Investigation of time-dependent reactions of H+ ions with variable and constant charge soils: a comparative study

A sampling-separation method and a dynamic monitoring method were used to investigate the time-dependent reactions of H⁺ ions with two contrasting types of soil, variable charge soils (VCS) and constant charge soils (CCS), by directly evaluating H⁺ ion consumption and other relevant consequences. The results for both CCS and VCS show that H⁺ ion consumption, increase in positive surface charge and increase in soluble Al are all characterized by a rapid step followed by a slow one. The higher the content of free Fe oxides in the soil, the larger the increase in positive surface charge and in H⁺ ion consumption in the initial rapid step. This is due mainly to protonation on external surfaces. The gradual increase in positive surface charge in the slow step for the 3 VCSs is a result of H⁺ ion diffusion to the reactive sites of Fe–OH on internal surfaces. The very low content of free Fe oxides on internal surfaces of the 2 CCSs render a negligible increase in positive surface charge in the slow step. For the 3 VCSs, the gradual consumption of H⁺ ions in the slow process is the result of protonation, Al dissolution and/or transformation into exchangeable acidity. For the 2 CCSs, however, the gradual consumption is mainly the result of Al dissolution and/or transformation into exchangeable acidity. The time-dependent Al dissolution from both VCS and CCS is influenced by several factors such as mineral components, solubility and dissolution rates of the soils, and H⁺ ion concentration in soil suspensions.     

A revised method for determining existing acidity in re-flooded acid sulfate soils

Titratable actual acidity (TAA) is a technique commonly used to estimate the existing pool of exchangeable H⁺ in acid sulfate soils (ASS). A widely adopted version of the TAA method involves titrating a 1M KCl suspension of oven-dry soil (1:40) with NaOH to a known pH endpoint. However, when ASS are subject to long term re-flooding during wetland remediation, former sulfuric horizons can develop substantial quantities of porewater Fe²⁺, non-sulfidic solid-phase Fe(II) and a variety of reduced inorganic sulfur (RIS) species (e.g. pyrite, mackinawite, greigite and elemental sulfur). For these sediments, an oven-drying approach may induce oxidation of the abundant Fe(II) and/or reactive RIS species, thereby generating H⁺ and leading to overestimation of existing in situ exchangeable H⁺. In this study, we compare TAA via the standard approach (1M KCl; 1:40; oven-dry soil, 4 hr extract; TAA_D) with an identical O₂-free extraction approach using wet-sediment (TAA_W). We apply both methods to former sulfuric horizon sediments from freshwater re-flooded ASS wetlands. There are significant (α = 0.01) differences (up to 12×) between TAA measured by the two methods, with the oven-dried standard approach overestimating TAA relative to the wet, O₂-free approach in 85% of cases. Despite the fact that all AVS-S and some S(0) was oxidised during the oven-drying process, the increases in TAA (TAA_D–TAA_W) show very weak correlation(s) with corresponding losses in RIS species or increases in water soluble sulfate and KCl extractable sulfate. However, oven-drying caused substantial loss of 1M KCl exchangeable Fe(II) and 1 M HCl-extractable Fe(II) and led to large increases in 1 M HCl-extractable Fe(III). These changes in Fe fractions displayed strong positive linear correlation (α = 0.01) with increases in TAA. Although this is not evidence of causality, it suggests that oxidation of Fe(II) species are playing an important role in the development of additional exchangeable H⁺ and may be largely responsible for the contrasting TAA derived by the two methods. The differences in TAA between the two methods are greatest in organic-rich surface sediments and are significantly positively correlated with total organic carbon content. These findings have major implications for accurately assessing TAA in re-flooded ASS wetlands.     

Net alkalinity and net acidity 2: Practical considerations

The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples.Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5–4) or near neutral (pH 6–7); ≈ 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6.The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze.The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO₂ and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= −net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH < 6.3 after oxidation had positive Hot Acidity. Samples with similar pH values before oxidation had dissimilar Hot Acidities due to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. Hot Acidity was approximately equal to net acidity calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity calculated from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was equivalent to that calculated based on complete aqueous speciation of Fe^II/Fe^III. Despite changes in the pH, alkalinity, and metals concentrations, the Hot Acidities were comparable for fresh and most aged samples.A meaningful “net” acidity can be determined from a measured Hot Acidity or by calculation from the pH, alkalinity, and dissolved metals concentrations. The use of net alkalinity = (Alkalinity_measured − Hot Acidity_measured) to design mine drainage treatment can lead to systems with insufficient Alkalinity to neutralize metal and H⁺ acidity and is not recommended. The use of net alkalinity = −Hot Acidity titration is recommended for the planning of mine drainage treatment. The use of net alkalinity = (Alkalinity_measured − Acidity_calculated) is recommended with some cautions.     

