Erratum to: Crystal growth during dike injection of MOR basaltic melts: evidence from preservation of local Sr disequilibria in plagioclase

Profiles of a total of 23 plagioclase crystals erupted within the 1982–1991 and 1993 flows of the Coaxial segment of the Juan de Fuca ridge, the 1996 flow of the North Gorda ridge, and from the Western Volcanic Zone of the ultra-slow spreading Gakkel Ridge, have been studied for variations in major and trace element concentrations. We derive equilibration times for the relatively rapidly diffusing Sr in mid-ocean ridge basalt (MORB) plagioclase crystals of the order of months to a few years in each case. All crystals preserve diffusive disequilibria of strontium and barium. Crystal residence times at MORB magmatic temperatures are thus significantly shorter, of the order of days to a few months at most, precluding prolonged crystal storage in axial magma chambers and instead pointing to rapid crystal growth (up to ~10⁻⁸ cm s⁻¹) and cooling (up to ~1°C h⁻¹) shortly prior to eruption of these samples. Growth of these crystals is therefore inferred to occur almost entirely within oceanic layer 2 during dike injection. Crystals that grew at lower crustal levels or earlier in the differentiation sequence appear to have been excluded from the erupted magmas, as might occur if most of the gabbroic rocks in oceanic layer 3 formed an interlocking crystal framework, with viscosities that are too high to carry earlier formed crystals with the melt. The vertical extent of eruptible, crystal-poor melt lenses within the gabbroic zone is constrained to ~1 m or less by considering the width of local equilibrium growth zones, equilibration times, and crystal settling velocities. This lengthscale is consistent with field evidence from ophiolites. Finally, crystal aggregates within the Gakkel ridge sample studied here are the result of synneusis within the propagating dike during melt ascent.     

Silicon isotopes in allophane as a proxy for mineral formation in volcanic soils

Weathering of basaltic ash in volcanic areas produces andosols, rich in allophane and ferrihydrite. Since the rate of mineral formation is very useful in climate and geochemical modelling, this study investigates Si isotope compositions of allophane as a proxy for mineral formation. Allophane formed in contrasting conditions in five Icelandic soil profiles displays silicon isotope signatures lighter than the basalt in less weathered soils (?0.64 ± 0.15‰), and heavier in more weathered organic-rich soils (+0.23 ± 0.10‰). The fate of the dissolved Si in those volcanic soils strongly depends on Al availability. In organic-rich soils, most of Al is humus-complexed, and the results support that Si precipitates as opaline silica by super-saturation, leaving an isotopically heavier dissolved Si pool to form allophane with uncomplexed Al. This study highlights that Si isotopes can be useful to record successive soil processes involved in mineral formation, which is potentially useful in environmental paleo-reconstruction.     

GEMSFIT: a generic fitting tool for geochemical activity models

GEMSFIT, a parallelized open-source tool for fitting thermodynamic activity models has been developed. It is the first open-source implementation of a generic geochemical-thermodynamic fitting tool coupled to a chemical equilibrium solver which uses the direct Gibbs energy minimization (GEM) approach. This enables speciation-based fitting of complex solution systems such as solid solutions and mixed solvents. The extendable framework of GEMSFIT provides a generic interface for fitting geochemical activity models at varying system compositions, temperatures and pressures. GEMSFIT provides the most common tools for statistical analysis which allow thorough evaluation of the fitted parameters. The program can receive input of measured data from a PostgreSQL database server or exported spreadsheets. The fitting tool allows for bound, linear, and nonlinear (in)equality-constrained minimization of weighted squared residuals of highly nonlinear systems over a wide temperature and pressure interval only limited by user-supplied thermodynamic data. Results from parameter regression as well as from statistical analysis can be visualized and directly printed to various graphical formats. Efficient use of the code is facilitated by a graphical user interface which assists in setting up GEMSFIT input files. The usage and resulting output of GEMSFIT is demonstrated by results from parameter regression of the extended universal quasichemical aqueous activity model for geothermal brines.     

Sunflower (Helianthus annuus): phytoextraction capacity for heavy metals on a mining-influenced area in Thuringia,Germany

On an uranium-mining-influenced area, sunflowers (Helianthus annuus) were grown on a small-scaled plot. Subsamples of sunflowers were harvested 34, 66, 96, 108, 140, and 170 days after sowing. Contents of Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Th, U, Zn, and rare earth elements (REEs, La–Lu) were determined in the sunflower shoots, as well as total and bioavailable contents of these 25 elements in the soil taken on the day of sowing and after the last harvest. Shoot contents alone were not sufficient to evaluate the extraction capacity of the sunflowers. Instead total extracted masses (product of biomass and element content) had to be calculated. The total extracted mass increased for most of the elements until 140 days after sowing. Bioconcentration factors (BCFs) as ratio between element content in shoot and soil, were calculated for this time to evaluate the phytoextraction efficiency. BCFs ≥1 (relating total soil contents) and thus a very effective extraction was calculated for Cd. The BCFs, based on mobile soil contents, were ≥1 for all elements, except for U and REEs (La–Lu). Consequently, the sunflower is able to extract many elements effectively from the direct harmful soil fraction. To reduce the contents of Cd and Ni down to levels, where the mining-influenced area could be classified as arable land would require 55 and 207 sunflower growth cycles. Although this is quite a long time, the uranium-mining-influenced area could be successively remediated, while growing biofuel crops, without interfering with food production.     

