An electrochemical study of Ni2+, Co2+, and Zn2+ ions in melts of composition CaMgSi2O6

Cyclic voltammetry has been done for Ni²⁺, Co²⁺, and Zn²⁺ in melts of diopside composition in the temperature range 1425 to 1575°C. Voltammetric curves for all three ions excellently match theoretical curves for uncomplicated, reversible charge transfer at the Pt electrode. This implies that the neutral metal atoms remain dissolved in the melt. The reference electrode is a form of oxygen electrode. Relative to that reference assigned a reduction potential of 0.00 volt, the values of standard reduction potential for the ions are $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.32 ± .01}\text{V}$, $\text{E}{}^1\text{(}\text{Co}{}^{\mathrm{2+}}\text{Co}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.45 ± .02}\text{V}$, and $\text{E}{}^1\text{(}\text{Zn}{}^{\mathrm{2+}}\text{Zn}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.53 ± .01}\text{V}$. The electrode reactions are rapid, with first order rate constants of the order of 10^?2 cm/sec. Diffusion coefficients were found to be 2.6 × 10^?6 cm²/sec for Ni²⁺, 3.4 × 10^?6 cm²/sec for Co²⁺, and 3.8 × 10^?6 cm²/sec for Zn²⁺ at 1500°C. The value of $\text{E1}$ ($\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0$, diopside) is a linear function of temperature over the range studied, with values of ?0.35 V at 1425°C and ?0.29 V at 1575°C. At constant temperature the value of $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{, 1525°C}$) was not observed to vary with composition over the range CaO · MgO · 2SiO₂ to CaO·MgO·3SiO₂ or from 1.67 CaO·0.33MgO·2SiO₂ to 0.5 CaO·1.5MgO·2SiO₂. The value for the diffusion coefficient for Ni²⁺ decreased by an order of magnitude at 1525°C over the compositional range CaO · MgO · 1.25SiO₂ to CaO · MgO · 3SiO₂. This is consistent with a mechanism by which Ni²⁺ ions diffuse by moving from one octahedral coordination site to another in the melt, with the same Ni²⁺ species discharging at the cathode regardless of the SiO₂ concentration in the melt.     

Seismic coupling and uncoupling at subduction zones

Seismic coupling has been used as a qualitative measure of the “interaction” between the two plates at subduction zones. Kanamori (1971) introduced seismic coupling after noting that the characteristic size of earthquakes varies systematically for the northern Pacific subduction zones. A quantitative global comparison of many subduction zones reveals a strong correlation of earthquake size with two other variables: age of the subducting lithosphere and convergence rate. The largest earthquakes occur in zones with young lithosphere and fast convergence rates, while zones with old lithosphere and slow rates are relatively aseismic for large earthquakes. Results from a study of the rupture process of three great earthquakes indicate that maximum earthquake size is directly related to the asperity distribution on the fault plane (asperities are strong regions that resist the motion between the two plates). The zones with the largest earthquakes have very large asperities, while the zones with smaller earthquakes have small scattered asperities. This observation can be translated into a simple model of seismic coupling, where the horizontal compressive stress between the two plates is proportional to the ratio of the summed asperity area to the total area of the contact surface. While the variation in asperity size is used to establish a connection between earthquake size and tectonic stress, it also implies that plate age and rate affect the asperity distribution. Plate age and rate can control asperity distribution directly by use of the horizontal compressive stress associated with the “preferred trajectory” (i.e. the vertical and horizontal velocities of subducting slabs are determined by the plate age and convergence velocity). Indirect influences are many, including oceanic plate topography and the amount of subducted sediments.All subduction zones are apparently uncoupled below a depth of about 40 km, and we propose that the basalt to eclogite phase change in the down-going oceanic crust may be largely responsible. This phase change should start at a depth of 30–35 km, and could at least partially uncouple the plates by superplastic deformation throughout the oceanic crust during the phase change.     