Ca-H-Al exchanges and aluminium mobility in two Chinese acidic forest soils: a batch experiment

Exchange reactions between Ca²⁺, H⁺ and Al species and their effects on the aluminium mobility in two Chinese acidic forest soils were studied. The study was based on a batch experiment using extractant solutions with different base cation (calcium) concentrations and pH. The experimental data showed that increased Ca²⁺ concentrations increased the release of soil hydrogen—and aluminium ions, especially from the more acid soil. In agreement with a cation exchange process, the treatment with Ca²⁺ extracts gave significantly decreased soil aluminium saturation (AlS) and increased calcium saturation (CaS) on the ion exchanger. Geochemical calculation using AlCHEMI program showed that activities of Al³⁺ in the extracts were all strongly under-saturated with respect to any gibbsite mineral in the studied pH region (i.e. below 4.1). There were instead apparently two different mechanisms controlling the activities of Al³⁺ in extracts. At pH between about 4.1 and 3.7, the Al³⁺ activity did not change significantly with pH. This is especially the case in the more acid soil. Apparently there are no sizeable pools available to release Al in this pH region. At pH below 3.7 (induced by higher Ca²⁺concentration) the activity of Al³⁺ increased with H⁺ though not in a pattern that complies with a gibbsite solubility control. An increase of base cation deposition would therefore mainly enhance the release of hydrogen ions between pH 4.1 and 3.7 and aluminium ions below pH 3.7 from Chinese mature acidic soils. This will cause an increased acidity of soil water in the short term and a decrease in the soil acidity in the long term. More attention should be paid to this fact in Chinese acid rain studies and control options.     

Studies on the solid acidity of heated and cation-exchanged montmorillonite using n-butylamine titration in non-aqueous system and diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy

The effects of heating and cation exchange on the solid acidity of montmorillonite were investigated using n-butylamine titration in non-aqueous system and diffuse reflectance Fourier transform infrared spectroscopy. The number of total, Brønsted, and Lewis acid sites showed the same modulation tendency with increasing heating temperature, reaching a maximum at 120 °C and subsequently decreasing until it reaches a minimum at 600 °C. The Lewis acid sites result from unsaturated Al³⁺ cations, and their number increased with the heating temperature due to the dehydration and dehydroxylation of montmorillonite. The generation and evolution of Brønsted acidity were mainly related to interlayer-polarized water molecules. Water adsorbed on the unsaturated Al³⁺ ions also acted as a Brønsted acid. The acid strength of the Brønsted acid sites was dependent on the polarization ability of the exchangeable cation, the amount of interlayer water, and the degree of dissociation of the interlayer water coordinated to exchangeable cations. All cation-exchanged montmorillonites exhibited different numbers of acid sites and various distributions of acid strength. Brønsted acidity was predominant in Al³⁺-exchanged montmorillonite, whereas the Na⁺- and K⁺-exchanged montmorillonites showed predominantly Lewis acidity. Moreover, Mg²⁺- and Li⁺-exchanged montmorillonites exhibited approximately equal numbers of Brønsted and Lewis acid sites. The Brønsted acidity of cation-exchanged montmorillonite was positively correlated with the charge-to-radius ratios of the cations, whereas the Lewis acidity was highly dependent on the electronegativity of the cations. The acid strengths of Al³⁺- and Mg²⁺-exchanged montmorillonites were remarkably higher than those of monovalent cation-exchanged montmorillonites, showing the highest acid strength (H ₀ ≤ ?3.0). Li⁺- and Na⁺-exchanged montmorillonites exhibited an acid strength distribution of ?3.0 < H ₀ ≤ 4.8, with the acid strength ranging primarily from 1.5 to 3.3 in Li⁺-exchanged montmorillonite, whereas only weaker-strength acid sites (1.5 < H ₀ ≤ 4.8) were present in K⁺-exchanged montmorillonite. The results of the catalysis experiments indicated that montmorillonite promoted the thermal decomposition of the model organic. The catalytic activity showed a positive correlation with the solid acidity of montmorillonite and was affected by cation exchange, which occurs naturally in geological processes.     

