Biogeochemical impact of a model western iron source in the Pacific Equatorial Undercurrent

Trace element distributions in the source waters of the Pacific Equatorial Undercurrent (EUC) show the existence of elevated total acid-soluble iron concentrations. This region has been suggested to contribute enough bioavailable iron to regulate interannual and interglacial variability in biological productivity downstream in the high-nitrate low-chlorophyll upwelling zone of the eastern equatorial Pacific. We investigated the advection and first-order biogeochemical impact of an imposed, data-based iron maximum in the western Pacific EUC using an ecosystem model forced by a global dynamical model. We imposed two source profiles of iron constrained by total acid-soluble iron measurements. Though the data for total acid-soluble iron included both dissolved and acid-soluble particulate iron species, we treated all of the total acid-soluble iron as if it was dissolved and bioavailable. A deeper (270 m) source was centered in the density horizon of the observed iron maximum and a shallower (180 m) source was located in the core of our model's EUC, where a dissolved iron maximum has been frequently postulated. These source runs were compared with a control run that contained no specific source of iron associated with the EUC. In the source runs elevated iron concentrations were simulated in the EUC across its entire zonal span, evident as a subsurface plume of dissolved iron slightly below the core of the EUC. In the control run there was no iron maximum associated with the EUC. Upwelling of iron-replete water in the central and eastern equatorial Pacific increased integrated primary productivity in the Wyrtki box (180°W:90°W, 5°S:5°N, 0:200 m) by 41% and 66% for the deeper and shallower iron perturbation, respectively. The source runs increased the realism of the zonal extent of HNLC conditions and the meridional distributions of biological productivity, relative to the control run. However, in the source simulations surface chlorophyll concentrations were too high by a factor of two and maximum surface nitrate concentrations were too low, relative to climatologies. The relative abundance of diatoms roughly doubled upon the input of additional iron, exceeding field observations. Though biogeochemical data are limited and we did not adjust parameters to optimize the model fits to observations, these results suggest that acid-soluble particulate iron supplied to the EUC in the western equatorial Pacific is unlikely to be entirely bioavailable.     

L'archivage des activités humaines par les neiges et glaces polaires : le cas du plomb

The investigation of the occurrence of lead in dated snow and ice from Greenland and Antarctica has played a major role in our understanding of the history of the pollution of the atmosphere of our planet by this metal. Such studies have however proved to be very demanding, mainly because of the extreme purity of polar snow and ice. Reliable measurements can be obtained only if ultra-clean and highly sensitive procedures are used, as pioneered by Clair Patterson. The Greenland data show evidence of large-scale pollution of the atmosphere of the Northern Hemisphere for lead as early as two millennia ago during Greco–Roman times, especially because of mining and smelting activities in southern Spain. It peaked at the end of the 1960s, with lead concentrations in snow about 200 times higher than natural values, before declining during recent times because of the fall in the use of leaded gasoline. Lead pollution in Antarctica was already significant at the end of the 19th century as a consequence of whaling activities, the traffic of coal-powered ships crossing the Cape Horn, and mining activities in South America, South Africa and Australia. After declining because of the opening of the Panama Canal, the great economic depression and World War II, it reached a maximum during the 1980s, with lead concentrations 20 times higher than natural values. Other studies focus on past natural variations of lead in ancient ice dated from the last climatic cycles. To cite this article: C. Boutron et al., C. R. Geoscience 336 (2004).     

Statistical distribution of rainy events characteristics and instantaneous hyetographs generation (Merguellil watershed in central Tunisia)

In semi-arid regions, variability of rainfall inputs is high at different time and space scales. Thus, intense and highly variable hydro-meteorological events, which generate both potential resource and hazards, are of major interest. The Merguellil watershed is characterized by a large majority of rainfall in the form of storms, particularly violent in spring and autumn. Storms of summer are short and violent and can be the origin of important floods. Due to the strong rainfall variability, precipitation and hydrological regime are very irregular. This is what led us to think of a detailed study of rainy events. It was founded that two statistical distributions of parameters characterizing events are dominated (log normal, exponential).Thus, our objective consists in studying, in its globality, the collected pluviographic data in order to make a synthesis and analysis which should make it possible the generation of fictitious events to better control the rainfall risk and to study the response of the watershed faces to several types of rainfall. As result, we obtained hyetographs of the height studied rain gauges. These hyetographs show several types of events that are well in conformity with the observed reality. This generation is an advantageous tool in terms of both its robustness and its performance. Its relevance is based on the analysis of the fine time structure of recorded rainfall events. It can be made over several years, and would permit us to avoid being constrained by sample size. Generating rainfall events provides extensive time-related rainfall data that are consistent at all time steps, and can be seen as solution, even partially, of data lack in hydrological study.     

