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.     

Seasonal DOC accumulation in the Black Sea: a regional explanation for a general mechanism

During three cruises in the Black Sea, organised in July 1995 and April–May 1997, biological and chemical parameters that can influence the carbon budget were measured in the water column on the NW shelf, particularly in the mixing zone with Danube River waters. We observed in early spring (end of April–May) conditions an important input of freshwater organisms that enhanced the microbial activity in the low salinity range. High bacterial activity regenerates nitrogen in the form of nitrates, but is also responsible for an important consumption of ammonium and phosphate, leading to a high N/P ratio and a strong deficit in phosphorus. The consequence is a limitation of phytoplankton development but also a production of carbohydrates that accumulate all along the salinity gradient. These mechanisms are responsible for a seasonal accumulation of dissolved organic carbon (DOC) that increases from 210 μM in winter to about 280 μM in summer. All this excess DOC disappears during winter, probably degraded by bacterial activity. The degradation of carbon-rich organic matter increases the phosphorus demand by bacteria bringing limitation to phytoplankton primary production.     

Lithospheric thickness beneath the southern Kenya Rift: implications from basalt geochemistry

Geochemical data are reported for samples from the flanks and floor of the southern Kenya Rift Valley in the Lake Magadi area, and from two central volcanoes located within the rift valley. Rift lavas include samples of Singaraini and Ol Tepesi basalts on the eastern flank, Kirikiti basalts from the western flank, and plateau trachytes from the rift valley floor. Central volcano samples are from Ol Esayeiti and Lenderut located on the eastern flank. The rift basalts are mildly ne-normative, moderately evolved (Mg#=0.39-0.62) alkali basalts and show an overall range in differentiation. Incompatible trace element abundances are moderately elevated (Nb=17-51; Zr=93-274; La=17-55 ppm) and show strongly coherent variations and constant inter-element ratios (e.g. Zr/Nb=4.2-5.5; Nb/Ta=17.5ǂ.4; (La/Sm)_n=7.3ǃ.1); isotope ratios are restricted in range (⁸⁷Sr/⁸⁶Sr=0.70393-0.70436; ¹⁴³Nd/¹⁴⁴Nd=0.51272-0.51280; ²⁰⁶Pb/²⁰⁴Pb=19.87-19.92; ²⁰⁷Pb/²⁰⁴Pb=15.68-15.70; ²⁰⁸Pb/²⁰⁴Pb=39.56-39.71). Central volcano lavas are more alkaline in character and include basanite (Ol Esayeiti; Mg# >60) and hawaiite to benmoreite (Lenderut; Mg#=0.48-0.38). Incompatible element ratio are similar to those of the rift basalts, although the chondrite normalised REE patterns are steeper (La/Sm)_n=17.4ǃ.2). ⁸⁷Sr/⁸⁶Sr (0.70358, 0.70391), ¹⁴³Nd/¹⁴⁴Nd (0.51280, 0.51267), ²⁰⁶Pb/²⁰⁴Pb (19.96,20.17), ²⁰⁷Pb/²⁰⁴Pb (15.66,15.76) and ²⁰⁸Pb/²⁰⁴Pb (39.80,40.00) ratios of Ol Esayeiti basanites are similar to the rift basalts, whereas the Lenderut lavas have unusually low¹⁴³Nd/¹⁴⁴Nd (0.512388-0.512453) ratios for their ⁸⁷Sr/⁸⁶Sr (0.70370-0.70481) ratios, and distinctly less radiogenic and variable Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb=17.93-19.01; ²⁰⁷Pb/²⁰⁴Pb=15.43-15.58; ²⁰⁸Pb/²⁰⁴Pb=37.91-39.14). An integrated model is developed in which the geochemical signature of the lavas is attributed to variable degrees of melting to depths within the garnet stability field, and in the presence of residual amphibole. The stability fields of these phases in P-T space indicates that the lavas must have formed within the sub-continental lithosphere rather than within the underlying ambient asthenosphere or a rising mantle plume. The subcontinental lithospheric mantle must therefore extend to a depth of at least 75 km beneath the Lake Magadi area, which contrasts with recent gravity models for the area, which infer that lithospheric mantle is absent beneath this section of the southern Kenya Rift.     

