Improving Internal Consistency of Standard State Thermodynamic Data for Sulfate Ion, Portlandite, Gypsum, Barite, Celestine, and Associated Ions

AbstractThermochemical measurements in the gypsum-portlandite-water system are actually better than those reflected in the thermodynamic properties of CODATA. It is argued that by careful choice of starting points and pathways and with new data, improvements in standard state properties can achieve improved consistency with solubilities of gypsum, portlandite, barite, witherite, celestine, and strontianite if better entropy estimates of these minerals are made

Sulfur geochemistry of hydrothermal waters in Yellowstone National Park, Wyoming, USA. III. An anion-exchange resin technique for sampling and preservation of sulfoxyanions in natural waters

A sampling protocol for the retention, extraction, and analysis of sulfoxyanions in hydrothermal waters has been developed in the laboratory and tested at Yellowstone National Park and Green Lake, NY. Initial laboratory testing of the anion-exchange resin Bio-Rad™ AG1-X8 indicated that the resin was well suited for the sampling, preservation, and extraction of sulfate and thiosulfate. Synthetic solutions containing sulfate and thiosulfate were passed through AG1-X8 resin columns and eluted with 1 and 3 M KCl, respectively. Recovery ranged from 89 to 100%. Comparison of results for water samples collected from five pools in Yellowstone National Park between on-site 1C analysis (U.S. Geological Survey mobile lab) and IC analysis of resin-stored sample at SUNY-Stony Brook indicates 96 to 100% agreement for three pools (Cinder, Cistern, and an unnamed pool near Cistern) and 76 and 63% agreement for two pools (Sulfur Dust and Frying Pan). Attempts to extract polythionates from the AG1-X8 resin were made using HCl solutions, but were unsuccessful. Bio-Rad™ AG2-X8, an anion-exchange resin with weaker binding sites than the AG1-X8 resin, is better suited for polythionate extraction. Sulfate and thiosulfate extraction with this resin has been accomplished with KCl solutions of 0.1 and 0.5 M, respectively. Trithionate and tetrathionate can be extracted with 4 M KCl. Higher polythionates can be extracted with 9 M hydrochloric acid. Polythionate concentrations can then be determined directly using ion chromatographic methods, and laboratory results indicate recovery of up to 90% for synthetic polythionate solutions using AG2-X8 resin columns

Ecological distribution and population physiology defined by proteomics in a natural microbial community

Community proteomics applied to natural microbial biofilms resolves how the physiology of different populations from a model ecosystem change with measured environmental factors in situ.The initial colonists, Leptospirillum Group II bacteria, persist throughout ecological succession and dominate all communities, a pattern that resembles community assembly patterns in some macroecological systems.Interspecies interactions, and not abiotic environmental factors, demonstrate the strongest correlation to physiological changes of Leptospirillum Group II.Environmental niches of subdominant populations seem to be determined by combinations of specific sets of abiotic environmental factors

Advances in structure elucidation of small molecules using mass spectrometry

The structural elucidation of small molecules using mass spectrometry plays an important role in modern life sciences and bioanalytical approaches. This review covers different soft and hard ionization techniques and figures of merit for modern mass spectrometers, such as mass resolving power, mass accuracy, isotopic abundance accuracy, accurate mass multiple-stage MS(n) capability, as well as hybrid mass spectrometric and orthogonal chromatographic approaches. The latter part discusses mass spectral data handling strategies, which includes background and noise subtraction, adduct formation and detection, charge state determination, accurate mass measurements, elemental composition determinations, and complex data-dependent setups with ion maps and ion trees. The importance of mass spectral library search algorithms for tandem mass spectra and multiple-stage MS(n) mass spectra as well as mass spectral tree libraries that combine multiple-stage mass spectra are outlined. The successive chapter discusses mass spectral fragmentation pathways, biotransformation reactions and drug metabolism studies, the mass spectral simulation and generation of in silico mass spectra, expert systems for mass spectral interpretation, and the use of computational chemistry to explain gas-phase phenomena. A single chapter discusses data handling for hyphenated approaches including mass spectral deconvolution for clean mass spectra, cheminformatics approaches and structure retention relationships, and retention index predictions for gas and liquid chromatography. The last section reviews the current state of electronic data sharing of mass spectra and discusses the importance of software development for the advancement of structure elucidation of small molecules

Geochemical modelling for mine site characterization and remediation

Although substantial advances in geochemical modelling have improved our ability to understand and improve mine site characterization and remediation, the limitations of modelling are often underappreciated. Modelers must have expertise in chemistry, geology, hydrology, geochemistry, and microbiology. Those who use codes must understand inorganic chemistry, thermodynamics, and kinetics for water-rock interactions. They must understand that code output is only useful insofar as they understand the limitations of the database and the built-in assumptions. A brief overview of geochemical code development in this paper reveals strengths and weaknesses in modelling capability. Because early predictions of water quality after mine closure often bear little resemblance to actual conditions, this approach should not be relied upon for permitting. Complex large-scale mine sites are not readily amenable to future predictions of hydrogeochemical conditions through modelling, however, modelling can constrain the possible and probable processes that give rise to specific water compositions. Modelling can also help guide remediation planning to find the most cost-effective alternative. Examples are provided for the Questa, New Mexico natural background study, the Summitville Mine, Colorado, and the Pinal Creek Basin, Arizona acid-contaminated aquifer