Biogeochemical processes in a clay formation in situ experiment: Part E - Equilibrium controls on chemistry of pore water from the Opalinus Clay, Mont Terri Underground Research Laboratory, Switzerland

The chemistry of pore water (particularly pH and ionic strength) is an important property of clay rocks being considered as host rocks for long-term storage of radioactive waste. Pore waters in clay-rich rocks generally cannot be sampled directly. Instead, their chemistry must be found using laboratory-measured properties of core samples and geochemical modelling. Many such measurements have been made on samples from the Opalinus Clay from the Mont Terri Underground Research Laboratory (URL). Several boreholes in that URL yielded water samples against which pore water models have been calibrated. Following a first synthesis report published in 2003, this paper presents the evolution of the modelling approaches developed within Mont Terri URL scientific programs through the last decade (1997-2009). Models are compared to the composition of waters sampled during dedicated borehole experiments. Reanalysis of the models, parameters and database enabled the principal shortcomings of the previous modelling efforts to be overcome. The inability to model the K concentrations correctly with the measured cation exchange properties was found to be due to the use of an inappropriate selectivity coefficient for Na-K exchange; the inability to reproduce the measured carbonate chemistry and pH of the pore waters using mineral-water reactions alone was corrected by considering clay mineral equilibria. Re-examination of the measured Ca/Mg activity ratios and consideration of the mineralogical composition of the Opalinus Clay suggested that Ca/Mg cation exchange rather than dolomite saturation may control the ratio of these ions in solution. This re-examination also suggests that the Ca/Mg ratio decreases with increasing pore-water salinity. Several possible reasons for this are proposed. Moreover, it is demonstrated that feldspar equilibria must not be included in Opalinus Clay modelling because feldspars are present only in very small quantities in the formation and because Na/K ratios measured in pore water samples are inconsistent with feldspar saturation. The principal need to improve future modelling is additional or better data on rock properties, in particular: (i) a more detailed identification of phases in the Opalinus Clay that include redox-sensitive elements together with evaluation of their thermodynamic properties; (ii) an improved understanding of the distribution of celestite throughout the Opalinus Clay for Sr/SO₄ concentrations control; (iii) improvements in analytic and thermodynamic data for Ca-Mg rock cation exchange and mineral chemical properties and (iv) the measurement of composition and stability constants of clay minerals actually present in the formation.     

Paleoclimate and Paleoenvironment of Gonghe Basin, Qinghai-Tibet Plateau, During the Lastdeglacial: Weathering, Erosion and Vegetation Cover Affect Clay Mineral Formation

With the analysis of the sources and formation mechanism of the clay minerals in the sediment core from the Dalianhai lake in the Gonghe Basin,northeastern Tibet-Qinghai Plateau,clay mineral composition proxies,grain-size and carbonate contents have been employed for high-resolution study in order to reconstruct East Asian Summer Monsoon （EASM） over the northeastern Tibet-Qinghai Plateau during the lastdeglacial.The study also extended to establish a relationship between vegetation cover changes and erosion during the last 14.5 ka with pollen record and clay mineral proxies.Smectite/kaolinite and smectite/（illite＋chlorite） ratios allow us to assess hydrolysis conditions in lowlands and/or physical erosion process in highlands of the Gonghe Basin.Before 12.9 Cal ka BP,both mineralogical ratios show low values indicative of strong physical erosion in the basin with a dominant cold and dry phase.After 12.9 Cal ka BP,an increase in both mineralogical ratios indicates enhanced chemical weathering in the basin associated with a warm and humid climate.The beginning of Holocene is characterized by high smectite/（illite＋chlorite） and smectite/kaolinite ratios that is synchronous as with deposition of many peat laminae,implying the best warm and humid conditions specifically between 8.0 to 5.5 Cal ka BP.The time interval after 5.0 Cai ka BP is characterized by a return to high physical erosion and low chemical weathering with dry climate conditions in the basin.Comparing variations of clay mineral assemblages with previous pollen results,we observe a rapid response in terms of chemical weathering and physical erosion intensity to a modification of the vegetation cover in the basin.     