The positions of H+, Li+ and Na+ impurities in beryl

Electron Paramagnetic Resonance (EPR) measurements show that Li⁺ impurities are located at two different positions in beryl, one in the crystal lattice and the other in the crystal channel. The position of the Li⁺ impurity in the lattice is generally assumed to be at the site of a missing Be²⁺ ion. It is shown that this is not the case, but that the Li⁺ ion is located in a tetrahedron formed by the oxygens of one side of the Be tetrahedron and the nearest oxygen in the channel ring. This Li site has the coordinates (0.423, 0.344, 0.167) and can only be occupied when the neighbouring Be site is empty. There are four such sites around every Be tetrahedron at the distance of 1.46 Å from the Be site. The distance from the Li site to the oxygens of the Li tetrahedron is 1.84 Å. This compares favourably with the much smaller distance of 1.65 Å in the Be tetrahedron. Protons in beryl are trapped at or near these Li sites. Na⁺ is known to be located at the 2b position at the center of the silicate rings, where it is stabilized by one water molecule located at each of the two surrounding 2a sites. This is also the position of Li⁺ in the beryl channel. It is found that the presence of Na⁺ in the ring of six oxygens reduces the radius of this ring. The Na⁺ impurity has also been supposed to be located at position 2a alone and at 2b stabilized by only one water molecule. It is now proposed that Na⁺ and H₂O are located together in the Al–Be plane when only one water molecule is associated with Na⁺. The water oxygen is located at or near 2a and Na is closer to the Be site in tetrahedral beryl and closer to the Al site in octahedral beryl. It is proposed that the water protons are also located in the Al–Be plane, which would mean that there exists a third type of water in beryl. The origin of protons and OH^? ions in beryl is discussed and it is suggested that the plugs in the beryl channels are CO ₃ ^2? ions. Diffusion of OH^? ions and natural radiation may have led to the creation of NO₃ and the blue colour of Maxixe beryl.     

Iron monosulfide formation and oxidation in drain-bottom sediments of an acid sulfate soil environment

Iron monosulfide formation and oxidation processes were studied in the extensively drained acid sulfate soil environment of the Tweed River floodplain in eastern Australia. Porewater profiles of pH, Eh, SO₄²⁻, Fe²⁺, Fe³⁺, Cl⁻, HCO₃⁻, and metals (Cd, Co, Cr, Cu, Ni, Pb and Zn) were obtained using in situ dialysis membrane samplers (`peepers'). Concentrations of acid volatile S (AVS), pyrite, total S, reactive Fe, total and organic C, simultaneously extracted metals (SEMs) and total elemental composition by X-ray fluorescence, were determined on sediment samples. The oxidation of pyrite in the surrounding landscape provides a source of acidity, Fe, Al, SO₄ and metals, which are exported into the drainage system where they accumulate in the sediments and porewaters. Negative porewater concentration gradients of SO₄²⁻ and Fe²⁺, and large AVS concentrations in the sediments, indicate Fe monosulfides form rapidly under reducing conditions and consume acidity and metals. Oxidation of the sediments during previous drought episodes has resulted in the conversion of monosulfides and pyrite to oxidised Fe minerals and the release of acidity, SO₄²⁻, Fe³⁺, and metals to the surface waters. These formation and oxidation cycles show that Fe monosulfides play an important role in controlling water quality in the drainage system.     

