Barite–pyrite mineralization of the Wiesbaden thermal spring system, Germany: a 500-kyr record of geochemical evolution

Barite–(pyrite) mineralizations from the thermal springs of Wiesbaden, Rhenish Massif, Germany, have been studied to place constraints on the geochemical evolution of the hydrothermal system in space and time. The thermal springs, characterized by high total dissolved solids (TDS) contents and predominance of NaCl, ascend from aquifers at 3–4 km depth and discharge at a temperature of 65–70°C. The barite–(pyrite) mineralization is found in upflow and discharge zones of the present‐day thermal springs as well as at elevations up to 50 m above the current water table. Hence, this mineralization style constitutes a continuous record of the hydrothermal activity, linking the past evolution with the present state of this geothermal system. The sulphur isotope signatures of the mineralization indicate a continuous decrease of the δ³⁴S of sulphate from +16.9‰ in the oldest barite to +10.1‰ in the present‐day thermal water. The δ³⁴S values of barite closely resemble various recently active thermal springs along the southern margin of the Rhenish Massif and contrast strongly with different regional ground and mineral waters. The mineralogical and isotopic signatures, combined with calculations based on uplift rates and the regional geological history, indicate a minimum activity of the thermal spring system at Wiesbaden of about 500 000 years. This timeframe is considerably larger than conservative models, which estimate the duration of thermal spring systems in continental intraplate settings to last for several 10 000 years. The calculated equilibrium sulphur isotope temperatures of coexisting barite and pyrite range between 65 and 80°C, close to the discharge temperature of the springs, which would indicate apparent equilibrium precipitation. Kinetic modelling of the re‐equilibration of the sulphate–sulphide pair during water ascent shows that this process would require 220 Myr. Therefore, we conclude that pyrite is formed from precursor Fe monosulphide phases, which rapidly precipitate in the near‐surface environment, preserving the isotope fractionation between dissolved sulphate and sulphide established in the deep aquifer. Equilibrium modelling of water–mineral reactions shows slight supersaturation of barite at the discharge temperature. Pyrite is already strongly supersaturated at the temperatures estimated for the aquifer (110°C) and processes in the near‐surface environment are most probably related to contact of the thermal water with atmospheric oxygen, resulting in formation of oxidized intermediate sulphur species and precipitation of Fe monosulphide phases, which subsequently recrystallize to pyrite.     

Development of successive karstic systems within the Baix Penedès Fault zone (onshore of the Valencia Trough,NW Mediterranean)

The Baix Penedès Fault zone records successive karstic systems. The outcrops studied correspond to different segments of the fault, which were temporarily connected and disconnected, allowing for different diagenetic processes to occur. The first karstic system affected the Mesozoic rocks due to subaerial exposure after Paleogene compression, an event characterized by widespread dissolution and the generation of vug and cavern porosity. The δ¹⁸O values of the dolomitic sediment filling the initial vuggy porosity are similar to those of the host dolomite, indicating that the sediment comes from the erosion and reworking of the host rock. The second karstic system is related to the upward propagation of the Baix Penedès Fault. This deformation was characterized by random‐fracture fabrics with dolomite cement and sediment. The stable isotopes values and Sr/Ca ratios of both the dolomite cement and sediments are similar to those of the host rock. In contrast, the more depleted δ¹³C values indicate the influence of soil‐derived CO₂ and the opening of the system to meteoric waters. During the third karstic event, the δ¹⁸O, δ¹³C, Sr/Ca ratios, and ⁸⁷Sr/⁸⁶Sr values of diagenetic cements suggest a marine signature, indicating that the karstic sediments were dolomitized under the influence of late Burdigalian‐Langhian marine waters. These marine waters were probably expelled from poorly buried sediments and circulated through faults producing dolomitization of the karstic sediments. A final karst system developed during a period of uplift and subaerial exposure. The δ¹⁸O values, the Mg/Ca and Sr/Ca ratios, and the high radiogenic values of the calcite cements formed during this period indicate precipitation from meteoric waters. The results of this study have implications for carbonate hydrocarbon reservoir analogs subject to karstic influence in the Valencia Trough and elsewhere.     

COMPOSITIONAL VARIATION IN ROMAN COLOURLESS GLASS OBJECTS FROM THE BOCHOLTZ BURIAL (THE NETHERLANDS)*

We investigated the major and trace element composition and Pb and Sr isotope characteristics of a series of about 20 colourless glass objects from a single high‐status Roman burial from the Netherlands (Bocholtz). The major elements show a relatively homogeneous group, with one outlier. This is corroborated by the Sr isotopes. Based on the Sb and Pb content, three major groups can be discerned, with two other outliers. This grouping is corroborated by the contents of the trace elements Bi, Sn, Ag, As and Mo, and by variations in lead isotopic ratios. On the basis of these results, we conclude that the glass of all objects was probably made with sand and lime from the same source. The variation in trace elements and lead isotope composition is most likely the result of variations in the composition of the sulphidic antimony ore(s) that were used to decolourize the glass. The composition of the Bocholtz glass is compared with that of other Roman glass, and implications for production models, trade and use of colourless glass objects are discussed. On the basis of isotopic and major element variation, we conclude that the antimony ore presumably originated from different mines.     

