M. Treuil

A RE-APPRAISAL OF THE USE OF TRACE ELEMENTS TO CLASSIFY AND DISCRIMINATE BETWEEN MAGMA SERIES ERUPTED IN DIFFERENT TECTONIC SETTINGS

Abstract The hygromagmatophile element composition of basic lavas from several tectonic environments are compared with the estimated composition of the primordial mantle. The observed variations are used to subdivide mid-ocean ridge basalts (MORB) into two main types according to the tectonic character of the ridge segment from which they were erupted. Ridge segments with positive residual gravity, depth and heat flow anomalies erupt E-type MORB which are predominantly enriched in the more hygromagmatophile elements, but also include magma types which are depleted in most of these elements. Both enriched and depleted E-type MORB can be distinguished from the basalts erupted at normal ridge segments (N-type MORB) by their La/Ta ratios (in E-type MORB La/Ta ∼10, in N-type MORB La/Ta is ∼15) and by Hf/Ta ratios (in E-type MORB Hf/Ta> 7, in N-type MORB Hf/Ta> 7). E-type MORB can be distinguished from the basalts erupted at ocean islands by their higher Hf/Ta ratios (>2). A Th-Hf-Ta triangular diagram is used to discriminate between the different ocean floor basalts as well as those erupted at destructive plate margins, which are depleted in Ta and Nb. This diagram can also distinguish between silicic lavas from the different tectonic environments as well as identifying lavas that have been contaminated with continental crust.

GEOCHEMISTRY OF BASALTS DRILLED IN THE NORTH-ATLANTIC BY IPOD LEG-49 - IMPLICATIONS FOR MANTLE HETEROGENEITY

Abstract IPOD Leg 49 recovered basalts from 9 holes at 7 sites along 3 transects across the Mid-Atlantic Ridge: 63°N (Reykjanes), 45°N and 36°N (FAMOUS area). This has provided further information on the nature of mantle heterogeneity in the North Atlantic by enabling studies to be made of the variation of basalt composition with depth and with time near critical areas (Iceland and the Azores) where deep mantle plumes are thought to exist. Over 150 samples have been analysed for up to 40 major and trace elements and the results used to place constraints on the petrogenesis of the erupted basalts and hence on the geochemical nature of their source regions. It is apparent that few of the recovered basalts have the geochemical characteristics of typical “depleted” midocean ridge basalts (MORB). An unusually wide range of basalt compositions may be erupted at a single site: the range of rare earth patterns within the short section cored at Site 413, for instance, encompasses the total variation of REE patterns previously reported from the FAMOUS area. Nevertheless it is possible to account for most of the compositional variation at a single site by partial melting processes (including dynamic melting) and fractional crystallization. Partial melting mechanisms seem to be the dominant processes relating basalt compositions, particularly at 36°N and 45°N, suggesting that long-lived sub-axial magma chambers may not be a consistent feature of the slow-spreading Mid-Atlantic Ridge. Comparisons of basalts erupted at the same ridge segment for periods of the order of 35 m.y. (now lying along the same mantle flow line) do show some significant inter-site differences in Rb/Sr, Ce/Yb, 87 Sr/ 86 Sr, etc., which cannot be accounted for by fractionation mechanisms and which must reflect heterogeneities in the mantle source. However when hygromagmatophile (HYG) trace element levels and ratios are considered, it is the constancy or consistency of these HYG ratios which is the more remarkable, implying that the mantle source feeding a particular ridge segment was uniform with respect to these elements for periods of the order of 35 m.y. and probably since the opening of the Atlantic. Yet these HYG element ratios at 63°N are very different from those at 45°N and 36°N and significantly different from the values at 22°N and in “MORB”. The observed variations are difficult to reconcile with current concepts of mantle plumes and binary mixing models. The mantle is certainly heterogeneous, but there is not simply an “enriched” and a “depleted” source, but rather a range of sources heterogeneous on different scales for different elements — to an extent and volume depending on previous depletion/enrichment events. HYG element ratios offer the best method of defining compositionally different mantle segments since they are little modified by the fractionation processes associated with basalt generation.