Trace-element composition and zoning in clinopyroxene- and amphibole-group minerals: Implications for element partitioning and evolution of carbonatites

The present work is a first comprehensive study of the trace-element composition and zoning in clinopyroxene- and amphibole-group minerals from carbonatites, incorporating samples from 14 localities worldwide (Afrikanda, Aley, Alnö, Blue River, Eden Lake, Huayangchuan, Murun, Oka, Ozernaya Varaka, Ozernyi, Paint Lake, Pinghe, Prairie Lake, Turiy Mys). The new electron-microprobe data presented here significantly extend the known compositional range of clinopyroxenes and amphiboles from carbonatites. These data confirm that calcic and sodic clinopyroxenes from carbonatites are not separated by a compositional gap, instead forming an arcuate trend from nearly pure diopside through intermediate aegirine–augite compositions confined to a limited range of CaFeSi₂O₆ contents (15–45 mol%) to aegirine with < 25 mol% of CaMgSi₂O₆ and a negligible proportion of CaFeSi₂O₆. A large set of LA-ICPMS data shows that the clinopyroxenes of different composition are characterized by relatively low levels of Cr, Co and Ni (≤ 40 ppm) and manifold variations in the concentration of trivalent lithophile and some incompatible elements (1–150 ppm Sc, 26–6870 ppm V, 5–550 ppm Sr, 90–2360 ppm Zr, and nil to 150 ppm REE), recorded in some cases within a single crystal. The relative contribution of clinopyroxenes to the whole-rock Rb, Nb, Ta, Th and U budget is negligible. The major-element compositional range of amphiboles spans from alkali- and Al-poor members (tremolite) to Na–Al-rich Mg- or, less commonly, Fe-dominant members (magnesiohastingsite, hastingsite and pargasite), to calcic–sodic, sodic and potassic–sodic compositions intermediate between magnesio-ferrikatophorite, richterite, magnesioriebeckite, ferri-nyböite and (potassic-)magnesio-arfvedsonite. In comparison with the clinopyroxenes, the amphiboles contain similar levels of tetravalent high-field-strength elements (Ti, Zr and Hf) and compatible transition elements (Cr, Co and Ni), but are capable of incorporating much higher concentrations of Sc and incompatible elements (up to 500 ppm Sc, 43 ppm Rb, 1470 ppm Sr, 1230 ppm Ba, 80 ppm Pb, 1070 ppm REE, 140 ppm Y, and 180 ppm Nb). In some carbonatites, amphiboles contribute as much as 25% of the Zr + Hf, 15% of the Sr and 35% of the Rb + Ba whole-rock budget. Both clinopyroxenes and amphiboles may also host a significant share (~ 10%) of the bulk heavy-REE content. Our trace-element data show that the partitioning of REE between clinopyroxene (and, in some samples, amphibole) and the melt is clearly bimodal and requires a revision of the existing models assuming single-site REE partitioning. Clinopyroxenes and amphiboles from carbonatites exhibit a diversity of zoning patterns that cannot be explained exclusively on the basis of crystal chemistry and relative compatibility of different trace-element in these minerals. Paragenetic analysis indicates that in most cases, the observed zoning patterns develop in response to removal of selected trace elements by phases co-precipitating with clinopyroxene and amphibole (especially magnetite, fluorapatite, phlogopite and pyrochlore). With the exception of magnesiohastingsite–richterite sample from Afrikanda, the invariability of trace-element ratios in the majority of zoned clinopyroxene and amphibole crystals implies that fluids are not involved in the development of zoning in these minerals. The implications of the new trace-element data for mineral exploration targeting REE, Nb and other types of carbonatite-hosted rare-metal mineralization are discussed.     

Review of vibroseis data acquisition and processing for better amplitudes: adjusting the sweep and deconvolving for the time-derivative of the true groundforce

The goal of vibroseis data acquisition and processing is to produce seismic reflection data with a known spatially-invariant wavelet, preferably zero phase, such that any variations in the data can be attributed to variations in geology. In current practice the vibrator control system is designed to make the estimated groundforce equal to the sweep and the resulting particle velocity data are cross-correlated with the sweep. Since the downgoing far-field particle velocity signal is proportional to the time-derivative of the groundforce, it makes more sense to cross-correlate with the time-derivative of the sweep. It also follows that the ideal amplitude spectrum of the groundforce should be inversely proportional to frequency. Because of non-linearities in the vibrator, bending of the baseplate and variable coupling of the baseplate to the ground, the true groundforce is not equal to the pre-determined sweep and varies not only from vibrator point to vibrator point but also from sweep to sweep at each vibrator point. To achieve the goal of a spatially-invariant wavelet, these variations should be removed by signature deconvolution, converting the wavelet to a much shorter zero-phase wavelet but with the same bandwidth and signal-to-noise ratio as the original data. This can be done only if the true groundforce is known. The principle may be applied to an array of vibrators by employing pulse coding techniques and separating responses to individual vibrators in the frequency domain. Various approaches to improve the estimate of the true groundforce have been proposed or are under development; current methods are at best approximate.     