Long internal waves in shear flows: topographic resonance and wave-induced global instability

Issues pertaining to a mechanism whereby long internal waves in shallow seas may give rise to enhanced rates of resuspension of sedimentary material are addressed. The proposed mechanism is intimately related to the creation of conditions in the bottom boundary layer which are favorable for flow separation and spontaneous onset of global instability. It is shown that long waves generated by topographic resonance and propagating upstream against the oncoming current, especially a sheared current, have a strong tendency to release a coherent, pulsating dynamics in their footprint. The passage-through-resonance problem for a sheared, stratified flow is considered, conditions for topographic resonance in the flow model are defined, and preliminary results for the unsteady dynamics in the boundary layer under the footprint of a long wave packet are presented.     

Water status in winter wheat grown under salt stress

1 IntroductionSalinization is one of the major problems in arid and semi-arid regions in relation to land use and in particular to agricultural production[1]. Excessive salinity leads to toxicity in crops and reduction of the availability of water to crops, by reducing the osmotic potential of the soil solution[2]. Movement of soil water induces solute transport, and solutes are transferred towards the ground surface by the upward soil-water movement caused by evaporation, resulting in an accu…     

Dissolution of well and poorly ordered kaolinites by an aerobic bacterium

Previous research by our group (e.g., [Chem. Geol. 132 (1996) 25; Geochim. Cosmochim. Acta 64 (2000) 1363]) has shown that an aerobic Pseudomonas mendocina bacterium enhances Fe(hydr)oxide dissolution in order to obtain Fe under Fe-limited conditions. The P. mendocina is incapable of utilizing Fe as a terminal electron acceptor and requires several orders of magnitude lower Fe concentrations than do dissimilatory Fe reducing bacteria. The research reported here compared the effects of the P. mendocina on dissolution of well and poorly ordered Clay Minerals Society Source Clay kaolinites KGa-1b and KGa-2, respectively, under Fe-limited conditions. KGa-1b and KGa-2 contain 0.04 and 0.94 bulk wt.% Fe, respectively, and their surface Fe/Si atomic RATIOS=0.008 and 0.012. Following strong cleaning of the kaolinites in 5.8 M HCl at 85 °C, the surface Fe/Si atomic ratios decreased to 0.004 and 0.008, respectively. Both kaolinites also developed a Si-enriched surface precipitate upon strong cleaning.

Because the P. mendocina take up Fe, we could not measure Fe release from the kaolinite directly, but rather had to monitor it indirectly by comparing microbial populations sizes under Fe-limited growth conditions. We found that microbial growth on uncleaned, weakly cleaned, and strongly cleaned kaolinites increased with the amount of Fe readily available to organic ligands as estimated by dissolution in 0.001 M oxalate (pH 3). This suggests that it is the amount of readily accessible Fe that controls Fe acquisition and hence microbial growth. The trend is based on only a relatively small range of kaolinite Fe contents, and the research thus needs to be expanded to include kaolinites with a broader range of bulk and surface Fe concentrations.

Significant enhancement of Al release was observed in the presence of the bacteria, along with generally some enhancement of Si release. This enhancement of kaolinite dissolution could be related to an observed pH increase from 7–8 to 9 in the presence of the bacteria and/or to production of Al chelating agents. The P. mendocina produce a variety of organic exudates, including siderophores [Chem. Geol. 132 (1996) 25; Geomicrobiology (2001b)], and further studies into the effects of the siderophores on Al complexation and on kaolinite dissolution are ongoing.     

Sampling for Purgeable Organic Compounds Using Positive-Displacement Piston and Centrifugal Submersible Pumps: A Comparative Study

Positive-displacement piston pumps that minimize sample agitation have no apparent advantage over centrifugal submersible pumps when used to collect ground water samples for analysis of low concentrations of purge-able organic compounds. Analytical uncertainties inherent in laboratory environments appear to influence analytical results of low-concentration purgeable organic compound samples more than either pump type or sampling team. Centrifugal submersible pumps are at least equally efficient as positive-displacement piston pumps in the recovery of carbon tetrachloride, 1,1,1-trichloroethane, trichloroethylene, and chloroform after sampling and analytical influences are made constant.     