Mobility and fluxes of major, minor and trace metals during basalt weathering and groundwater transport at Mt. Etna volcano (Sicily)

Abstract The concentrations and fluxes of major, minor and trace metals were determined in 53 samples of groundwaters from around Mt Etna, in order to evaluate the conditions and extent of alkali basalt weathering by waters enriched in magma-derived CO 2 and the contribution of aqueous transport to the overall metal discharge of the volcano. We show that gaseous input of magmatic volatile metals into the Etnean aquifer is small or negligible, being limited by cooling of the rising fluids. Basalt leaching by weakly acidic, CO 2 -charged water is the overwhelming source of metals and appears to be more extensive in two sectors of the S-SW (Paterno) and E (Zafferana) volcano flanks, where out flowing groundwaters are the richest in metals and bicarbonate of magmatic origin. Thermodynamic modeling of the results allows to evaluate the relative mobility and chemical speciation of various elements during their partitioning between solid and liquid phases through the weathering process. The facts that rock-forming minerals and groundmass dissolve at different rates and secondary minerals are formed are taken into account. At Mt. Etna, poorly mobile elements (Al, Th, Fe) are preferentially retained in the solid residue of weathering, while alkalis, alkaline earth and oxo-anion-forming elements (As, Se, Sb, Mo) are more mobile and released to the aqueous system. Transition metals display an intermediate behavior and are strongly dependent on either the redox conditions (Mn, Cr, V) or solid surface-related processes (V, Zn, Cu). The fluxes of metals discharged by the volcanic aquifer of Etna range from 7.0 × 10 −3 t/a (Th) to 7.3 × 10 4 t/a (Na). They are comparable in magnitude to the summit crater plume emissions for a series of elements (Na, K, Ca, Mg, U, V, Li) with lithophile affinity, but are minor for volatile elements. Basalt weathering at Mt Etna also consumes about 2.1 × 10 5 t/a of magma-derived carbon dioxide, equivalent to ca. 7% of contemporaneous crater plume emissions. The considerable transport of some metals in Etna’s aquifer reflects a particularly high chemical erosion rate, evaluated at 2.3∗10 5 t/a, enhanced by the initial acidity of magmatic CO 2 -rich groundwater.

Rare earths in barites: distribution and effects on aqueous partitioning

Abstract A large variety of barites collected from marine and continental environments was analyzed by neutron activation for the rare-earth elements (REE) La, Ce, Sm, Eu and Dy. Relative to chondrites, all barites show a decrease of the lighter REE from La toward Eu. The abundance and distribution of rare earths in barites show a distinction of barite types. Deep-sea barites have large REE concentrations as do other authigenic deep-sea minerals and display the chondrite normalized Eu minimum, but not the negative Ce anomaly, of sea water. Other barites, mostly on land, some hydrothermal, and others of shallow marine origin, display lower total Ree concentrations. Chondrite normalized positive Eu anomalies are displayed by those varieties of reducing sedimentary and metamorphic origin. Distribution of REE in barite can be attributed both to crystallographic constraints of substitution, and to solution complexing of REE in the precipitating medium. Plots of rare earth partitioning versus effective ion size suggest that the decreasing enrichment toward Eu for all barite types is caused by crystallographic constraints due to contraction of the substituting REE ion sizes relative to the size of the host Ba ion. Solution effects on REE substitution in barite can be evaluated by writing solid solution distribution equations based on mass action of REE and Ba sulfates and the lanthanide (Ln) solution species Ln (CO3)−54), LnSO+4, LnCl+2 and LnF+2. Under normal sea water conditions, solution complexing plays a minor role. However, increased alkalinities of reducing sediments and increased brine chlorinities could cause significant complexing and deplete REE heavier than Eu. Besides Dy in barites, this could be true for aqueous precipitation of REE in general.

