On the pH-dependent formation constants of iron(III)-sulfur(IV) transient complexes

An experimental study is described of Fe(III)-S(IV) formation constants measured as a function of pH (1–3), ionic strength (0.2–0.5 M) and [Fe(III)] _T (2.5–5.0×10^–4 M) using a continuous-flow spectrophotometric technique to make observations 160 ms after mixing. Preliminary experiments using pulse-accelerated-flow (PAF) spectrophotometry to measure rate constants on a microsecond timescale are also described. The conditional formation constant at 25 °C can be modeled with the following equation: {ie307-1} where {ie307-2}K ₇ andK ₈ can be interpreted as intrinsic constants for the coordination of HSO ₃ ^– by FeOH²⁺ and Fe³⁺, respectively, but until further evidence is obtained they should be regarded as fitting constants. PAF spectrophotometry showed that the initial reaction of Fe(III) with S(IV) (pH 2.0) is characterized by a second-order rate constant of 4×10⁶ M^–1 s^–1 which is comparable to rate of reaction of FeOH²⁺ with SO ₄ ^2– . However, the PAF results should be regarded as preliminary since unexpected features in the initial data indicate that the reaction may be more complex than expected.     

Kinetics of redox cycling of iron coupled with fulvic acid

The kinetics of conversion of iron(III) (hydr)oxides to ferrous iron mediated by fulvic acid have been investigated in order to improve the understanding of the redox cycling of iron at the oxic-anoxic boundary in natural waters. Under the conditions similar to natural waters, fulvic acid is able to reduce the iron(III) (hydr)oxide. The kinetics of the reaction depend on the reactivity of iron(III) (hydr)oxides and the reducing power of the fulvic acid. The rate of reaction is 60 nm/h obtained under following conditions: total concentration of Fe(III) 1.0 × 10^–4 M, pH 7.5, fulvic acid 5 mg/L. The rate is considered as a net result of reduction and oxidation in the > Fe^III-OH/Fe(II) wheel coupled with fulvic acid. In a real natural water system, reductants other than fulvic acid may be of importance. The results obtained in the laboratory, however, provide evidence that the Fe(OH)₃(s)/Fe(II) redox couple is able to act as an electron-transfer mediator for the oxidation of natural organic substances, such as fulvic acid by molecular oxygen either in the absence of microorganisms or as a supplement to microbial activity.     

冀西北长城纪宣龙式铁矿层中微体植物化石的发现及其意义

本文研究的是笔者等在冀西北长城系串岭沟组宣龙式铁矿层中发现的微体植物化石,这些化石都保存在铁质叠层石(肾状赤铁矿)和铁质核形石(鲕状赤铁矿)的基本层中。微化石以丝状体为主,部分为球状体。归属于原核生物蓝藻门颤藻科的两个属和色球藻科的一个属。化石层同位素年龄约在1800—1757Ma。这些化石与北美冈弗林特组微化石比较,既有些相似,又有些区别。该化石的发现为研究铁矿的成因,指示沉积环境及层位对比都很有意义。     

Visualization experiments of iron precipitates: Application for in-situ arsenic remediation

Laboratory experiments were carried out to acquire more insight and understanding of the phenomena associated with the in-situ arsenic remediation. Visualization techniques are the most informative for the detection of Fe(II) while flowing in soils. Green Rust (GR) was considered as representative of in-situ iron precipitates. In a visualization flat cell, the change in color of GR to orange, due to oxidation, was monitored by a digital camera and the images were analyzed giving the spatial and temporal distribution of Fe(II). Moreover, both oxygen and pH changes in time were recorded in two sections along the flow direction in the cell. The measured and calculated concentration profiles were compared and the actual reaction rates were predicted. The reaction rate constants measured in this study, under flowing conditions, are in a good agreement with the values obtained from batch experiments reported in the literature.     

Environmental aspects of selected trace metals in soils and waters surrounding Singaran Nala, Raniganj Coalfield

The Raniganj Coalfield is the oldest coalfield in India that has been continuously and extensively mined since the late eighteenth century. The present study reports a geochemical investigation and environmental quality assessment using soil and water in the area surrounding a stream, locally known as Singaran Nala （Nala means storm water drains in Bengali）, in the Raniganj Coalfield. Soil （top soil, mud, silty clay and laterite） and rock samples （sandstone and shale） were collected from the study area and were analyzed for trace metals （Cr, Cu, Fe, Mn, Ni and Zn）. Surface waters from the stream and the Damodar River as well as ground waters from hand pumps and underground mine pits were collected. Water samples were analyzed for major ions （Na^＋, Ca^2＋, Mg^2＋, Cl^-, HNO3^- and SO4^2-） and trace metals （Cu, Fe, Mn, Ni, and Zn）. Trace metal concentrations in soil samples are found higher than the average world soil composition. Nevertheless, trace metal （Cr, Cu, Ni and Zn） concentrations in soils exceed or reach the maximum allowable concentrations （MAC） proposed by the European Commission for agricultural soils. In particular, Ni concentrations exceed the typical value for cultivated soils. Chromium, Cu and Ni concentrations in laterite and Cr concentration in topsoil exceed the ecotoxicological limit.     

Speciation of adsorbed arsenate on the surface of hydrous iron oxide

Adsorption of arsenate on hydrous iron oxide is an important process controlling geochemical cycling of arsenic in environment as well as the fate of arsenic-bearing mining wastes. The widely accepted view on the mechanism of adsorption is that arsenate is adsorbed via bidentate binuclear inner-sphere complexation. In this study, we characterized the arsenate-hydrous iron oxide sorption solids synthesized at pH=3-8 using Fourier transformed infrared spectroscopy （FTIR） and X-ray diffraction （XRD）. It has been determined that poorly crystalline ferric arsenate developed on the surface of iron oxide when arsenate was sorbed at acidic pH, while at alkaline pH the adsorption of arsenate was via bidentate complexation.     