Major and trace elements in igneous rocks from apollo 15

The concentrations of major and trace elements have been determined in igneous rocks from Apollo 15. All materials analyzed have typical depletions of Eu except for minerals separated from sample 15085. Four samples have concentrations of trace elements that are similar to those of KREEP. The samples of mare basalt from Apollo 15 have higher concentrations of FeO, MgO, Mn, and Cr and lower concentrations of CaO, Na₂O, K₂O, and rare-earth elements (REE) as compared to the samples of mare basalt from Apollos 11, 12, and 14. The samples can be divided into two groups on the basis of their normative compositions. One group is quartz normative and has low concentrations of FeO while the other is olivine normative and has high concentrations of FeO. The trace element data indicate that the samples of olivine normative basalt could be from different portions of a single lava flow. At least two and possible three parent magmas can be identified from the samples of the quartz normative group on the basis of their concentration ratios of Sm to Eu. Within each group, the compositions of the samples appear to be related by crystallization of olivine or pyroxene. Significant variations of the ratio of concentration of Sm to Eu cannot be produced without plagioclase-liquid equilibrium. The source material of mare basalt may be depleted in Eu. Alternatively, the magmas may have assimilated a small volume of material similar to KREEP.Paper dedicated to Prof. Harold C. Urey on the occasion of his 80th birthday on 29 April 1973.     

Regional-scale hydrothermal alteration in the Central Blake River Group,western Abitibi subprovince,Canada: implications for VMS prospectivity

The Late Archean Blake River Group is a thick succession of predominantly mafic volcanic rocks within the southern zone of the Abitibi greenstone belt. It contains a number of silicic volcanic centers of different size, including the large Noranda volcanic complex, which is host to 17 past-producing volcanogenic massive sulfide deposits. The Noranda complex consists of a 7- to 9-km-thick succession of bimodal mafic and felsic volcanic rocks erupted during five major cycles of volcanism. Massive sulfide formation coincided with a period of intense magmatic activity (cycle III) and the formation of the Noranda cauldron. Hydrothermal alteration in these rocks is interpreted to reflect large-scale hydrothermal fluid flow associated with rapid crustal extension and rifting of the volcanic complex. The alteration includes abundant albite, chlorite, epidote and quartz (silicification), which exhibit broad stratigraphic and structural control and correlate with previously mapped whole-rock oxygen isotope zonation. The Mine Sequence volcanic rocks are characterized by abundant iron-rich chlorite (Fe/Fe+Mg >0.5), hydrothermal amphibole (ferroactinolite) and coarse-grained epidote of clinozoisite composition (<10 wt% Fe ₂O ₃). Volcanic rocks of the pre-cauldron sequences, which contain only subeconomic stringer mineralization, are characterized by less abundant chlorite and mainly fine-grained epidote (>10 wt% Fe ₂O ₃) lacking the clinozoisite solid solution. Alteration in the Mine Sequence volcanic rocks persists along strike well beyond the limits of the main ore deposits (as far as several tens of kilometers) and can be readily distinguished from greenschist facies metamorphic assemblages at a regional scale. The lack of similar alteration in the pre-cauldron sequences is consistent with limited ¹⁸O-depletion and suggests that the early history of the volcanic complex did not support large-scale, high-temperature fluid flow in these rocks. Comparisons with a much smaller, barren volcanic complex in nearby Ben Nevis township reveal important differences in the alteration mineralogy between volcanoes of different size, with implications for area selection during regional-scale mineral exploration. The Ben Nevis Complex consists of a 3- to 4-km-thick succession of mafic, intermediate and felsic volcanic rocks centered on a small subvolcanic intrusion. Alteration of the volcanic rocks comprises mainly low-temperature assemblages of prehnite, pumpellyite, magnesium-rich chlorite (Fe/Fe+Mg <0.5), iron-rich epidote (>10 wt% Fe ₂O ₃) and calcite. Actinolite ± magnetite alteration occurs proximal to the intrusive core of the complex, but the limited extent of this alteration indicates only local high-temperature fluid circulation adjacent to the intrusion. A distal zone of carbonate alteration is located 4–6 km from the center of the volcano. Although iron-bearing carbonates are present locally within this zone, the absence of siderite argues against a high-temperature origin for this alteration. These observations do not offer positive encouragement for the existence of a fossil geothermal system of sufficient size or intensity to have produced a large massive sulfide deposit.     

