Frank McDermott

Controls on trace element (Sr-Mg) compositions of carbonate cave waters: implications for speleothem climatic records

Abstract At two caves (Clamouse, S France and Ernesto, NE Italy), cave drip and pool waters were collected and sampled at intervals over a 2–3 year period. Mg/Ca and Sr/Ca concentration ratios, corrected for marine aerosols, are compared with those of bedrocks and, in some cases, aqueous leachates of soils and weathered bedrocks. Cave waters do not lie along mixing lines between calcite and dolomite of bedrock carbonate, but typically show enhanced and covarying Mg/Ca and Sr/Ca. Four factors are considered as controlling processes. (1) The much faster dissolution rate of calcite than dolomite allows for the possibility of increase of Mg/Ca if water–rock contact times are increased during drier conditions. A theoretical model is shown to be comparable to experimental leachates. (2) Prior calcite precipitation along a flow path is a powerful mechanism for generating enhanced and covarying Mg/Ca and Sr/Ca ratios. This mechanism requires the solution to lose CO 2 into pores or caverns. (3) Incongruent dolomite dissolution has only limited potential and is best regarded as two separate processes of dolomite dissolution and calcite precipitation. (4) selective leaching of Mg and Sr with respect to Ca is shown to be important in leachates from Ernesto where it appears to be a phenomenon of calcite dissolution. In general selective leaching can occur whenever Ca is sequestered into precipitates due to freezing or drying of soils, or if there is derivation of excess Sr and Mg from non-carbonate species. The Ernesto cave has abundant water supply which in the main chamber is derived from a reservoir with year-round constant P CO 2 of around 10 −2.4 and no evidence of calcite precipitation in the karst above the cave. Two distinct, but overlying trends of enhanced and covarying Mg/Ca and Sr/Ca away from the locus of bedrock compositions are due to calcite precipitation within the cave and, at a variable drip site, due to enhanced selective leaching at slow drip rates. Mg-enhancement in the first chamber is due to a more dolomitic bedrock and longer residence times. The Clamouse site has a less abundant water supply and presents geochemical evidence of prior calcite precipitation, both in the cave and in overlying porous dolomite/dedolomitized limestone bedrock. Initial P CO 2 values as high as 10 −1 are inferred. Experimental incubations of Clamouse soils which generated enhanced P CO 2 and precipitated CaCO 3 had compositions similar to the karst waters. Calcite precipitation is inferred to be enhanced in drier conditions. Hydrological controls on cave water chemistry imply that the trace element chemistry of speleothems may be interpretable in palaeohydrological terms. Drier conditions tends to promote not only longer mean residence times (enhancing dolomite dissolution and hence Mg/Ca), but also enhances degassing and calcite precipitation leading to increased Mg/Ca and Sr/Ca.

Cenozoic K-rich adakitic volcanic rocks in the Hohxil area, northern Tibet : Lower-crustal melting in an intracontinental setting

It is generally accepted that the Cenozoic potassic volcanic rocks of northern Tibet were derived from a lithospheric mantle source. Here we report new chronological, geochemical, and isotopic data for the Miocene (ca. 18-15 Ma) K-rich adakitic volcanic rocks from the Hohxil area of the Songpan-Ganzi block in northern Tibet. We contend that these rocks were generated by partial melting of the mafic lower crust, in an intracontinental setting unrelated to subduction of oceanic crust. The Hohxil rocks exhibit high Sr/Y and La/Yb ratios, high Sr and La contents, but low Yb and Y concentrations, similar to adakites formed by slab melting associated with subduction. However, their relatively low e N d values (-2.09 to -4.58); high 8 7 Sr/ 8 6 Sr (0.7072-0.7075), Th/U, Th/Ba, and Rb/Ba ratios; and distinctive potassium enrichments (K 2 O > Na 2 O) are very different from the composition of typical adakites. In addition, those K-rich adakitic rocks with the highest SiO 2 contents (>61 wt%) exhibit the lowest 8 7 Sr/ 8 6 Sr ratios and highest e N d values and are the oldest Cenozoic volcanic rocks exposed in the Songpan-Ganzi block, suggesting that they were derived neither directly from a mantle source nor by differentiation of a shoshonitic magma. Taking into account the composition of lower-crustal mafic xenoliths in Tibet, as well as the tectonic and geophysical evidence, we conclude that the Hohxil adakitic magmas were produced by partial melting of amphibole-bearing eclogites with a K-rich mafic bulk composition, in the lower part (≥∼55 km) of the thickened northern Tibetan crust. Partial melting of the lower crust may have been triggered by dehydration release of fluids from sedimentary materials in the southward-subducted continental lithosphere.

