QUATERNARIA NOVA , Vol. VII, 2000-2003, 1-15.

F. Antonioli*, S. Silenzi**, M. Gabellini**, M. Mucedda***


Holocene continental climatic and environmental records on ice volume, air temperature and amount of precipitation are available from studies of ice cores, lake levels and pollen (Dansgard et al., 1993; Huntley and Prentice, 1988; Guiot et al., 1993). However, ice core records are restricted to high latitudes or altitudes, and lake records are strongly limited in time and space. Theoretically, speleothems can provide reliable continental palaeoclimatic information because they are less affected by post-depositional processes than surficial sediments.

This paper presents new data on the d18 O isotopic composition of an Holocene actively growing stalagmite sampled in the Grotta Verde, in Sardinia (Italy), by reporting 14 C age, d18O ratio and growth rates. Speleothems bear valuable palaeoclimatic information in terms of variations in their chemical and stable isotopic compositions through time. A number of proxies in speleothems can be used to extract palaeoclimatic information. Among them, the most commonly used is the variation in oxygen isotopes composition, which is a function of depositional temperature that affects oxygen fractionation between water and calcite and the oxygen isotopic composition of cave drip water that is closely related to mean local precipitation. The second parameter is a function of the longterm cumulative change in a number of competing factors, including, for
* ENEA -Casaccia,Via Anguillarese 301,00060 S.Maria di Galeria Roma,Italy ** ICRAM,Central Institute for Marine Research,Via Casalotti,300,00163 Roma,Italy *** Gruppo Speleologico Sassarese, Sassari, Italy


example, d18 O of the moisture source in the seawater, the temperature gradient between sites of moisture source and precipitation, temperature of vapour condensation in clouds, and the amount of precipitation. The majority of speleothems show a negative relationship between d18O values of calcite and palaeotemperatures. However, a positive relationship may be present in speleothems from areas subject to a temperate maritime western coast climate, such as Ireland, Norway and Tasmania (see Tab. 3 for referenc es). The speleothem growth rate is another important palaeoclimatic indicator that was not widely used previously due to the lack of sufficient high-quality radiometric dating. Speleothem growth is a complex function of calcium concentration in drip water, water supply, and carbon dioxyde concentration in the soil, all of which are climatically related. Water supply (drip rate) is directly correlated with effective precipitation over cave catchments.

THE GROTTA VERDE CAVE The promontory of Capo Caccia is a N-S elongated promontory bounded by steep cliffs, located on the north-western side of Sardegna (Italy), about 12 km West of Alghero (Fig. 1). It mainly consists of limestone, dolomitic limestones and dolostones, Mesozoic in age. A weak deformation reached the sedimentary succession during alpine tectonogenesis, when Sardinia was the foreland to the western alpine belt. Later extensional deformation occurred during the opening of western Mediterranean basins in the Palaeocene-early Neogene, and minor blocksfaulting occurred until recently. Carbonate rocks are mostly affected by high angle normal faults which down-throw towards the western continental margin. Normal fault and associated fractures pivoted the late Neogene Quaternary morphogenesis, which modelled the present configuration of the promontory and individuated karst system along structural discontinuities. Inside the carbonate successions several caves (Mucedda et al., 1997), presently located both below and above sea level, were formed during the late Neogene-Quaternary. Among them the Grotta Verde (Mucedda, 1988) represents one of the most relevant caves due to its remarkable extension, but above all for the exceptional size of the speleothems, whose columns are up to 20 m in height (Fig. 2). The entrance of the cave is at +88 m and leads to an impressive half emerged vaulted room about 25 m high. Huge columns decorate the foyer and are covered by green mosses to which the cave owes

its name; after the cave becomes a narrow descending meander that leads, among other lateral branches, to a terminal room occupied by a little lake at the same outside sea level altitude. The submerged part of the lake is formed by a sub-vertical hole dipping into a small room at –8,5 m containing a neolitic necropolis (now flooded by the sea) Antonioli et al. (1998), Fig. 3. The cave is still active, in many zones is assisted to a water dripping.

Fig. 1 Location of the study area.


Fig. 2: View of the foyer of Grotta Verde, showing columns 35 m high.

M ATERIALS AND METHODS Our first goal was to identify a cave with a very high- growth rate speleothem: the Grotta Verde cave seemed well-suited for this purpose in that it is located in a temperate area with abundant precipitation and presents 35 meters-long columns. In this work we show 14 C data and oxygen isotope time series from a higrowth rate speleothem. To acquire palaeoclimatic data with a temporal


δ18 O Sample (per mil PDB) n. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 -4.17 -4.46 -4.69 -4.08 -3.99 -3.79 -3.53 -4.40 -4.04 -4.78 -4.62 -4.51 -4.77 -4.83 -4.69 -4.86 -4.48 -5.16 -4.60 -4.32 -4.67 -4.59 -4.56 -4.36 -4.20 -4.56 -4.68 -4.76 -4.34 ?