Chemical transfer between mantle xenoliths and basic magmas: Evidence from oceanic magma chambers. The trinity ophiolite (northern California)

The Trinity ophiolite consists of small magma chambers inside a large mantle body. Xenoliths of mantle peridotite occur both in gabbroic cumulates along the walls and in the matrices of ultrabasic breccias on the floors of the magma chambers. Field relationships and petrographic data suggest that these fragments of original mantle peridotite were modified by contact with basic magmas by modal metasomatism. Quantitative elemental mass transfers determined from the composition, volume and density variations of reacting minerals demonstrate both closed and open system conditions for the major (Si, Al, Ti, Na, Ca, Fe and Mg) and trace elements (Cr, Ni). In the open system, material gains and losses provide information on the composition of the fluid taking part in the metasomatic reaction.

During a first stage of metasomatism the mantle xenoliths were affected by high-temperature reactions at 600 to 925°C. They resulted from the interaction between solid mantle lherzolites and basic melts. The reactions are:

1. (1)those forming orthopyroxene-magnetite simplectite

2. (2)those forming plagioclase-magnetite corona

3. (3)clinopyroxene+spinel I→pargasitic hornblende+spinel II.

Chemical interactions between the upper mantle and oceanic magma chambers occurred as soon as the basic magmas had ascended through the upper mantle. The chemically modified magmas, within oceanic magma chambers, were depleted in Ti, Fe and Na. This could partly explain regional variations of the chemical compositions of primary magmas produced beneath slow-spreading ridges. The breakdown of olivine to orthopyroxene and magnetite participates in the control of the partition of magnetic Fe---Ti oxides between oceanic crust and mantle.

During the second stage, the serpentinization of olivine and the production of talc were superimposed on the products of the first stage. These reactions require large amounts of H₂O. The hydrothermal fluid was probably seawater. It circulated in the brecciated area along the walls and floors of the magma chambers located at shallow depths. Such structural discontinuities thus played the role of penetration channels favoring seawater circulation in the oceanic crust.

All the chemical reactions examined suggest a significant open-system element transfer by infiltrating melts or circulating fluids. The results of this study suggest that caution is required in the interpretation of mineralogical and chemical information provided by mantle xenoliths carried to the surface by ascending magmas.     

The challenge of dating early pleistocene fossil teeth by the combined uranium series–electron spin resonance method: the Venta Micena palaeontological site (Orce,Spain)

The palaeontological site of Venta Micena (Orce, Andalusia, Spain) lies in the eastern sector of the Guadix–Baza basin, one of the best documented areas in Europe for Plio‐Pleistocene biostratigraphy. The combination of biochronological and palaeomagnetic results, combined with the radiometric data obtained for Atapuerca Sima del Elefante, indicated that the Venta Micena stratum was formed between the Jaramillo and Olduvai palaeomagnetic events, most likely between 1.22 and 1.77 Ma. Five fossil teeth from two outcrops (sites A and B) were selected to assess the potential of combined uranium series–electron spin resonance (US‐ESR) dating of Early Pleistocene sites. Although the US‐ESR results of the first outcrop showed a large scatter between the three teeth, the mean age of 1.37 ± 0.24 Ma can be considered a reasonable age estimate for Venta Micena. The mean ESR age of 0.62 ± 0.03 Ma obtained for site B seems to be a severe underestimation when compared with the independent age control. This underestimation is attributed to a relative recent U‐mobilization event that led to some U‐leaching. The results show that any ESR age calculations of old samples are extremely sensitive to variations in the measured ²³⁰Th/²³⁴U ratios in dental tissues. Although the results demonstrate that ESR can in principle be applied to Early Pleistocene sites, they also reveal the complexity of dating such old teeth. It is necessary to continue research in several directions, such as study of the behaviour of ESR signals in old teeth and understanding recent U‐mobilization processes, to improve the reliability of the combined US‐ESR dating method applied to Early Pleistocene times, a period for which the number of available numerical dating techniques is very limited. Copyright © 2011 John Wiley & Sons, Ltd.     