Evaluation of aluminum speciation in surface waters in China and its environmental risk assessment

As the ongoing global research on acid precipitation is developing in depth, more and more attention has been paid to the ecological effects of aluminum (Al) due to its toxicity to plants and animals, which is caused by acid precipitation. As a very serious problem of terrestrial and aquatic environmental acidification occurs in China, especially in southwestern China, a systematic investigation of Al speciation in these regions is very important. In this paper, the Al speciation results of surface waters in China are reported and its ecological impacts is evaluated. More than 100 water samples were collected from about twenty provinces of China. Driscoll's Al speciation scheme combined with the modified MINQEL computer model is used for speciation of Al. This study shows that the ecological impacts of acidification are quite different between China and Western countries, because of different geographical environments and geological settings. In Western countries, acidification is mainly caused by NO₂^-. Due to low concentrations of K⁺, Na⁺, Ca²⁺, Mg²⁺, the buffer capacities of soil and water are weak. Therefore, natural waters can be acidified to pH<5 very easily, resulting in a considerable mobilization of Al and worsening of the ecological environment. In China, acid precipitation is mainly in the form of sulfuric acid. In northwestern China, concentrations of K⁺, Na⁺, Ca²⁺, Mg²⁺ are high in soil and surface waters. This leads to much higher capacity and a high resistance ability to acidification. The pH values of waters in this region are high (around 7) and no serious Al toxicity is found at present. However, in northeastern and southeastern China, the soil is rich in Al (unsaturated aluminosilicates in northeastern China, saturated aluminosilicates in north and central China, aluminum-rich soil in southeastern and southwestern China). The concentrations of K⁺, Na⁺, Ca²⁺, Mg²⁺ in soil and waters are lower than those of northwestern China. Therefore the buffer capacity is limited. Numerous surface waters have already been acidified and pH values declined to 5. The impacts of Al toxicity on ecological systems in these regions are very serious, especially in Jiangxi, Hubei Provinces and Chongqing Municipality.     

Mineral chemistry and chemical zoning in tourmalines, Pampa del Tamboreo, San Luis, Argentina

Tourmalinites that are distally associated with tungsten deposits of the Pampa del Tamboreo area, San Luis, Argentina, contain tourmalines retaining evidence for its origin and evolution. Tourmaline grains uncommonly contain small grains of detrital tourmaline. Analysis of a single detrital tourmaline grain reveals that it is a Ca-rich “oxy-dravite”. Proximal to the detrital cores there are inner domains of asymmetric tourmaline overgrowths that developed during low grade metamorphism. Volumetrically dominant tourmaline overgrowths in the outer domain are concentrically zoned aluminous dravite and “oxy-dravite” with Al/(Al + Fe + Mg) = 0.71–0.74 and Mg/(Mg + Fe) = 0.64–0.71. Variability of Al is primarily controlled by the deprotonation substitution R + OH⁻ = Al + O²⁻ (where R = Fe + Mg), and is a function of the activity of H₂O. A likely evolutionary scenario is one in which volcanogenic material is altered by hydrothermal fluids in the sea floor resulting in an aluminous and magnesian residuum. With further hydrothermal circulation and incipient metamorphism, boron-rich fluids are expelled from metasedimentary and metavolcanic basement rocks and develop Mg-rich tourmalinites in the aluminous, magnesian host rocks. The tourmalinization process occurs over a range of metamorphic conditions and with fluids of variable activity of H₂O.     

Seasonal variations in the composition of mine drainage-contaminated groundwater in Dalarna, Sweden

Groundwater down-gradient from a mine rock dump in Dalarna, Sweden was sampled from the onset of snowmelt runoff (April) until October in order to investigate seasonal variations in groundwater composition. The results demonstrate that considerable variation in solute concentration (Al, Cu, Fe, SO₄²⁻, Zn) and acidity occurs in groundwater; the greatest change in solute concentrations occurs during the melting of the snow cover, when sulfide oxidation products are flushed from the rock dump. During this period, groundwater flow is concentrated near the soil surface with an estimated velocity of 1 m/day. Groundwater acidity varied by a factor of four closest to the rock dump during the sampling period, but these variations were attenuated with distance from the rock dump. Over a distance of 145 m, groundwater pH increases from 2.5 to 4.0 and acidity decreases from 3–13 to 0.8–1.1 meq/L, which is the combined effect of ferric iron precipitation and aluminosilicate weathering. As a result of flushing from the upper soil horizons, peaks in total organic carbon and ammonium concentrations in groundwater are observed at the end of snowmelt. In soils impacted by acidic surface runoff, the sequential extraction of C horizon soils indicates the accumulation of Cu in well-crystallized iron oxyhydroxides in the upper C horizon, while Cu, Fe, Ni and Zn accumulate in a well-crystallized iron oxyhydroxide hardpan that has formed 2.5m below the ground surface. Surface complexation modeling demonstrates that SO₄²⁻ and Cu adsorb to the abundant iron oxyhydroxides at pH < 4, while Zn adsorption in this pH range is minimal.     