Age determination Yr BP

Age determination δ18 O Sample Yr BP (per mil PDB) n. 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 -4.18 -4.55 -4.15 -3.89 -4.29 -4.18 -4.69 -4.36 -3.74 -3.45 -3.30 -3.89 -3.66 -2.97 -3.36 -3.93 -3.88 -3.36 -4.39 -4.41 -3.41 -4.02 -4.70 -5.02 -4.93 -4.74 -5.42 -5.58 -5.06 ? Active (1998) ?



C AMS 1030 Yr

C AMS 480 Yr

C 679 Yr


scanning of detail, we used a diamond drill 1-1.5 mm wide. Slabs were cut along the growth axis, starting from the bottom of the speleothem to the active layer. The speleothem is 167 mm in length. 58 samples were collected and analysed for oxygen isotopic records. For the isotopic analysis, each sample (200±100 mg) was powdered, then vacuumed at 350°C for 30 min to pyro- lize the organic matter; the powder (30±10 mg) was treated with 100% H3 PO4 at 25°C for 6 hrs. The CO2 released by the reaction was purified by using liquid nitrogen-ethyl alcohol slashed at about –80°C, and measured by a Finnigan Delta massspectrometer. Mean standard deviation of d O18 measurements was typically ±0.1 permil (2 s). The data were reported as δ units relative to Pee Dee Belemnite standard (per mil PDB; Tab. 1).

Fig. 3: A section of the Grotta Verde showing the stalagmite sampling zone.

Radiocarbon dating was performed with both 14 C α-spectrometry and AMS analysis (Tab. 2). The samples for 14 C analysis were cut in correspondence of the first oxygen isotope sample (sample n° 1, AMS dating; see Fig. 4), in correspondence of the lowest data of the oxygen isotope time series (named sample 43, AMS dating) and in correspondence of the oxygen isotope samples number 23-25. The latter analysis was carried out in order to get a control value for growth rates, to acquire more information about time series and to control the availability of the AMS dates.


Lab code 28373 R- 3538 28374

Conventional age 14 C (yrs BP) 1030±40 679±70 480±50

δ 13C (permil PDB) -10.6 –8.24 -8.5

Corresponding δ 18O sample 1 23-25 43

Meth. AMS 14 C AMS

AMS dating was carried out in the Geochron Lab, USA; 14 C dating was carried out in the Radiocarbon Lab of the University of Rome La Sapienza, Italy. In this preliminary work we did not consider any dilution factor for radiocarbon adjustment, on the basis of the very high growth rate and the low thickness of limestones over the top of the cave.

Fig. 4: Section of the stalagmite with: analyses (numbers 1 - 58).


C age (big arrows), and sampling points of d 18 O

RESULTS AND DISCUSSION The uncalibrated age of the sampled speleothem starts 1030 yrs BP until to the actively growing layer, (Tab. 2). Ages provided on the Grotta Verde speleothem show very high growth rates. The calculated growth rates (Fig

5) are: 196 mm/kyr for the period 920 –1271 AD, 266 mm/kyr for the period 1271-1470 and 85 mm/kyr from 1470 to the present day. These growth rates are remarkably high when compared with previous works, and are probably the highest ever recorded in temperate areas (the highest growth rate known so far is 350 mm\kyr, in the tropical area of Oman, Tab. 3).
180 160 140 120 100 80 60 40 20 0

Length (mm)

85 mm/ky 266 mm/ky

196 mm/ky
1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000


Fig. 5: Growth rate of the studied speleothem.

By using the d18 O measurements and their precise ages, we emphasized the study of palaeoclimatic archive utilizing a stalagmite composed of inorganic calcite. Precipitation of this mineral is accompanied by a wellknown isotopic fractionation of -0.22 ‰/°C due to the temperature effect 18 16 (O'Neil et al., 1969). O/ O calcite ratio generally owns an inverse correlation (Epstein et al., 1953). The rain water d18 O values, that will be related with the speleothem growth, depend from latitude (Hays & Grossman, 1991), distance between the sea-ocean and the cave, and regional climate of the cave location (Rozanski et al., 1993). The interaction among these main factors could be influenced the relationship between d18O values and corresponding temperatures. The evidences of historical and geological climate changes during the period of the Grotta Verde speleothem growth, as discussed below, show that the δ 18 O measured in the calcite of the Grotta Verde appears to be very close to the temperature changes, and follows an inverse correlation (hi-temperature/low d18 O), as reported in Epstein et al. (1953). d18 O measurements, resumed in Fig. 6, varied from a maximum of – 2.97 permil PDB to a minimum value –5.58 permil PDB, with the active value of -5.06 permil PDB; the ∆18 O is –2.61.