Trace element and SrNdPb isotopic constraints on a three-component model of Kamchatka Arc petrogenesis

The Kamchatka arc (Russia) is located in the northwestern Pacific Ocean and is divided into three segments by major sub-latitudinal fault zones (crustal discontinuities). The southern (SS) and central (CS) segments are associated with the subduction of old Pacific lithosphere, whereas the northern, inactive segment (NS) was formed during westward subduction of young (< 15 Ma) Komandorsky Basin oceanic crust. Further segmentation of the arc is outlined by the development of the Central Kamchatka Depression (CKD) intra-arc rift, which is oriented parallel to the arc and is splitting the CS into the active Eastern Volcanic Front (EVF) and the largely inactive, rear-arc Sredinny Range. The NS volcanics (15-5 Ma) include calc-alkaline lavas, shoshonites, adakites, and Nb-enriched arc basalts. Isotopically all magma types share high 143Nd/144Nd ratios of 0.512976-0.513173 coupled with variable 87Sr/86Sr (0.702610-0.70356). NS lavas plot within or slightly above the Pacific MORB field on the Pb isotopic diagrams. The EVF volcanoes have more radiogenic 143Nd/144Nd (0.51282-0.513139) and 208Pb/204Pb (38.011–38.1310) than the NS lavas. CKD lavas display MORB-like Nd isotope ratios at slightly elevated 87Sr/86Sr values accompanied by a slightly less radiogenic Pb composition. Kamchatka lavas are thought to be derived from a MORB-like depleted source modified by slab-derived siliceous melts (adakites) and fluids (NS), or fluids alone (CS and SS). The NS and EVF lavas may have been contaminated by small fractions of a sedimentary component that isotopically resembles North Pacific sediment. Petrogenesis in the Kamchatka arc is best explained by a three-component model with depleted mantle wedge component modified by two slab components. Slab-derived hydrous melts produced incompatible element characteristics associated with northern segment lavas, while hydrous slab fluids caused melting in the depleted mantle below the southern and central segments of the Kamchatka arc. Trace element characteristics of Kamchatka lavas appear to be controlled by slab fluids or melts, while radiogenic isotope ratios which are uniform throughout the arc reflect depleted composition of sub-arc mantle wedge.

Calcite Fabrics, Growth Mechanisms, and Environments of Formation in Speleothems from the Italian Alps and Southwestern Ireland

Five fabrics were identified in Alpine and Irish caves on the basis of morphological and microstructural characteristics, and re- lated to growth mechanisms and growth environment. Columnar and fibrous fabrics grow when speleothems are continuously wet, and from fluids at near-equilibrium conditions (low supersaturation; SIcc , 0.35), through the screw dislocation mechanism. The highly defective microcrystalline fabrics form at the same supersaturation range as co- lumnar fabric but under variable discharge and the presence of growth inhibitors. Dendritic fabrics, which have the highest density of crystal defects, develop in disequilibrium conditions (high supersaturation) un- der periodic very low-flow-regime periods that result in prolonged out- gassing. Cave calcareous tufa forms in disequilibrium conditions. Only the calcite crystals of fabrics formed at low supersaturation seem to precipitate near-isotopic-equilibrium conditions.