XANES analysis of the mechanisms of arsenic removal in biological iron and manganese treatment unit

Biological iron and manganese removal utilizing indigenous iron and manganese oxidizing bacteria （IRB hereafter） in groundwater can also be applied to arsenic removal according to our pilot-scale test. The arsenic removal probably occurred through sorption and complexation of arsenic to iron and manganese oxides formed by enzymic action of IRB. We investigated the chemical properties of iron and manganese oxides in IRB floc and the valence state of arsenic sorbed to the floc to clarify the mechanisms of the arsenic [especially As （Ⅲ）] removal. The floc samples were collected from two drinking water plants using IRB （Jyoyo and Yamatokoriyama, Japan）, and our pilot - scale test site where arsenic and iron removal using IRB is under way （Mukoh, Japan）. The Jyoyo and Yamatokoriyama IRB floc samples were subjected to As （Ⅲ） and As（Ⅴ） sorption experiments. The elemental composition of the floc samples was measured. XANES spectra were collected on As, Fe and Mn K-edges at synchrotron radiation facility Spring 8 （Hyogo, Japan）. FT-IR and the X-ray diffraction spectra of the samples were also obtained. The IRB floc contained ca. 35 % Fe, 0.3%-3.5% Mn and 2%-6% P. The samples were highly amorphous and contained ferrihidrites and hydrated iron phosphate. According to XANES analyses of IRB, As associated with IRB was in ＋5 valence state when As （Ⅲ） （or As （Ⅴ）） was added in laboratory sorption test, Fe in ＋3 valence state, and Mn a mixture of＋3 and ＋4 valence states. Small shift was observed in the XANES spectra of IRB on As K-edge as the equilibration time of the sorption experiment was increased. Gradual oxidation of a small amount of As （Ⅲ） associated with IRB or change in arsenic binding with sorption site were the probable mechanism.     

Permeability of Hydraulic Fills and Barricade Bricks

Permeability is one of the most important parameters in the design of hydraulic backfilling of mine stopes. A simple and reproducible method was developed for preparing reconstituted hydraulic fill sample in the laboratory, that is representative of the hydraulic fill in the mine stope, replicating the slurry sedimentation process taking place in the mine. Constant head and falling head permeability tests were carried out on the samples, giving consistent results. A brick permeameter was developed to study the flow characteristics of the porous barricade bricks under one-dimensional flow, simulating the flow conditions in the mine. Three different methods were used to determine the permeability of the brick and the results showed very good agreement. This is the first rational attempt to measure the permeability of the porous barricade bricks that are used to close the horizontal access drives in the mines, thus retaining the hydraulic fill. The measurements show that the permeability of the barricade brick is about two to three orders of magnitude greater than that of the hydraulic fill.     

The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt

This study examines the removal of dissolved metals during the oxidation and neutralization of five acid mine drainage (AMD) waters from La Zarza, Lomero, Esperanza, Corta Atalaya and Poderosa mines (Iberian Pyrite Belt, Huelva, Spain). These waters were selected to cover the spectrum of pH (2.2–3.5) and chemical composition (e.g., 319–2,103 mg/L Fe; 2.85–33.3 g/L SO₄⁼) of the IPB mine waters. The experiments were conducted in the laboratory to simulate the geochemical evolution previously recognized in the field. This evolution includes two stages: (1) oxidation of dissolved Fe(II) followed by hydrolysis and precipitation of Fe(III), and (2) progressive pH increase during mixing with fresh waters. Fe(III) precipitates at pH < 3.5 (stages 1 and 2) in the form of schwertmannite, whereas Al precipitates during stage 2 at pH 5.0 in the form of several hydroxysulphates of variable composition (hydrobasaluminite, basaluminite, aluminite). During these stages, trace elements are totally or partially sorbed and/or coprecipitated at different rates depending basically on pH, as well as on the activity of the SO₄⁼ anion (which determines the speciation of metals). The general trend for the metals which are chiefly present as aqueous free cations (Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Co²⁺, Ni²⁺) is a progressive sorption at increasing pH. On the other hand, As and V (mainly present as anionic species) are completely scavenged during the oxidation stage at pH < 3.5. In waters with high activities (> 10⁻¹) of the SO ₄⁼ ion, some elements like Al, Zn, Cd, Pb and U can also form anionic bisulphate complexes and be significantly sorbed at pH < 5. The removal rates at pH 7.0 range from around 100% for As, V, Cu and U, and 60–80% for Pb, to less than 20% for Zn, Co, Ni and Mn. These processes of metal removal represent a significant mechanism of natural attenuation in the IPB.     

江苏省矿山的主要生态环境问题及治理对策

江苏的经济发展较快,对矿产资源的需求量亦大。多年来的无序开采,对生态环境造成很大的破坏和影响,出现了山体植被遭受破坏、土地被占用、环境受污染、诱发地面沉降、地面塌陷等一系列问题,已影响到国民经济的发展。随着省人大和省政府关于限制开山采石和保护环境等政策、法规出台和落实,近几年乱采滥挖现象基本得到了有效的遏制。人们的环保意识得到了加强,不少矿山已逐步开始对环境治理,且初见成效。文章介绍了江苏生态环境现状、存在的主要问题和治理对策,以期引起各级政府和广大民众在对矿产资源开采的同时更要注重环境保护。