Site Name Argentarola Cave

Geographical location


Growth rate (mm/ky) 17 40 100 266 130 47

Climate during max growth warm\ wet cold\dry cold\dry cold\dry warm\ wet -

Age method

Relationship between d18 O Vicinity of values and climate trend the oceans (wet-warm or dry-cold) + negative + wet + negative + wet no d O18 measurements + negative + wet and warmer no d O18 measurements + negative + wet and cooler + negative + wet with the exception of LIA + negative + dry + negative + wet + negative + dry and cooler + negative + dry + negative + wet and warmer + negative + wet and warmer 1 1 3 1 3 2

Argentarola island Bard et al., 2002 Italy Marettimo island P. Martini Cave Antonioli et al., 2001 Italy 3 Texas cave Texas-USA Musgrove et al., 2002 Grotta Verde Carlsbard cavern Crag cave Sardinia, Italy New Mexico, USA Ireland This work Polyak & Asmerom, 2001 Mc Dermott et al., 2001 Frisia et al 2000 Verheyden et al., 2000 Bar-Mattew et al., 2000 Xia et al., 2001 Linge et al. 2001 Helstrom & McCullok, 2001 Burns et al., 2001

TIMS dating Th/U dating TIMS dating AMS


TIMS dating TIMS dating and annual lamina counting TIMS dating and annual lamina counting TIMS dating TIMS dating TIMS dating TIMS dating TIMS dating TIMS dating and annual lamina counting

Ernesto cave Pere Noel cave Soreq cave Lynds cave Rana Nettlebed cave Hoti Cave

North Italy Belgium Israel Tasmania - AU Northern-Norway New Zeland Oman

120 65 90 35 55 350*

8.5 - 0 max Present 13-2 max 7 0-140 9,2 5,1 max 7.5 0.25 4.0 max costant 30-0 max 7-8 0-325 max 0.7

cold\dry costant warm\ wet warm\ wet

3 3 2 2 2 2 2

* High air temperatures (~25°C) in the cave, as well as constantly high drip rates are probably the main causative factors leading to the exceptionally high growth rates recorded.

d18 O time series evidences that between the year 1000 AD and the year 1350 AD the isotopic records show a clear low d18 O period (Fig. 6); this trend seems very stable over time. Several climatic indicators (markers) indicate warm and humid conditions for the period from 1400 to 800 yr BP (Iriondo, 1999).


1030±40 yr BP (AMS)

679±70 yr BP

480±50 yr BP (AMS)


-5 δ18 O (PDB) -4


900 1000 1100 1200 1300

1400 1500 Yr AD 1600 1700 1800

1900 2000

Fig. 6: d 18 O values with 14 C age.

Indeed, until the X century and for 500 years it is possible to note a climate variation, commonly described as the Medieval Warm Period (MWP; e.g. Crowley and North, 1991); this period is approximately dated between 1080 and 1350 AD (see Hass, 1996 and references therein). The isotopic records (Fig. 6) show three clear oscillation, with d18O values more positive than the actual during the period crossing 1400 AD, the years 1650 AD and 1850 AD; this oscillation might correspond to the climatic cooling phase known as Little Ice Age (LIA). The LIA is a cold climatic interval that occurred from the middle of the 15th century to the 19th century (Jones and Bradley, 1992; Mann et al., 1998; Watanabe et al., 2001).


After the LIA evidence, we observed the warming trend that characterized the last century. The decrease in d18O values from the lows of the LIA data to the highs of the Present Day data was -2.61 permil PDB. The record obtained on the studied stalagmite also shows a cold peak in the last portion: this is in agreement with evidences of the LIA followed by a temperature rise, as described, for instance, in Dahl-Jensen et al. (1998) and in Mann et al. (1998). This rise in temperature ended around the yrs 1930 –1940 AD, and was followed by a relatively cold period between the yrs 1940 and 1995. The δ 18O trend is also in good agreement with the Dahl-Jensen et al. (1998) reconstruction (Fig. 7). Such reconstruction, based on the GRIP temperature histograms, indicates that for the last 1000 years the Medieval Warm Period (1000 AD) show 1°C warmer than the present, and the LIA show two minimums, at 1500 and 1850 AD. The LIA is followed by a temperature rise culminating around 1930 AD and by a cooling between 1940 and 1995. This last evidence is also visible in the North Atlantic Oscillation (NAO) index (Jones et al., 1997), that is one of the major modes of variability of the Northern Hemisphere atmosphere. It is evident by comparing fig. 5 and 6, that older period of concretioning has higher growth rates than the second one; this could be indicative of a relatively more abundant precipitation during the age corresponding to the MWP age than during the last five centuries. The isotopic evidences, in addition to the radiocarbon ages, suggest that the Grotta Verde speleothem oscillations cover a period over the last 1000 years; the δ 18 O signal of the speleothem, very close to the sea, is clearly interpretable in terms of climate trend by an inverse correlation: an increase/decrease of temperature corresponds to a decrease/increase of delta values, correlated with wet/dry conditions.