The primordial chondritic nature and large-scale heterogeneities in the mantle: evidence from high and low partition coefficient elements in oceanic basalts

Large-scale heterogeneities in the mantle are investigated through trace elements measured in oceanic basalts from different locations in the Atlantic and Pacific oceans. The study relies upon the physico-chemical properties of the elements and their classification according to their partition coefficients. High partition coefficient elements (Co, Ni, Cr) have concentrations in peridotite that are not sensitive to solid-liquid equilibrium (partial melting); the mantle should therefore be homogeneous with respect to these elements. The ratios of elements that have equal or very similar low partition coefficients (Y/Tb, Zr/Hf and Nb/Ta) are constant in all samples studied, despite their large concentration range. These ratios are equal to chondritic ratios and favour a chondritic nature for the primordial mantle. The La/Ta ratio shows two values, either 9 or 18, which are closely related to topography (9 for topographic highs). When the difference between partition coefficients of two hygromagmaphilic elements increases, the local variations observed for their ratio can be interpreted either as local heterogeneities of mantle sources or as the effect of magmatic processes (e.g. partial melting).

Natural and EDTA-complexed lanthanides used as a geochemical probe for aquifers: a case study of Orleans valley's alluvial and karstic aquifers

The transit of chemical elements within the different parts of Orleans valley’s aquifer is studied by two complementary methods. Those methods rely on the fractionation of lanthanides (Ln) during their migration in natural waters. The first method consists in studying natural lanthanides patterns within the watershed, at its entries and exits. The second one lies on multi-tracer experiments with Ln-EDTA complexes. This work is completed through an observation network consisting of 52 piezometers set on a sand and gravel quarry, and the natural entries and exits of the aquifer. Orleans valley’s aquifer, which is made of an alluvial watershed lying on a karstic aquifer, is mainly fed by the Loire river via a large karstic network. At the entries of the aquifer (Loire river at Jargeau), the Ln concentrations in the dissolved fraction (< 0,22 μm) vary with the flow of the river. During floods, Loire river waters display bulk continental crust-like Ln compositions with a slight enrichment in heavy Ln from Dy to Lu. When the Loire river flow becomes low level, the crust-normalised Ln patterns show a depletion in light Ln whereas Lu concentrations remain identical. The same evolution spatially occurs between the entries and exits of the karstic network. Spring waters are depleted in light Ln relative to the Loire river whereas heavy Ln (Yb, Lu) remain constant during transit. Furthermore, the depletion in light Ln increases with the distance between entries and exits. Tracer experiments using EDTA-complexed Ln within and between the alluvial and calcareous parts of the watershed have shown that complexed Ln are fractionated across all these geological strata. The recoveries of tracers always follow the order light Ln heavy Ln. On the other hand, the filtration of alluvial groundwater with high colloids content induces no significant Ln fractionation when the solution contains no strong chelating agent. Hence, the transit of natural and artificial Ln in Orleans valley aquifer can be explained by two complementary processes. (1) Decanting/filtering or, on the opposite, stirring of colloids. Those processes induce no important Ln fractionation. (2) Exchanges of Ln between solute complexes, colloids and sediments due to the presence of strong chelating agents. Those exchanges fractionate the Ln in the order of their stability constants. Considering the natural Ln fractionation that occurs in the Loire river and in the studied aquifer, the carbonates, the stability constants of which follow the order light Ln < heavy Ln, are the best candidates as natural strong chelating agents. From the hydrodynamic point of view, both tracer experiments and natural Ln concentrations show that the transfer of elements within the alluvial watershed is pulsed by the Loire river movements. During an ascent phase, the elements migrate away from and perpendicularly to the karstic channels direction. During the river descent, horizontal flows are quasi absent and migrations are mainly vertical from the alluvia down to the calcareous part of the aquifer. Due to those hydrodynamic characteristics, alluvia and non fissured limestone have a high dynamic confining capacity. Elements with high affinity for solid or colloidal phases (e.g. light Ln) have an increased confining capacity in the whole aquifer, by sorption and colloid filtration within the alluvia and at the alluvial-calcareous interface, and by colloid decanting within the karstic channels. Overall, this model combines two components. The first one, hydrodynamical, results from the repartition of the loads pulsed by river Loire through the karst. The second one physico-chemical, results from the element distribution mainly controlled by colloide/solute complexes exchange coefficients.