Soil geochemical signature of urbanization and industrialization – Chicago, Illinois, USA

The concentrations of 45 elements in ambient (not obviously disturbed) surface soils were determined for 57 sites distributed throughout the city of Chicago, Illinois in the upper Midwestern United States. These concentrations were compared to soils from 105 sites from a largely agricultural region within a 500-km radius surrounding the city and to soils collected from 90 sites across the state of Illinois. Although the bulk composition of the Chicago urban soils reflects largely natural sources, the soils are significantly enriched in many trace elements, apparently from anthropogenic sources. The median concentration of Pb in Chicago soils is 198 mg/kg, a 13-fold enrichment compared to regional concentrations. Zinc (median 235 mg/kg), Cu (59 mg/kg), and Ni (31 mg/kg) are also enriched from 2- to 4-fold in Chicago soils and all four elements show strong mutual correlations. These elevated concentrations are most likely related to vehicular and roadway sources and represent uneven distribution across the city as airborne material. Other airborne particulate material from a combination of fossil fuel combustion, waste incineration, and steel production may contribute to apparent elevated concentrations in Chicago soil of Fe (median 2.9%), Mo (5 mg/kg), V (82 mg/kg) and S (0.09%). Chicago soils are enriched from about 1.6- to 3-fold in these elements. Enrichments in P and Se may be caused by direct addition of phosphate fertilizer to parklands, lawns and gardens. The density of the sampling (1 site per 10 km²) is inadequate to define the distribution of the observed enrichments within the city or to predict soil compositions for most of the areas between sample sites, but does provide a statistically significant signature of the history of urban and industrial activity within the city in contrast to the surrounding agricultural lands.     

Mobility of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric O2: an experimental study

 The major aim was to increase our knowledge on the behaviour of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric oxygen. Samples of this type of sediment collected in a previous investigation at eight sites in western Finland were digested in HClO₄-HNO₃-HCl-HF at 200  °C and in HCl:HNO₃:H₂O at 95  °C (aqua regia), and subjected to extractions with ammonium acetate and hydrogen peroxide. Metals and S in the leachates were determined with ICP-AES. The results of the chemical analyses are compared with previously reported experimental data. The concentrations of Al and Fe in the sulphide-bearing fine-grained sediments are about 7% and 5%, respectively. Of the trace metals studied, Mn is most abundant followed in decreasing order by V>Cr>Ni>Cu>Co. On oxidation of the sediments, high proportions of Co, Mn and Ni, intermediate proportions of Cu but low proportions of Fe, Al, Cr and V are released. The extent of the release of a metal on oxidation is controlled either by (1) the level to which the pH of the sediments drops on oxidation (Al, Cu, Cr, V), (2) the amount of the metal associated with easily reduced phases (metal sulphides) in the sediments (Ni, Co) or (3) the sum of the amount associated with reduced phases and adsorbed on soil compounds (Mn). No control of the release of Fe on oxidation of the sediments was identified. Based on the results of the study it is argued that artificial drainage and the subsequent oxidation of sulphide-bearing sediments will result in extensive leaching of Co, Mn and Ni, moderate leaching of Cu and limited leaching of Cr and V into drainages. The major elements, Fe and Al, have the potential to be mobilised and leached in large amounts, though the proportions mobilised/leached will remain low. It is suggested that the identification of sulphide-bearing sediments with a high potential of metal release should be based on determination of metals in easily mobilised reduced compounds (dissolved e.g. in H₂O₂) and of the level to which the pH of the sediments drops on oxidation. Received: 16 October 1997 · Accepted: 9 March 1998     

Sulfide oxidation and distribution of metals near abandoned copper mines in coastal environments,Prince William Sound,Alaska, USA