Kokchetavite: a new potassium-feldspar polymorph from the Kokchetav ultrahigh-pressure terrane

Kokchetavite, a new polymorph of K-feldspar (KAlSi₃O₈), has been identified as micrometer-size inclusions in clinopyroxene and garnet in a garnet-pyroxene rock from the Kokchetav ultrahigh-pressure terrane, Kazakhstan. Kokchetavite has a hexagonal structure with a =5.27(1) Å, c=7.82(1) Å, V=188.09 ų, Z=1, and is found to be associated with phengite + /-cristobalite (or quartz) + siliceous glass ± phlogopite/titanite/calcite/zircon, occurring as multi-phase inclusions in clinopyroxene and garnet. It is concluded that kokchetavite could not be an exsolution phase in host minerals. Instead, it might be metastably precipitated from an infiltrated K-rich melt during rock exhumation. Alternatively, although less likely, kokchetavite might be derived from dehydration of K-cymrite, which, in turn, was formed at high pressures. In either case, kokchetavite is a metastable polymorph of K-feldspar.     

Integrating lysimeter drainage and eddy covariance flux measurements in a groundwater recharge model

Abstract

Field-scale water balance is difficult to characterize because controls exerted by soils and vegetation are mostly inferred from local-scale measurements with relatively small support volumes. Eddy covariance flux and lysimeters have been used to infer and evaluate field-scale water balances because they have larger footprint areas than local soil moisture measurements. This study quantifies heterogeneity of soil deep drainage (D) in four 12.5-m² repacked lysimeters, compares evapotranspiration from eddy covariance (ET_EC) and mass balance residuals of lysimeters (ETwb_Lys), and models D to estimate groundwater recharge. Variation in measured D was attributed to redirection of snowmelt infiltration and differences in lysimeter hydraulic properties caused by surface soil treatment. During the growing seasons of 2010, 2011 and 2012, ETwb_Lys (278, 289 and 269 mm, respectively) was in good agreement with ET_EC (298, 301 and 335 mm). Annual recharge estimated from modelled D was 486, 624 and 613 mm for three calendar years 2010, 2011 and 2012, respectively. In summary, lysimeter D and ET_EC can be integrated to estimate and model groundwater recharge.

Editor D. Koutsoyiannis     

微波消解ICP-AES法测定石油样品中镍钒铝硅

Ni、V、Al、Si是石油的天然组分。其中Ni和V来源于形成石油的原始物质,它们易形成大而复杂的分子,从而使沸点非常高。含Ni和V的化合物在提炼过程中无法蒸馏,不能很经济地从燃料中去除。Ni、V、Al、Si在燃烧时会生成不同的氧化物,沉积在化学反应器(如发动机)的冷却器表面,形成黏着物并引起腐蚀;另外这些元素可能灭活提炼过程中的催化剂。可见,测定Ni、V、Al、Si对于炼油工业非常重要。1仪器样品消解采用奥地利安东帕公司(Anton Paar GmbH)生产的Multiwave 3000微波消解系统,配有8位超高压转子。消解后的样品中痕量元素的分析用Optima 3000电感耦合等离子体发射光     

Impacts of extreme weather on wheat and maize in France: evaluating regional crop simulations against observed data

Extreme weather conditions can strongly affect agricultural production, with negative impacts that can at times be detected at regional scales. In France, crop yields were greatly influenced by drought and heat stress in 2003 and by extremely wet conditions in 2007. Reported regional maize and wheat yields where historically low in 2003; in 2007 wheat yields were lower and maize yields higher than long-term averages. An analysis with a spatial version (10?×?10?km) of the EPIC crop model was tested with regards to regional crop yield anomalies of wheat and maize resulting from extreme weather events in France in 2003 and 2007, by comparing simulated results against reported regional crops statistics, as well as using remotely sensed soil moisture data. Causal relations between soil moisture and crop yields were specifically analyzed. Remotely sensed (AMSR-E) JJA soil moisture correlated significantly with reported regional crop yield for 2002–2007. The spatial correlation between JJA soil moisture and wheat yield anomalies was positive in dry 2003 and negative in wet 2007. Biweekly soil moisture data correlated positively with wheat yield anomalies from the first half of June until the second half of July in 2003. In 2007, the relation was negative the first half of June until the second half of August. EPIC reproduced observed soil dynamics well, and it reproduced the negative wheat and maize yield anomalies of the 2003 heat wave and drought, as well as the positive maize yield anomalies in wet 2007. However, it did not reproduce the negative wheat yield anomalies due to excessive rains and wetness in 2007. Results indicated that EPIC, in line with other crop models widely used at regional level in climate change studies, is capable of capturing the negative impacts of droughts on crop yields, while it fails to reproduce negative impacts of heavy rain and excessively wet conditions on wheat yield, due to poor representations of critical factors affecting plant growth and management. Given that extreme weather events are expected to increase in frequency and perhaps severity in coming decades, improved model representation of crop damage due to extreme events is warranted in order to better quantify future climate change impacts and inform appropriate adaptation responses.