Paleohydrology of Andean saline lakes from sedimentological and isotopic records, Northwestern Argentina

The paleohydrological evolution of several high altitude, saline lakes located in the southernmost Altiplano (El Peinado and San Francisco basins, Catamarca province, NW Argentina) was reconstructed applying sedimentological, geochemical and isotopic techniques. Several playa lakes from the San Francisco basin (26° 56 S; 68° 08 W, 3800-3900 m a.s.l.) show evidence of a recent raise in the watertable that led to modern deposition of carbonate and diatomaceous muds. A 2 m - long core from El Peinado Lake (26° 29 59 S, 68°05 32 W, 3820 m a.s.l.) consists of calcitic crusts (unit 3), overlaid by an alternation of macrophyte-rich and travertine clast- rich, laminated muds (unit 2), and topped by travertine facies (unit 1). This sedimentary sequence illustrates a paleohydrological evolution from a subaerial exposure (unit 3) to a high lake stand (unit 2), and a subsequent smaller decrease in lake level (unit 1). The ¹³C_{organic matter}record also reflects the lake transgression between units 3 and 2. Although there is a general positive correlation between ¹⁸O_carbonate and salinity proxies (Na, Li and B content), the large data dispersion indicates that other factors besides evaporation effects control chemical and isotopic composition of lakewater. Consequently, the oxygen isotopic composition cannot be interpreted exclusively as an indicator of salinity or evaporation ratio. The degassing of CO₂ during groundwater discharge can explain the enriched ¹³C values for primary carbonates precipitated. The carbon budget in these high altitude, saline lakes seems to be controlled by physical rather than biological processes.The Altiplano saline lakes contain records of environmental and climatic change, although accurate ¹⁴C dating of these lacustrine sediments is hindered by the scarcity of terrestrial organic material, and the large reservoir effects. Sedimentologic evidence, a ²¹⁰Pb-based chronology, and a preliminary U/Th chronology indicate a very large reservoir effect in El Peinado, likely as a result of old groundwaters and large contributions of volcanic and geothermal ¹⁴C-free CO₂ to the lake system. Alternative chronologies are needed to place these paleorecords in a reliable chronological framework. A period of increased water balance in the San Francisco basin ended at about 1660 ± 82 yr B.P. (calendar yr U/Th age), and would correlates with the humid phase between 3000 and 1800 yr B.P detected in other sites of the southern Altiplano. Both, ²¹⁰Pb and preliminary U/Th dating favor a younger age for the paleohydrological changes in El Peinado. The arid period reflected by subaerial exposure and low lake levels in unit 3 would have ended with a large increase in effective moisture during the late 17th century. The increased lake level during deposition of unit 2 would represent the period between AD1650 - 1900, synchronous to the Little Ice Age. This chronological framework is coherent with other regional records that show an abrupt transition from more arid to more humid conditions in the early 17th century, and a change to modern conditions in the late 19th century. Although there are local differences, the Little Ice Age stands as a significant climatic event in the Andean Altiplano.     

Ferrihydrite dissolution by pyridine-2,6-bis(monothiocarboxylic acid) and hydrolysis products

Pyridine-2,6-bis(monothiocarboxylate) (pdtc), a metabolic product of microorganisms, including Pseudomonas putida and Pseudomonas stutzeri was investigated for its ability of dissolve Fe(III)(hydr)oxides at pH 7.5. Concentration dependent dissolution of ferrihydrite under anaerobic environment showed saturation of the dissolution rate at the higher concentration of pdtc. The surface controlled ferrihydrite dissolution rate was determined to be 1.2 × 10⁻⁶ mol m⁻² h⁻¹. Anaerobic dissolution of ferrihydrite by pyridine-2,6-dicarboxylic acid or dipicolinic acid (dpa), a hydrolysis product of pdtc, was investigated to study the mechanism(s) involved in the pdtc facilitated ferrihydrite dissolution. These studies suggest that pdtc dissolved ferrihydrite using a reduction step, where dpa chelates the Fe reduced by a second hydrolysis product, H₂S. Dpa facilitated dissolution of ferrihydrite showed very small increase in the Fe dissolution when the concentration of external reductant, ascorbate, was doubled, suggesting the surface dynamics being dominated by the interactions between dpa and ferrihydrite. Greater than stoichiometric amounts of Fe were mobilized during dpa dissolution of ferrihydrite assisted by ascorbate and cysteine. This is attributed to the catalytic dissolution of Fe(III)(hydr)oxides by the in situ generated Fe(II) in the presence of a complex former, dpa.