The oxidation of sulfide-rich rocks, mostly leftover debris from Cu mining in the early 20th century, is contributing to metal contamination of local coastal environments in Prince William Sound, Alaska. Analyses of sulfide, water, sediment, precipitate and biological samples from the Beatson, Ellamar, and Threeman mine sites show that acidic surface waters generated from sulfide weathering are pathways for redistribution of environmentally important elements into and beyond the intertidal zone at each site. Volcanogenic massive sulfide deposits composed of pyrrhotite and (or) pyrite + chalcopyrite + sphalerite with subordinate galena, arsenopyrite, and cobaltite represent potent sources of Cu, Zn, Pb, As, Co, Cd, and Hg. The resistance to oxidation among the major sulfides increases in the order pyrrhotite ? sphalerite < chalcopyrite ? pyrite; thus, pyrrhotite-rich rocks are typically more oxidized than those dominated by pyrite. The pervasive alteration of pyrrhotite begins with rim replacement by marcasite followed by replacement of the core by sulfur, Fe sulfate, and Fe–Al sulfate. The oxi dation of chalcopyrite and pyrite involves an encroachment by colloform Fe oxyhydroxides at grain margins and along crosscutting cracks that gradually consumes the entire grain. The complete oxidation of sulfide-rich samples results in a porous aggregate of goethite, lepidocrocite and amorphous Fe-oxyhydroxide enclosing hydrothermal and sedimentary silicates. An inverse correlation between pH and metal concentrations is evident in water data from all three sites. Among all waters sampled, pore waters from Ellamar beach gravels have the lowest pH (∼3) and highest concentrations of base metals (to ∼25,000 μg/L), which result from oxidation of abundant sulfide-rich debris in the sediment. High levels of dissolved Hg (to 4100 ng/L) in the pore waters probably result from oxidation of sphalerite-rich rocks. The low-pH and high concentrations of dissolved Fe, Al, and SO₄ are conducive to precipitation of interstitial jarosite in the intertidal gravels. Although pore waters from the intertidal zone at the Threeman mine site have circumneutral pH values, small amounts of dissolved Fe²⁺ in the pore waters are oxidized during mixing with seawater, resulting in precipitation of Fe-oxyhydroxide flocs along the beach–seawater interface. At the Beatson site, surface waters funneled through the underground mine workings and discharged across the waste dumps have near-neutral pH (6.7–7.3) and a relatively small base-metal load; however, these streams probably play a role in the physical transport of metalliferous particulates into intertidal and offshore areas during storm events. Somewhat more acidic fluids, to pH 5.3, occur in stagnant seeps and small streams emerging from the Beatson waste dumps. Amorphous Fe precipitates in stagnant waters at Beatson have high Cu (5.2 wt%) and Zn (2.3 wt%) concentrations that probably reflect adsorption onto the extremely high surface area of colloidal particles. Conversely, crystalline precipitates composed of ferrihydrite and schwertmannite that formed in the active flow of small streams have lower metal contents, which are attributed to their smaller surface area and, therefore, fewer reactive sorption sites. Seeps containing precipitates with high metal contents may contribute contaminants to the marine environment during storm-induced periods of high runoff. Preliminary chemical data for mussels (Mytilus edulis) collected from Beatson, Ellamar, and Threeman indicate that bioaccumulation of base metals is occurring in the marine environment at all three sites.     

ARD generation and corrosion potential of exposed roadside rockmass at Boeun and Mujoo,South Korea

Acid rock drainage (ARD) is a longstanding problem often associated with the resulting corrosion due to the acidity generated from sulfidic oxidation. To evaluate characteristics of ARD and corrosion, samples from the road side rock mass of Boeun and Mujoo were analysed using X-ray diffraction, acid/base accounting and Leaching tests. The results indicated that many samples had a pyritic origin and can be regarded as acid-generating rocks. The Leaching test showed that the average pH of the leachates of samples from both Boeun and Mujoo were moderately acidic, ranging from 3 to 4. Interestingly, as acidity increases from pH 4, the SO₄₋, Fe, Al and Mg concentrations increase abnormally. Samples from roadside slope of Mujoo showed high corrosive potential. Maximum sulfide oxidation rate of a sample taken from Mujoo was as high as 5,166 mg/kg/week.     

