Silvia Frisia

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.

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.

Increasing Australian–Indonesian monsoon rainfall linked to early Holocene sea-level rise

The Australian–Indonesian summer monsoon affects rainfall variability across the Indo–Pacific region. Reconstructions of monsoon strength from stalagmites show that precipitation increased from 11,000 to 7,000 years ago, as rising global sea level caused the flooding of the Indonesian continental shelf. The Australian–Indonesian summer monsoon affects rainfall variability and hence terrestrial productivity in the densely populated tropical Indo–Pacific region. It has been proposed that the main control of summer monsoon precipitation on millennial timescales is local insolation1,2,3, but unravelling the mechanisms that have influenced monsoon variability and teleconnections has proven difficult, owing to the lack of high-resolution records of past monsoon behaviour. Here we present a precisely dated reconstruction of monsoon rainfall over the past 12,000 years, based on oxygen isotope measurements from two stalagmites collected in southeast Indonesia. We show that the summer monsoon precipitation increased during the Younger Dryas cooling event, when Atlantic meridional overturning circulation was relatively weak4. Monsoon precipitation intensified even more rapidly from 11,000 to 7,000 years ago, when the Indonesian continental shelf was flooded by global sea-level rise5,6,7. We suggest that the intensification during the Younger Dryas cooling was caused by enhanced winter monsoon outflow from Asia and a related southward migration of the intertropical convergence zone8. However, the early Holocene intensification of monsoon precipitation was driven by sea-level rise, which increased the supply of moisture to the Indonesian archipelago.

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.

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.

Climate variability in the SE Alps of Italy over the past 17 000 years reconstructed from a stalagmite record

Stalagmite SV1 from Grotta Savi, located at the SE margin of the European Alps (Italy), is the first Alpine speleothem that continuously spans the past c. 17kyr. Extension rate and δ18Oc record for the Lateglacial probably reflect a combination of temperature and rainfall, with rainfall exerting the dominant effect. Low speleothem calcite δ18 Oc values were recorded from c. 14.5 and 12.35 kyr, during GI-1 (Bolling— Allerod) interstadial, which in our interpretation, was warm and wet. The GS-1 (Younger Dryas) was characterized by a shift to heavier δ18 Oc, coinciding with δ13Cc enrichment and extremely low extension rate (<8 μm/year). These characteristics indicate that GS-1 climate was cool and dry in the SE Alps. Calibration using historical data revealed that there is a positive δ18Oc/dT relationship. A 1°C rise in mean annual temperature should correspond to c. 2.85% increase of SV-1 δc18Oc. We reconstructed a slow and steady temperature rise of c. 0.5°C since 10 kyr BP, in broad agreement with reconstructions from pollen data for SE Europe. Stalagmite SV1 indicates that climate variability in the SE Alps has been influenced by the Mediterranean Sea for the past c. 17 kyr.

Calcite Moonmilk: Crystal Morphology and Environment of Formation in Caves in the Italian Alps

ABSTRACT Calcite moonmilk, which is a cave deposit formed of calcite crystals and water, is found in many caves in the Italian Alps. These modern and ancient deposits are formed of fiber calcite crystals, 50-500 nm wide and 1 to > 10 µm long, and polycrystalline chains that have few crystal defects. Radiocarbon dating indicates that most moonmilk deposits in these caves are fossil and that for most precipitation ceased 6400 cal years BP, at the end of the mid-Holocene Hypsithermal. In the caves of the Italian Alps, the optimal conditions for formation of calcite moonmilk are: (1) a temperature range of 3.5-5.5°C, (2) low discharge volumes of seepage waters that are slightly supersaturated (SICAL = 0.0 to 0.2), and (3) relative humidity that is at or close to 100%. Microbial activity apparently did not play an active role in the formation of the calcite moonmilk. Conditions for moonmilk formation are typically found in caves that are located beneath land surfaces, which are soil covered and support a conifer forest. Precipitation of the fiber calcite crystals apparently involved very slow flow of slightly supersaturated fluids. The fact that moonmilk appears to form under a narrow range of environmental conditions means that this cave deposit has potential as a paleoclimatic indicator in high alpine karst areas.

North Atlantic storm track changes during the Last Glacial Maximum recorded by Alpine speleothems

The European Alps are an effective barrier for meridional moisture transport and are thus uniquely placed to record shifts in the North Atlantic storm track pattern associated with the waxing and waning of Late-Pleistocene Northern Hemisphere ice sheets. The lack of well-dated terrestrial proxy records spanning this time period, however, renders the reconstruction of past atmospheric patterns difficult. Here we present a precisely dated, continuous terrestrial record of meteoric precipitation in Europe between 30 and 14.7 ka. In contrast to present-day conditions, our speleothem data provide strong evidence for preferential advection of moisture from the South across the Alps supporting a southward shift of the storm track during the local Last Glacial Maximum (that is, 26.5–23.5 ka). Moreover, our age control indicates that this circulation pattern preceded the Northern Hemisphere precession maximum by ~3 ka, suggesting that obliquity may have played a considerable role in the Alpine ice aggradation.