Holocene climate variability in Europe: Evidence from δ18O, textural and extension-rate variations in three speleothems

Time-series O isotope profiles for three U–Th dated stalagmites have revealed that for much of the Holocene, a site on the Atlantic seaboard (SW Ireland) exhibits first-order δ18O trends that are almost exactly out of phase with coupled δ18O curves from two southern European sites (SE France and NW Italy). In the Irish stalagmite (CC3 from Crag Cave, SW Ireland), low δ18O at 10,000 cal yr BP reflects cool conditions. By the early to mid-Holocene (9000–6000 cal yr BP) δ18O had increased, reflecting the onset of warmer conditions on the Atlantic seaboard. This shift to higher δ18O was accompanied by a marked increase in the stalagmite extension rate, reinforcing our interpretation that this was a period of relative warmth. Except for an episode of increased extension rate about 5500 yr ago, δ18O in the Crag stalagmite exhibits a gradual decrease, accompanied by declining extension rates between 7800 and 3500 cal yr BP, interpreted as a cooling trend. There is evidence for increases in both δ18O and stalagmite extension rate in the period from 3500 cal yr BP to the present day suggesting a return to warmer conditions on the Atlantic seaboard. In the stalagmite from NW Italy (ER76, Grotta di Ernesto, Trentino province) the early-Holocene (c. 9200-7800 cal yr BP) is characterised by high δ18O, probably indicative of warm and/or dry conditions. Exceptionally low δ18O from 7800 to 6900 cal yr BP at this site reflects a well-defined wet phase (Cerin wet phase). In the last three millennia, this stalagmite exhibits a shift to lower δ18O, interpreted as some combination of cooler and/or wetter conditions. Unlike the Irish stalagmite, the Italian sample does not show a correlation between δ18O and extension rate. Instead, its extension rate correlates roughly with δ13C, presumably reflecting a climate-driven vegetation change. In the early Holocene, δ18O in the French stalagmite (CL26, Grotte de Clamouse, Herault province, SE France) was low relative to its Holocene average. For much of the period since c. 3500 cal yr BP this stalagmite exhibits higher δ18O than in the early Holocene, suggesting warmer conditions. Like the Irish stalagmite, the French sample exhibits a well-defined correlation between δ18O and extension rate. Had drip-water availability been the dominant control on δ18O at this semi-arid site then higher δ18O would have been accompanied by lower, not higher extension rates. This suggests strongly that temperature rather than rainfall amount was the dominant control at this site. While conclusions regarding the patterns of climate variability on a continent scale must remain tentative because of the limited number of stalagmites studied we argue that early Holocene warm conditions on the Atlantic seaboard (Irish site) coincided with relatively cool conditions at the Clamouse site. By c. 3500 yr ago the pattern appears to have been reversed.

Late Holocene annual growth in three Alpine stalagmites records the influence of solar activity and the North Atlantic Oscillation on winter climate

Annual growth rates and the ratio of dark to light-colored calcite within single annual laminae in three contemporaneously deposited Holocene speleothems from Grotta di Ernesto, an Alpine cave in northern Italy, respond to changes in surface temperature rather than precipitation. Based on monitoring of present-day calcite growth, and correlation with instrumental data for surface climatic conditions, we interpret a higher ratio of dark to light-colored calcite and the simultaneous thinning of annual laminae as indicative of colder-than-present winters. Such dark and thin laminae occur in those parts of the three stalagmites deposited from AD 1650 to 1713 and from AD 1798 to 1840, as reconstructed through lamina counting. These periods correspond to the well-known Maunder and Dalton Minima of solar activity. An 11-yr cyclicity in growth rate, coupled with reduced calcite deposition during the historic minima of solar activity, is indicative of a solar influence on lamina thickness. Spectral analysis of the lamina thickness data also suggests that the North Atlantic Oscillation variability influenced winter temperatures. Based on the present-day controls on cave calcite formation, we infer that high-frequency changes in solar activity modulated the seasonal duration of soil CO2 production.

Aragonite-Calcite Relationships in Speleothems (Grotte De Clamouse, France): Environment, Fabrics, and Carbonate Geochemistry

ABSTRACT In Grotte de Clamouse (France), aragonite forms in a variety of crystal habits whose properties reflect the conditions of formation. Prolonged degassing and evaporation yield needle aragonite, which is more enriched in 18O and 13C than aragonite ray crystals, which form near isotopic equilibrium. At present, aragonite ray crystals form at the tops of stalagmites at very low discharge (0.00035 ml/ min), and when fluid Mg/Ca ratio is > 1.1. Temperature and evaporation do not seem to have a significant role in their formation. The presence of aragonite in stalagmites should be indicative of a decrease in drip rate related to either dry climate conditions or local hydrology. Fossil aragonite was in part replaced by calcite in a time frame 13C signal and U content), and preserved aragonite relicts (up to 16 weight %). The isotope signal of different aragonite habits may reflect conditions of formation rather than climate parameters. The real extent of aragonite-to-calcite transformation may be underestimated when replacement calcite inherits both textural and chemical properties of the precursor.