Reassessing the management of groundwater use from sandy aquifers: acidification and base cation depletion exacerbated by drought and groundwater withdrawal on the Gnangara Mound, Western Australia

The combined effects of low rainfall, groundwater withdrawal in excess of 300 GL/year and reduced recharge in areas covered by pine plantations has caused the water table in a sandy unconfined aquifer on the Gnangara Mound in Western Australia to drop by up to 5 m and aquifer storage to decline by about 500 GL over the last 20 years. Groundwater has become acidic in areas of high drawdown, with pH values typically being less than 5.0 at the water table, and elevated concentrations of SO₄ ^2?, Al, Fe, Zn, Cu, Ni and Pb. Trends of increasing acidity and base cation concentrations in deep water supply wells in the Mirrabooka wellfield indicate that about 0.7 keq/ha/year of base cations are being leached from soil within cones of depression of pumping wells. These results indicate that the assessment of the sustainable yields of aquifers under conditions of low rainfall needs to consider geochemical interactions between groundwater, aquifer sediments, soils and vegetation, and not be just based on aquifer hydraulics and water-balance changes.     

Hydrogeologic and environmental impact of amjhore pyrite mines,India

Drainage from active and inactive pyrite mines has produced chemical and physical pollution of both ground- and surface water in Amjhore region. In the present case, chemical pollution is caused by exposing pyrite minerals to oxidation or leaching, resulting in undesirable concentrations of dissolved materials. Pyrite mining suddenly exposed large quantities of sulfides to direct contact with oxygen, and oxidation proceeds rapidly, resulting in acidity and release of metal (Fe) and sulfates to the water system, eventually resulting in water pollution in the region. The magnitude and impact of the problem is just being recognized and, as the present and the future projected demand for clean water is of top priority, the present studies were undertaken.Mine drainage includes water flowing from the surface and underground mines and runoff or seepage from the pyrite mines. This article describes the various hydrologic factors that control acid water formation and its transport. The mine drainage is obviously a continuing source of pollution and, therefore, remedial measures mainly consisting of a double-stage limestone-lime treatment technique have been suggested. The present results will be used to develop an alternative and more effective abatement technology to mitigate acid production at the source, namely, the technique of revegetation of the soil cover applied to the waste mine dump material.Water quality change is discussed in detail, with emphasis on acidity formed from exposed pyrite material and on increase in dissolved solids. Preventive and treatment measures are recommended.     

Reaction mechanisms,physical conditions,and mass transfer during hydrothermal alteration of mica and feldspar in granitic rocks from south-central Maine,USA

Samples of granitic rock from south-central Maine contain primary igneous minerals altered by hydrothermal fluids. The reaction mechanisms (by which the over-all mineralogical change during the alteration was accomplished) involve several different mineral-fluid reactions at different reaction sites in the rock. The reactions involve both molecular and charged species in solution. The different reaction sites correspond to alteration of different primary igneous minerals. Biotite is partially converted to chlorite+sphene; microcline to muscovite; plagioclase to various combinations of muscovite, epidote, and calcite. The different reaction sites are linked by exchange of ions: some reaction sites produce ions consumed at other sites and vice versa. Physical conditions during the hydrothermal event are estimated from mineralogical and thermochemical data: P = 3,500 (±300) bars; T =425 ° (± 25 °)C. The fluid was characterized by X _{CO 2} = 0–0.13; ln([K⁺]/[H⁺ ]) = 10.0; ln([Ca²⁺]/[H⁺]²)=9.1; ln([Na⁺]/[H⁺]) = 10.5; Fe/(Fe+Mg) = 0.95. Amounts of secondary minerals in altered rock, when compared to the inferred mineral reactions that formed them, indicate that small but significant amounts (0.01–0.3mol/ 1,000cm³ altered rock) of CO₂, H₂O, H⁺, and K⁺ were added to the granites by fluids during the alteration, as well as lesser amounts (< 0.01–0.03 mol/1,000cm³ altered rock) of Mg²⁺, Fe²⁺, Fe³⁺, Mn²⁺, Na⁺, and Ti⁴⁺. The sole element leached from the granitic rocks during alteration was Ca in amounts 0.1–0.3 mol/1,000 cm³ rock. By estimating the composition of the hydrothermal fluids before and after reaction with the granites and by measuring the amount of material added to or subtracted from the granites during the alteration, the amount and volume of hydrothermal fluid involved can be calculated. Two independent calculations require minimum volumes in the range 100–1,000 cm³ fluid/1,000cm³ altered rock to participate in the hydrothermal event.     