GEM-Selektor geochemical modeling package: revised algorithm and GEMS3K numerical kernel for coupled simulation codes

Reactive mass transport (RMT) simulation is a powerful numerical tool to advance our understanding of complex geochemical processes and their feedbacks in relevant subsurface systems. Thermodynamic equilibrium defines the baseline for solubility, chemical kinetics, and RMT in general. Efficient RMT simulations can be based on the operator-splitting approach, where the solver of chemical equilibria is called by the mass transport part for each control volume whose composition, temperature, or pressure has changed. Modeling of complex natural systems requires consideration of multiphase–multicomponent geochemical models that include nonideal solutions (aqueous electrolytes, fluids, gases, solid solutions, and melts). Direct Gibbs energy minimization (GEM) methods have numerous advantages for the realistic geochemical modeling of such fluid–rock systems. Substantial improvements and extensions to the revised GEM interior point method algorithm based on Karpov’s convex programming approach are described, as implemented in the GEMS3K C/C+?+ code, which is also the numerical kernel of GEM-Selektor v.3 package (http://gems.web.psi.ch). GEMS3K is presented in the context of the essential criteria of chemical plausibility, robustness of results, mass balance accuracy, numerical stability, speed, and portability to high-performance computing systems. The stand-alone GEMS3K code can treat very complex chemical systems with many nonideal solution phases accurately. It is fast, delivering chemically plausible and accurate results with the same or better mass balance precision as that of conventional speciation codes. GEMS3K is already used in several coupled RMT codes (e.g., OpenGeoSys-GEMS) capable of high-performance computing.     

State of geoscientific research within the lorandite experiment (LOREX)

The LORandite EXperiment (acronym LOREX) is the only geochemical solar neutrino experiment still actively persued. The Tl-mineral lorandite, TlAsS₂, occurs in the ore deposit Allchar, Macedonia, close to the border of Greece. The polychronous and polygenetic Sb-As-Tl-Au Allchar deposit was formed by complex physico-chemical processes occurring in a heterogeneous geological environment and by interaction of polyphase hydrothermal fluids with the surrounding magmatic, sedimentary and metamorphic rocks. The genesis of ore mineralization is related to the products of polyphase magmatic activity of Pliocene age (~6.5 to ~1.8?Ma) and its spatial location was controlled by magmatic, structural and lithological factors. The Allchar deposit comprises several orebodies of various shapes, textural-structural characteristics and element associations. Thallium mineralization, which is of significance for the LOREX project, has been proved in two locations: (i) ore body Crven Dol in the northern part and (ii) ore body Centralni Deo in the central part of the Allchar deposit. The age of Tl-mineralization is 4.22?Ma at the Crven Dol locality and 4.31?Ma at Rudina near to the Centralni Deo locality. The present depth of ore mineralization from the present soil surface is about 30?m to 140?m, whereas the paleodepth of its formation is considerably bigger. Using the method of quantitative geomorphological analysis, and AMS- and MS-measurements of cosmogenic radionuclides ²⁶Al, ²¹Ne, and ³He, the erosion rate has been established to be ~70?m/Ma in the broader area of the Crven Dol locality and ~130?m/Ma in the Centrani Deo of the Allchar deposit. On the basis of these erosion rates and ages of Tl-mineralization, we have calculated the paleo-depth of Lorandite to be ca 180?m?±?35?m to 420?m?±?80?m. Geochemical and mineralogical investigations on lorandite in particular its trace elements (Pb, U, and Th), the quantity of lorandite in the two ore bodies, the geological age and the paleo depth of Tl-mineralization have provided encouraging results and indicate the feasibility of the LOREX project.     

Hydrogeology of the Kabul Basin (Afghanistan), part II: groundwater geochemistry

Shallow groundwater is the main source for drinking water in Kabul, Afghanistan. It comes from a multitude of shallow hand-pumped wells spread over the whole city area. The groundwater is characterised by slightly oxic redox conditions. Interactions with aquifer carbonates lead to near-neutral pH and high degrees of hardness. The mostly negative water budget of the Kabul Basin is the result of strong evaporation which leads to an increase in salt and also of some undesirable constituents, e.g. borate. Several years of drought have aggravated this problem. The shallow groundwater in the city has received tremendous amounts of pollution due to a lack of proper waste disposal and sewage treatment. Common indicators are elevated concentrations of nutrients such as nitrate and faecal bacteria. The high infant mortality can at least partially be attributed to the insufficient water hygiene. Acid generated during the mineralisation of the wastewater is hidden due to the strong pH buffering capacity of the groundwater system. Redox and pH conditions preclude significant mobilisation of trace metals and metalloids.