Magnesium isotope systematics of the lithologically varied Moselle river basin, France

Magnesium and strontium isotope signatures were determined during different seasons for the main rivers of the Moselle basin, northeastern France. This small basin is remarkable for its well-constrained and varied lithology on a small distance scale, and this is reflected in river water Sr isotope compositions. Upstream, where the Moselle River drains silicate rocks of the Vosges mountains, waters are characterized by relatively high ⁸⁷Sr/⁸⁶Sr ratios (0.7128-0.7174). In contrast, downstream of the city of Epinal where the Moselle River flows through carbonates and evaporites of the Lorraine plateau, ⁸⁷Sr/⁸⁶Sr ratios are lower, down to 0.70824.Magnesium in river waters draining silicates is systematically depleted in heavy isotopes (δ²⁶Mg values range from −1.2 to −0.7‰) relative to the value presently estimated for the continental crust and a local diorite (−0.5‰). In comparison, δ²⁶Mg values measured in soil samples are higher (∼0.0‰). This suggests that Mg isotope fractionation occurs during mineral leaching and/or formation of secondary clay minerals. On the Lorraine plateau, tributaries draining marls, carbonates and evaporites are characterized by low Ca/Mg (1.5-3.2) and low Ca/Sr (80-400) when compared to local carbonate rocks (Ca/Mg = 29-59; Ca/Sr = 370-2200), similar to other rivers draining carbonates. The most likely cause of the Mg and Sr excesses in these rivers is early thermodynamic saturation of groundwater with calcite relative to magnesite and strontianite as groundwater chemistry progressively evolves in the aquifer. δ²⁶Mg of the dissolved phases of tributaries draining mainly carbonates and evaporites are relatively low and constant throughout the year (from −1.4‰ to −1.6‰ and from −1.2‰ to −1.4‰, respectively), within the range defined for the underlying rocks. Downstream of Epinal, the compositions of the Moselle River samples in a δ²⁶Mg vs. ⁸⁷Sr/⁸⁶Sr diagram can be explained by mixing curves between silicate, carbonate and evaporite waters, with a significant contribution from the Vosgian silicate lithologies (>70%). Temporal co-variation between δ²⁶Mg and ⁸⁷Sr/⁸⁶Sr for the Moselle River throughout year is also observed, and is consistent with a higher contribution from the Vosges mountains in winter, in terms of runoff and dissolved element flux. Overall, this study shows that Mg isotopes measured in waters, rocks and soils, coupled with other tracers such as Sr isotopes, could be used to better constrain riverine Mg sources, particularly if analytical uncertainties in Mg isotope measurements can be improved in order to perform more precise quantifications.     

Early Pleistocene climate changes in the central Mediterranean region as inferred from integrated pollen and planktonic foraminiferal stable isotope analyses

Vegetation inherited from a Pliocene subtropical climate evolved through obliquity oscillations and global cooling leading to modern conditions. An integrated, highly time-resolved record of pollen and stable isotopes (δ¹⁸O and δ¹³C of Globigerina bulloides) was obtained to understand vegetation responses to Early Pleistocene climate changes. Continental and marine responses are compared in the Central Mediterranean region with a particular consideration of environmental changes during anoxic events.Pollen data illustrate vegetation dynamics as follows: [1] development of mesothermic elements (warm and humid conditions); [2] expansion of mid- and high-altitude elements (cooler but still humid conditions); and [3] strengthening of steppe and herb elements (cooler and dry conditions). These successions correlate with precession. δ¹⁸O variations recorded by Globigerina bulloides define two cycles (MIS 43-40) related to obliquity. At northern low- to mid-latitudes, the pollen signal records temperature and wetness changes related to precession even during global climate changes induced by obliquity. This may result in unexpected increasing wetness during glacial periods, which has to be considered specific to the Central and Eastern Mediterranean region. Lastly, an analysis of anoxic events reveals that enhanced runoff is indicated by increasing frequency of the riparian trees Liquidambar and Zelkova.