Effects and quantification of acid runoff from sulfide-bearing rock deposited during construction of Highway E18, Norway

The Highway E18 between the cities of Grimstad and Kristiansand, southern Norway, constructed in the period 2006–2009, cuts through sulfide-bearing rock. The geology of this area is dominated by slowly-weathering gneiss and granites, and oxidation of fresh rock surfaces can result in acidification of surface water. Sulfide-containing rock waste from excavations during construction work was therefore deposited in three waste rock deposits off-site. The deposits consist of 630,000–2,360,000 metric tons of waste rock material. Shell sand and limestone gravel were added in layers in adequate amounts to mitigate initial acid runoff in one of the deposits. The shell sand addition was not adequate in the two others. The pH in the effluents from these two was reduced from 4.9–6.5 to 4.0–4.6, and Al concentrations increased from below 0.4 mg/L to 10–20 mg/L. Stream concentrations of trace metals increased by a factor of 25–400, highest for Ni, and then in decreasing order for Co, Mn, Cd, Zn and Cu. Concentrations of As, Cr and Fe remained unchanged. Ratios of Co/Ni and Cd/Zn indicate that the metal sources for these pair of metals are sphalerite and pyrite, respectively. Based on surveys and established critical limits for Al, surface waters downstream became toxic to fish and invertebrates. The sulfur release rates were remarkably stable in the monitoring period at all three sites. Annual sulfur release was 0.1–0.4% of the total amount of sulfur in the deposit, indicating release periods of 250–800 years. Precipitates of Al-hydroxysulfates, well-known from mining sites, were found at the base of the deposits, in streams and also along the ocean shore-line. The effects of added neutralization agents in the deposits and in treatment areas downstream gradually decreased, as indicated by reduced stream pH over time. Active measures are needed to avoid harmful ecological effects in the future.acceptedVersio

Effects and quantification of acid runoff from sulfide-bearing rock deposited during construction of Highway E18, Norway

The Highway E18 between the cities of Grimstad and Kristiansand, southern Norway, constructed in the period 2006–2009, cuts through sulfide-bearing rock. The geology of this area is dominated by slowly-weathering gneiss and granites, and oxidation of fresh rock surfaces can result in acidification of surface water. Sulfide-containing rock waste from excavations during construction work was therefore deposited in three waste rock deposits off-site. The deposits consist of 630,000–2,360,000 metric tons of waste rock material. Shell sand and limestone gravel were added in layers in adequate amounts to mitigate initial acid runoff in one of the deposits. The shell sand addition was not adequate in the two others. The pH in the effluents from these two was reduced from 4.9–6.5 to 4.0–4.6, and Al concentrations increased from below 0.4 mg/L to 10–20 mg/L. Stream concentrations of trace metals increased by a factor of 25–400, highest for Ni, and then in decreasing order for Co, Mn, Cd, Zn and Cu. Concentrations of As, Cr and Fe remained unchanged. Ratios of Co/Ni and Cd/Zn indicate that the metal sources for these pair of metals are sphalerite and pyrite, respectively. Based on surveys and established critical limits for Al, surface waters downstream became toxic to fish and invertebrates. The sulfur release rates were remarkably stable in the monitoring period at all three sites. Annual sulfur release was 0.1–0.4% of the total amount of sulfur in the deposit, indicating release periods of 250–800 years. Precipitates of Al-hydroxysulfates, well-known from mining sites, were found at the base of the deposits, in streams and also along the ocean shore-line. The effects of added neutralization agents in the deposits and in treatment areas downstream gradually decreased, as indicated by reduced stream pH over time. Active measures are needed to avoid harmful ecological effects in the future

Negative pH, efflorescent mineralogy, and consequences for environmental restoration at the Iron Mountain Superfund site, California

The Richmond Mine of the Iron Mountain copper deposit contains some of the most acid mine waters ever reported. Values of pH have been measured as low as −3.6, combined metal concentrations as high as 200 g/liter, and sulfate concentrations as high as 760 g/liter. Copious quantities of soluble metal sulfate salts such as melanterite, chalcanthite, coquimbite, rhomboclase, voltaite, copiapite, and halotrichite have been identified, and some of these are forming from negative-pH mine waters. Geochemical calculations show that, under a mine-plugging remediation scenario, these salts would dissolve and the resultant 600,000-m(3) mine pool would have a pH of 1 or less and contain several grams of dissolved metals per liter, much like the current portal effluent water. In the absence of plugging or other at-source control, current weathering rates indicate that the portal effluent will continue for approximately 3,000 years. Other remedial actions have greatly reduced metal loads into downstream drainages and the Sacramento River, primarily by capturing the major acidic discharges and routing them to a lime neutralization plant. Incorporation of geochemical modeling and mineralogical expertise into the decision-making process for remediation can save time, save money, and reduce the likelihood of deleterious consequences