Calcium isotope (δCa) fractionation along hydrothermal pathways, Logatchev field (Mid-Atlantic Ridge, 14°45′N)

We investigate the Logatchev Hydrothermal Field at the Mid-Atlantic Ridge, 14°45′N to constrain the calcium isotope hydrothermal flux into the ocean. During the transformation of seawater to a hydrothermal solution, the Ca concentration of pristine seawater ([Ca]_SW) increases from about 10 mM to about 32 mM in the hydrothermal fluid endmember ([Ca]_HydEnd) and thereby adopts a δ^44/40Ca_HydEnd of −0.95 ± 0.07‰ relative to seawater (SW) and a ⁸⁷Sr/⁸⁶Sr isotope ratio of 0.7034(4). We demonstrate that δ^44/40Ca_HydEnd is higher than that of the bedrock at the Logatchev field. From mass balance calculations, we deduce a δ^44/40Ca of −1.17 ± 0.04‰ (SW) for the host-rocks in the reaction zone and −1.45 ± 0.05‰ (SW) for the isotopic composition of the entire hydrothermal cell of the Logatchev field. The values are isotopically lighter than the currently assumed δ^44/40Ca for Bulk Earth of −0.92 ± 0.18‰ (SW) [Skulan J., DePaolo D. J. and Owens T. L. (1997) Biological control of calcium isotopic abundances in the global calcium cycle. Geochim. Cosmochim. Acta61,(12) 2505-2510] and challenge previous assumptions of no Ca isotope fractionation between hydrothermal fluid and the oceanic crust [Zhu P. and Macdougall J. D. (1998) Calcium isotopes in the marine environment and the oceanic calcium cycle. Geochim. Cosmochim. Acta62,(10) 1691-1698; Schmitt A. -D., Chabeaux F. and Stille P. (2003) The calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance. Earth Planet. Sci. Lett. 6731, 1-16]. Here we propose that Ca isotope fractionation along the fluid flow pathway of the Logatchev field occurs during the precipitation of anhydrite. Two anhydrite samples from the Logatchev Hydrothermal Field show an average fractionation of about Δ^44/40Ca = −0.5‰ relative to their assumed parental solutions. Ca isotope ratios in aragonites from carbonate veins from ODP drill cores indicate aragonite precipitation directly from seawater at low temperatures with an average δ^44/40Ca of −1.54 ± 0.08‰ (SW). The relatively large fractionation between the aragonite precipitates and seawater in combination with their frequent abundance in weathered mafic and ultramafic rocks suggest a reconsideration of the marine Ca isotope budget, in particular with regard to ocean crust alteration.     

Phytoreduction and volatilization of mercury by ascorbate in Arabidopsis thaliana, European beech and Norway spruce

Mercury vapor (Hg⁰) emission from plants contributes to the atmospheric Hg cycle. Young barley (Hordeum vulgare L.) plants grown on a hydroponic cultivation medium containing Hg(II) have previously been shown to increase their Hg⁰ emission significantly by reduction of Hg(II) with endogenous ascorbic acid. Regarding the potential contribution to the Hg cycle from the vast forest-covered areas, it was important to investigate this mechanism in trees. The increase in Hg⁰ emission from young European beech plants cultivated on a HgCl₂ medium exceeded that from controls by ca. tenfold and was proportional to the Hg(II) concentration. From these experiments, a flux of 12.8 μg Hg⁰/h/m² was estimated at an exposure of the roots to 20 μM Hg(II). Mercury vapor release from homogenates of Norway spruce needles exceeded that from European beech leaves by a factor of 2.3–4, i.e. in proportion to the reported AA concentrations; the reduction was maximal at alkaline pH which is typical for AA. The 8.4-fold difference in Hg⁰ release between homogenates from wild-type Arabidopsis thaliana and from its AA-deficient mutant vtc 1-1 also paralleled the reported difference in AA levels of both species. It is concluded that the phytoreduction and vaporization of Hg by AA is an important mechanism as much for Hg detoxification in trees as for Hg emission to the atmosphere. The efficiency of this process seems to result from the optimal coordination of transfer and biochemical transformation of mercuric ions and Hg vapor. There is no evidence for a relevant difference in the mechanisms of biogenic Hg(II) reduction between grass plants and trees.     