Element fluxes associated with subduction related magmatism

Destructive plate margin magmas may be subdivided into two groups on the basis of their rare earth element (REE) ratios. Most island arc suites have low Ce/Yb, and remarkably restricted isotope ratios of 87Sr/86Sr = 0.7033, 143Nd/144Nd = 0.51302, 206Pb/204Pb = 18.76 , 207Pb/204Pb = 15.57, and 208Pb/204Pb = 38.4. However, they also have Rb/Sr (0.03), Th/U (2.2) and Ce/Yb (8.5) ratios which are significantly less than accepted estimates for the bulk continental crust. The high Ce/Yb suites have higher incompatible element contents, more restricted heavy REE, and much more variable isotope ratios. Such rocks are found in the Aeolian Islands, Grenada, Indonesia and Philippines, and their isotope and trace element features have been attributed both to contributions from subducted sediment, and/or old trace element enriched material in the mantle wedge. It is argued that for isotope and trace element models the slab component can usefully be taken to consist of subducted sediment and altered mid-ocean ridge basalts, since these may contain ca. 80% of the water in the subducted slab, and the distinctive trace element features of arc magmas are generally attributed to the movement of material in hydrous fluids. The isotope data indicate that not more than 15% of the Sr and Th in an average arc magma were derived from subducted material, and that the rest were derived from the mantle wedge. The fluxes of elements which cannot be characterized isotopically are more difficult to constrain, but for most minor and trace elements the slab derived contribution in arc magmas is too small to have a noticeable effect on the residual slab.

Annual to sub-annual resolution of multiple trace-element trends in speleothems

This study aims to establish evidence for the widespread existence of preserved high-resolution trace element variations in speleothems that may have climatic significance. Ion microprobe analysis of speleothems reveals that annual to sub-annual variations in element chemistry exist at five, shallow western European cave sites (Crag Cave, County Kerry and Ballynamintra, County Waterford, Ireland; Uamh an Tartair, Sutherland, Scotland; Grotte Pere-Noël, Belgium; Grotta di Ernesto, NE Italy) with widely varying climatic, geomorphic and geological settings. The variations are not restricted to species (Mg, Sr and Ba) known to substitute directly for Ca in the calcite lattice, but include H, F, Na and P. Phosphorus (as phosphate) displays the greatest variability and may have the most significance as a proxy for the seasonal temperature cycle because of its role as a nutrient element. The technique allows estimation of growth rate of speleothems at any interval of interest, which is one of several possible uses in palaeoclimatology.

Elemental U and Th variations in island arc rocks: implications for U-series isotopes

Isotope and trace element data from well characterised arc suites are used to identify contributions from fluids and subducted sediments in arc rocks. U-series isotopes are then used to argue that the fluid and sediment components are characterised by different transfer times through the mantle wedge. U, but not Th, is readily mobilised in the fluid component. Th behaves as a high field strength element (HFSE), and the negative array between Th/Ce and Nd isotopes indicates that significant amounts of the Th and by implication other HFSE, in arc rocks are derived from sediments in the subducted slab. These elements may therefore only be regarded as conservative in the sense that they are not mobilised in the fluid component. As the fluid component contains U, but little if any Th, the resultant (238U/ 230Th) disequilibria may be used to estimate transfer times for the fluid component, and these are typically 30–120 ka. In contrast, rocks with a greater contribution from subducted sediments (high Th/Ce and low 143Nd/144Nd) tend to have (238U/ 230Th) ∼ 1, and low 10Be, suggesting transfer times of several million years. Overall, the Th, LREE and Ta contents of many arc rocks are dominated by the sediment component which is probably partial melts of sediments in the subducted slab. It is estimated that ∼ 30% of the Th in subducted sediments is returned to the crust in arc magmas. The fractionation of U/Th and Sm/Nd requires that average continental crust was generated in the presence of residual garnet, presumably by processes early in Earth history that were different from those at recent plate margins.