduce loadings to the bay have been successful.     

黄河中游响应气候变化和地表相对抬升发育阶地研究

揭示河流系统响应气候变化和地表抬升的机制是理解流域地貌演化以及水系发育过程的基础,其核心难题是如何充分认识它们在阶地发育中扮演的角色.以往的研究倾向于分开讨论气候变化和地表抬升在河流阶地发育中的作用,认为河流堆积/侧蚀和下切行为分别与冰期和间冰期气候对应,或者将阶地作为地表抬升的直接证据.首先,从上下游河段对比的视角初...     

The effects of ionic strength and organic matter on virus inactivation at low temperatures: general likelihood uncertainty estimation (GLUE) as an alternative to least-squares parameter optimization for the fitting of virus inactivation models

This study examined how the inactivation of bacteriophage MS2 in water was affected by ionic strength (IS) and dissolved organic carbon (DOC) using static batch inactivation experiments at 4 °C conducted over a period of 2 months. Experimental conditions were characteristic of an operational managed aquifer recharge (MAR) scheme in Uppsala, Sweden. Experimental data were fit with constant and time-dependent inactivation models using two methods: (1) traditional linear and nonlinear least-squares techniques; and (2) a Monte-Carlo based parameter estimation technique called generalized likelihood uncertainty estimation (GLUE). The least-squares and GLUE methodologies gave very similar estimates of the model parameters and their uncertainty. This demonstrates that GLUE can be used as a viable alternative to traditional least-squares parameter estimation techniques for fitting of virus inactivation models. Results showed a slight increase in constant inactivation rates following an increase in the DOC concentrations, suggesting that the presence of organic carbon enhanced the inactivation of MS2. The experiment with a high IS and a low DOC was the only experiment which showed that MS2 inactivation may have been time-dependent. However, results from the GLUE methodology indicated that models of constant inactivation were able to describe all of the experiments. This suggested that inactivation time-series longer than 2 months were needed in order to provide concrete conclusions regarding the time-dependency of MS2 inactivation at 4 °C under these experimental conditions.     

Reply to the Discussion by John Nott on ‘Coarse‐sand beach ridges at Cowley Beach,north‐eastern Australia: Their formative processes and potential as records of tropical cyclone history’ by Tamura et al. (2018), Sedimentology,65, 721–744

Tamura et al. (2018) refined our understanding of formative processes that have resulted in a series of coarse‐sand beach ridges at Cowley Beach in north‐eastern Australia. Nott (2018) claimed that there are several shortcomings in the findings Tamura et al. (2018) presented. However, his criticism mostly derived from his misunderstanding of the data and discussion presented in Tamura et al. (2018), which thus should be clarified here. This reply also reiterates how his method for estimating the magnitude of past tropical cyclones from beach ridges is inconsistent with our observations of beach morphology and beach‐ridge formative processes.