The hydrochemistry of a semi-arid pan basin case study: Sua Pan,Makgadikgadi, Botswana

This study presents results on the fluid and salt chemistry for the Makgadikgadi, a substantial continental basin in the semi-arid Kalahari. The aims of the study are to improve understanding of the hydrology of such a system and to identify the sources of the solutes and the controls on their cycling within pans. Sampling took place against the backdrop of unusually severe flooding as well as significant anthropogenic extraction of subsurface brines. This paper examines in particular the relationship between the chemistry of soil leachates, fresh stream water, salty lake water, surface salts and subsurface brines at Sua Pan, Botswana with the aim of improving the understanding of the system’s hydrology. Occasionally during the short wet season (December–March) surface water enters the saline environment and precipitates mostly calcite and halite, as well as dolomite and traces of other salts associated with the desiccation of the lake. The hypersaline subsurface brine (up to TDS 190,000 mg/L) is homogenous with minor variations due to pumping by BotAsh mine (Botswana Ash (Pty) Ltd.), which extracts 2400 m³ of brine/h from a depth of 38 m. Notable is the decrease in TDS as the pumping rate increases which may be indicative of subsurface recharge by less saline water. Isotope chemistry for Sr (⁸⁷Sr/⁸⁶Sr average 0.722087) and S (δ³⁴S average 34.35) suggests subsurface brines have been subject to a lithological contribution of undetermined origin. Recharge of the subsurface brine from surface water including the Nata River appears to be negligible.     

Weed species diversity on arable land of the dryland areas of central Tanzania: impacts of continuous application of traditional tillage practices

This paper presents findings from a study that assessed influence of continuous application of a particular traditional tillage practice on weed species richness, diversity and composition and identifies weed species with positive benefits to the communities in semi-arid areas of Mpwapwa district, central Tanzania. In this area farmers apply three different traditional tillage practices which are no-till (NT), shallow tillage (ST) and Ridging System (RT). A total of 36 farm fields were surveyed in 2006/2007 cropping season where 63 weed species from 26 families were identified. Analysis of variance indicated significant differences between practices (p < 0.05), with NT practice having highest weed species richness and diversity. Among the five more prevalent weed species appearing, Bidens lineariloba was observed to exist in all the three practices. Community representatives during focus group discussions indicated 9 weed species out of 63 identified to have beneficial uses. These species are Cleome hirta, Amaranthus graecizans, Bidens lineoriloba, Bidens pilosa, Dactyloctenium aegyptium, Launaea cornuta, Heteropogon contortus, Tragus berteronianus and Trichodesma zeylanicum. Their main uses include leaf-vegetable, medicines, fodder and materials for thatching. From this study NT has highest weed species richness and diversity which therefore suggests that much more time is needed for weeding in this practice compared to other practice which was the farmers’ concern. It was also noted that although weed species have negative effects in crop production and production costs, they still play a vital role in food security and for the health of different people in marginal areas as well as for the complete ecosystem including micro and macrofauna.     

Detection of free vertical convection and double-diffusion in groundwater monitoring wells with geophysical borehole measurements

Two algorithms for in-situ detection and identification of vertical free convective and double-diffusive flows in groundwater monitoring wells or boreholes are proposed. With one algorithm the causes (driving forces) and with the other one the effects (convection or double-diffusion) of vertical transport processes can be detected based on geophysical borehole measurements in the water column. Five density-driven flow processes are identified: thermal, solutal, and thermosolutal convection leading to an equalization, as well as saltfingers and diffusive layering leading to an intensification of a vertical density gradient. The occurrence of density-driven transport processes could be proven in many groundwater monitoring wells and boreholes; especially shallow sections of boreholes or groundwater monitoring wells are affected dramatically by such vertical flows. Deep sections are also impaired as the critical threshold for the onset of a density-driven flow is considerably low. In monitoring wells or boreholes, several sections with different types of density-driven vertical flows may exist at the same time. Results from experimental investigations in a medium-scale testing facility with high aspect ratio (height/radius = 19) and from numerical modeling of a water column agree well with paramters of in-situ detected convection cells.     

Discussion of the Möller radiation chart

Summary M?ller's assumptions for the carbon dioxide-water vapor overlap region, which lead to the construction of his radiation chart, are reinvestigated in the light of modern theory. A new radiation chart, taking into account the carbon dioxide-water vapor overlap, is constructed using water vapor and carbon dioxide absorption data as furnished byM?ller andElsasser respectively. The results of the radiative fluxes computed from the new chart are compared with equivalent results using the original M?ller and the revised Elsasser radiation diagrams, as well as with measurements.

---

Zusammenfassung Die Berechtigung derM?llerschen Annahme zur getrennten Behandlung von Kohlens?ure- und Wasserdampfabsorption zwecks Konstruktion eines atmosph?rischen Strahlungsdiagrammes wird im Lichte der modernen Theorie diskutiert. Ein neues Strahlungspapier wird vorgelegt, das die gleichzeitige Anwesenheit von Kohlens?ure und Wasserdampf im gleichen Spektralbereich berücksichtigt. Dieses beruht auf Wasserdampf- und Kohlens?uredaten, die vonM?ller undElsasser vorgegeben wurden. Nach dem neuen Strahlungsdiagramm berechnete Werte werden mit Me?werten und theoretischen Werten verglichen, die mit dem ursprünglichen M?llerschen und mit dem verbesserten Elsasserschen Strahlungspapier ermittelt wurden.