Chemistry of the Ferraria thermal water, S. Miguel Island, Azores: mixing and precipitation processes

The Ferraria thermal water emerges at the sea level in the Ferraria lava delta (western edge of S. Miguel Island, Azores) with temperature of ca. 60°C and pH varying between 5.4 and 6.2. It is of sodium chloride type, resulting from ca. 50% seawater mixing with an acid brackish, at ≈100°C, denoting the presence of significant CO₂(g) and the progress of water–rock interactions in open system conditions. The thermal Na–Cl water is strongly enriched with Sr and Mn and, comparatively, has low concentrations in Al, Fe and As. These elements are removed from the solution as critical conditions for the formation of several neo-formed mineral phases are gradually attained. Thermodynamic equilibrium calculations are consistent with this interpretation, showing that the thermal fluid can precipitate Fe³⁺-(hydr-)oxides, kaolinite and non-crystalline silica. Wells logging show fracture planes and pores fully/partly filled up with polyphase botryoidal aggregates mostly composed of goethite + ferrihydrite and displaying variable adsorbed contents of Si, P and As. These neo-formed phases result from the pristine fluid oxidation due to seawater mixing; its precipitation is easily affected by pH and redox variations of the brackish, due to volcanic gases pressure alterations, and fluid pressure or flow-velocity oscillation in the fractured aquifer.     

Mineralogical characterization of saprolite at the FRC background site in Oak Ridge,Tennessee

The Field Research Center (FRC) including five contaminated sites and a clean background area was established in Oak Ridge, Tennessee, as a part of the U.S. Department of Energy’s Natural and Accelerated Bioremediation Research (NABIR) program. This study investigates the mineralogy and mineralogical pathways of saprolite at the FRC background site to provide a fundamental basis for the remediation strategy for contaminated sites. The background site is underlain interbedded shales, siltstones, and limestones with nearly identical characteristics to the contaminated sites. Bulk samples of saprolite were collected by hand picking approximately at 1 m depth (C horizon) from the soil surface. The soil pH of 4.3 and cation exchange capacity (CEC) of 10.5 cmol/kg measured are in the range of the typical shallow depth saprolite layer in this area. Total Fe by citrate-bicarbonate-dithionate (CBD) and ammonium oxalate extractable (amorphous) were 17.6 and 0.61 g/kg, respectively. Total Mn extracted by NH₂OH·HCl was 0.17 g/kg. X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses indicate that quartz, illite, and microcline (K-feldspar) are the dominant minerals, occupying 95% of mineral composition. The saprolite samples analyzed have shown characteristics of oxic conditions overall, and the degrees of weathering for three sampling locations were various, most for S1 and least for S3, likely influenced either by the flow channels developed through saprolite or by seasonal fluctuation of the groundwater table. The source of the manganese oxide that observed from the site is likely to be Mn-rich muscovite in the shale or Mn-rich biotite in the blackish band in the limestone. The results such as abundant Mn and Fe contents identified encouraging prospects for conducting remediation projects in FRC sites.     

The passivation of calcite by acid mine water. Column experiments with ferric sulfate and ferric chloride solutions at pH 2

Column experiments, simulating the behavior of passive treatment systems for acid mine drainage, have been performed. Acid solutions (HCl or H₂SO₄, pH 2), with initial concentrations of Fe(III) ranging from 250 to 1500 mg L⁻¹, were injected into column reactors packed with calcite grains at a constant flow rate. The composition of the solutions was monitored during the experiments. At the end of the experiments (passivation of the columns), the composition and structure of the solids were measured. The dissolution of calcite in the columns caused an increase in pH and the release of Ca into the solution, leading to the precipitation of gypsum and Fe–oxyhydroxysulfates (Fe(III)–SO₄–H⁺ solutions) or Fe–oxyhydroxychlorides (Fe(III)–Cl–H⁺ solutions). The columns worked as an efficient barrier for some time, increasing the pH of the circulating solutions from 2 to 6–7 and removing its metal content. However, after some time (several weeks, depending on the conditions), the columns became chemically inert. The results showed that passivation time increased with decreasing anion and metal content of the solutions. Gypsum was the phase responsible for the passivation of calcite in the experiments with Fe(III)–SO₄–H⁺ solutions. Schwertmannite and goethite appeared as the Fe(III) secondary phases in those experiments. Akaganeite was the phase responsible for the passivation of the system in the experiments with Fe(III)–Cl–H⁺ solutions.