CONCLUSION The last 1000 yrs climatic instability was clearly demonstrated by the high-resolution study of a speleothem sampled in the Italian coast, NW Mediterranean. The unusual growth rate of the speleothem sampled in the Grotta Verde, together with the climatic and hydrological characteristics of the Western Sardinia, have provided the results expected. 14 C ages have actually concurred to assess that the studied stalagmite has grown during last 1000 yr, and showed that the growth rate was one of the highest ever recorded: 266mm\yr, about 0.6 ky BP.

900 -6.00

1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000


δ 18 O








δ 18 O


-34.4 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000

Fig. 7: Grotta Verde speleothem d O values (a), temperature change during the last 1000 yrs according to Dahl-Jensen et al 1998 (b), a Monte Carlo inverse method has been used for the temperature profiles measured down through the Greenland Ice Core Project (GRIP, Dansgard et al. 1993) borehole (black curve), at the summit of the Greenland Ice Sheet, and the Dye 3 borehole 865 km further south (grey curve). The last graph (c) reports the d18 O original data of GRIP core. Note the good correlation between the speleothem and the ice-core signal over time: high growth-rate speleothems can provide reliable records for both the Mediterranean region and for global-scale changes.


The d18O values obtained from the Grotta Verde carbonate, showed significant changes in the local water budget during the past 1 ka. Between 1050 and 1400 Yr AD, wet and probably warmer conditions prevailed in the region; the mean of the d18 O values is comprised between -4.4 and -4.9 PDB, with a maximum of -5.2. This climatic and temporal trend confirms that we are in the so-called Medieval Warm Period (MWP). After the 1500 and until 1750 AD, with an exception in 1700 and for a duration of approximately 250 years, a climatic trend dry\cold is evidenced, marked by a reduced rainfall and temperature. The average of the d18O values during this temporal range has been maintained around -3,3 with a maximum value of -3. These observations confirm that the data are situated in the in the socalled Little Ice Age (LIA). The last portion of the graph enhances a wet and warm period that seems to coincide with the Modern Climate Optimum (MCO). In the literature, the Medieval Warm Period (MWP) is approximately centred in 1080-1350 AD (e.g. Linge et al., 2001); the Little Ice Age (LIA) is centred during the period between the years 1600 and 1850 AD ( e.g. Jones and Bradley, 1992; Mann et al., 1998; Watanabe et al., 2001), while the Modern Climate Optimum (MCO) is centred in the middle of the 20th century AD (e.g. in Hass, 1996). This coincidence with the global climatic behaviour has pushed us to provide 14 C ages without corrections; in the near future hydrological, climatic measures and datings using TIMS method will be carried out within the Grotta Verde, in order to assess the effective variations of T° and the calibration of the age. On the basis of the data exposed in table 3, it has been possible to establish that rainfall, temperature or the vicinity of the oceans could have influenced the formation and growth of the speleothems, but the relationship (positive or negative values) between d18O values and climate trend (wetwarm or dry-cold) shows a behaviour that cannot be determined a priori and should be seen case by case. In conclusion, we have shown that the records obtained with high growth-rate speleothems of the NW Mediterranean region are reliable not only for assessing local and regional- scale climate variability, but also for investigating global-scale climatic and environmental changes that took place during the late Holocene. AKNWOLGEMENT We thank S. Frisia for some data of tab 3 and P. Montagna for help in sampling the stalagmite.

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In this study, variations in d 18 O ratios in an Holocene Italian speleothem are interpreted in terms of changes in temperature and hydrological conditions, induced by changes in Western Europe climate. A stalagmite of 17 cm in length was sampled in a cave very near the sea, the Grotta Verde, located on the NW coast of Sardinia (Capo Caccia). Ages were provided using a 14 C AMS technique and analysed for delta d18 O ratio. The results indicate an exceptionally high grow rate (266 mm\ 1000 yrs) and a trend strongly correlated with climate, with the presence of an evident dry\cold peak showing the LIA (Little Ice Age) and a wet\warm peak showing the MWP (Medieval Warm Period).