---

Résumé Au vu des théories modernes, on discute l'hypothèse formulée parM?ller et sa justification, hypothèse selon laquelle il est nécessaire de traiter séparément l'absorption du dioxyde de carbone et celle de la vapeur d'eau lors de l'établissement d'un diagramme du rayonnement atmosphérique. On propose alors un nouvel abaque qui tient compte de la présence simultanée du dioxyde de carbone et de la vapeur d'eau dans la même région spectrale. Cet abaque s'appuie sur les valeurs données parM?ller et parElsasser, valeurs valables pour ces deux gaz. On compare le résultat de calculs effectués avec ce nouvel abaque à des mesures et à des valeurs théoriques ces dernières étant basées tant sur les travaux originaux deM?ller que sur l'abaque amélioré deElsasser.

---

---

With 4 Figures     

The volcano-magnetic effect

Summary A geometrically simple volcano is considered, havig a spherical magma chamber of 2.5 km radius centred at 10 km depth. The Curie point isotherm is assumed to be a plane at 20 km depth, except for the spherical volume which is also non-magnetic. The stress pattern in the vicinity of the spherical chamber, due to regional stress of sufficient intensity to cause an eruptions, is used to calculate the change in magnetization which results from the piezomagnetic effect through the volume of solid rock. The consequent magnetic field anomaly at the surface is then obtaied by numerical integration of the dipole law of force over the stressed volume. For rocks of the type found on the volcanic island of St. Vincent (West Indies), this model gives a maximum local volcano-magnet c effect of about 7 gammas.     

Trace element diagenesis in pyrite-rich sediments of the Achterwasser lagoon, SW Baltic Sea

The early diagenesis of trace elements (V, Cr, Co, Cu, Zn, As, Cd, Ba, U) in anoxic sediments of the Achterwasser, a shallow lagoon in the non-tidal Oder estuary in the Baltic Sea, was investigated in the context of pyrite formation. The dissolved major redox parameters show a two-tier distribution with transient signals in the occasionally re-suspended fluid mud layer (FM) and a permanently established diagenetic sequence in the sediment below. Intense microbial respiration leads to rapid depletion of O₂ within the uppermost mm of the FM. The reduction zones of Mn, Fe and sulfate overlap in the FM and in the permanently anoxic sediment section which appears to be a typical feature of estuarine sediments, under low-sulfate conditions. Degrees of pyritization (DOP) range from 50% in the FM to remarkably high values > 90% at 50 cm depth. Pyrite formation at the sediment surface is attributed to the reaction of Fe-monosulfides with intermediate sulfur species via the polysulfide pathway. By contrast, intense pyritization in the permanently anoxic sediment below is attributed to mineral growth via adsorption of aqueous Fe-sulfide complexes onto pyrite crystals which had originally formed in the surface layer.The studied trace elements show differential behavior patterns which are closely coupled to the diagenetic processes described above: (i) Zn, Cu and Cd are liberated from organic matter in the thin oxic layer of the sediment and diffuse both upwards across the sediment/water boundary and downwards to be trapped as monosulfides, (ii) V, Cr, Co and As are released during reductive dissolution of Mn- and Fe-oxyhydroxides, (iii) U removal from pore water occurs concomitantly to Fe reduction in the FM and is attributed to reduction of U(VI) to U(IV), (iv) the Ba distribution is controlled by reductive dissolution of authigenic barite in the sulfate reduction zone coupled with upward diffusion and re-precipitation. The incorporation of trace elements into pyrite is most intense for Co, Mn and As, intermediate for Cu and Cr and little to negligible for U, Zn, Cd, V and Ba. The observed trend is largely in agreement with previous studies and may be explained with differing rates for ligand exchange. Slow and fast ligand exchange and thus precipitation kinetics are also displayed by downcore increasing (Mn, Cr, Co and As) or constantly low (Zn, Cu, Cd) pore water concentrations. The downward increasing degrees of trace metal pyritization (DTMP) for Co, Cu, Zn and As are, in analogy to pyrite growth, assigned to adsorption of sulfide complexes or As oxyanions onto preexisting pyrite minerals.     

Properties of structure and function of cadmium-binding proteins/peptides from Euglena gracilis

Euglena gracilis makes two small Cd-binding proteins/peptides (Cd-BP I and Cd-BP II) in response to exposure to Cd²⁺. These proteins migrate slower than mammalian Cd-metallothionein (Cd-Mt) through Sephadex G-75, but like Cd-Mt also contain Zn and are separated into two species when chromatographed over a DEAE column. Both BPs are much less stable than Cd-Mt under acidic conditions. One source of this instability is that at least Cd-BP II contains acid-labile sulfide co-ordinated to the metals. It has been quantitated in Cd-BP II and shown to have a value of 1·25 ± 0·10 S²⁻/Cd. The reactivity of the Cd-binding sites in ligand substitution and thioldisulfide exchange reactions has been assessed. The reactions of Cd-BP I and II with pyridylazoresorcinol (PAR) were slow and displayed complex kinetic behavior. Similarly, both Cd-BPs react slowly and with complicated kinetics with 5,5′-dithiobis-(2-nitrobenzoate).