A SCULPTURAL MARBLE OF PRIME QUALITY IN ANTIQUITY—THE DOLOMITIC MARBLE OF THE SIVEC MOUNTAINS IN MACEDONIA

This paper presents analytical data on a major occurrence of fine‐grained dolomitic marble in the Sivec Mountains, close to the city of Prilep in today's former Yugoslavian Republic of Macedonia. This is the first presentation of an analytical database of a large‐scale source of fine‐grained dolomitic marble, whose ancient use can be demonstrated by tool marks and archaeological evidence. Many traces of ancient mining have fallen victim to a big modern quarrying operation in this area, which for decades has produced high‐quality blocks of marble (‘Macedonian Carrara’) and exported them all over the world. A combination of different analytical methods is used to characterize the marbles and to present a database for investigating ancient artefacts made of fine‐grained dolomites. Petrographic investigations revealed the very homogeneous micro‐fabric of this marble, which is of high purity with very low silicate contamination and has a maximum grain‐size of 1 mm. In addition to analysis of the stable isotopes, trace element analyses of carbonate lattice elements (Mg, Fe, Mn and Sr) were performed. An alternative method, the analysis of the chemical composition of the inclusion fluids, was also employed. On the basis of these techniques, a multivariate discrimination analysis was performed, and a clear separation of the different dolomitic marbles (Thasos, Ephesos, Proconnesos and Karacasu) was obtained. Finds of artefacts of high artistic quality made from this dolomite prove the existence of a significant workshop in the neighbourhood of the Sivec quarries. Because of its vulnerability to weathering, this fine‐grained dolomitic marble was used preferentially for indoor applications. Sculptures of prime artistic quality made of Sivec marble have so far been found in several locations of the Republic of Macedonia.     

Fluid mapping in deeply buried Ordovician paleokarst reservoirs in the Tarim Basin,western China

The storage spaces within deeply buried Ordovician paleokarst reservoirs in the Tarim Basin are mostly secondary and characterized by strong heterogeneity and some degree of anisotropy. The types of fluids that fill the spaces within these reservoirs are of great importance for hydrocarbon exploration and exploitation. However, fluid identification from seismic data is often controversial in this area because the seismic velocity for this particular reservoir could be significantly influenced by many factors, including pore shapes, porosity, fluid types, and mineral contents. In this study, we employ the differential effective medium‐Gassmann rock physics model to interpret and discuss the characteristics of conventional karstic carbonate reservoirs in the Tarim Basin that are filled with different fluids (oil, gas, and water) using logging data and thus objectively build corresponding fluid identification criteria. These criteria are subsequently evaluated by amplitude versus offset (AVO) forward analysis based on typical logging data and further applied to ascertain the reservoir fluid types in two different areas in the Tarim Basin based on prestack inversion results. For conventional carbonate reservoirs, gas can be distinguished from heavy oil and water, but heavy oil and water are broadly similar on seismic data. For condensate carbonate reservoirs, water can be differentiated from light oil (i.e., condensates) and gas, but light oil and gas demonstrate substantial similarities in terms of their seismic responses. The predicted fluid results are in good agreement with the results of drilling and oil testing. In particular, modeling the seismically resolvable reservoirs in the carbonate strata in the Tarim Basin, which have needle‐ and sphere‐shaped storage spaces (pore aspect ratio > 0.3) and clay content that is lower than 5%, indicates that fluid properties could be properly evaluated if the porosity is larger than 5% for conventional carbonate reservoirs and >7% for condensate carbonate reservoirs.     

Regional groundwater flow and interactions with deep fluids in western Apennine: the case of Narni‐Amelia chain (Central Italy)

The elemental fluxes and heat flow associated with large aquifer systems can be significant both at local and at regional scales. In fact, large amounts of heat transported by regional groundwater flow can affect the subsurface thermal regime, and the amount of matter discharged towards the surface by large spring systems can be significant relative to the elemental fluxes of surface waters. The Narni‐Amelia regional aquifer system (Central Italy) discharges more than 13 m³ sec^?1 of groundwater characterised by a slight thermal anomaly, high salinity and high pCO₂. During circulation in the regional aquifer, groundwater reacts with the host rocks (dolostones, limestones and evaporites) and mixes with deep CO₂‐rich fluids of mantle origin. These processes transfer large amounts of dissolved substances, in particular carbon dioxide, and a considerable amount of heat towards the surface. Because practically all the water circulating in the Narni‐Amelia system is discharged by few large springs (Stifone‐Montoro), the mass and energy balance of these springs can give a good estimation of the mass and heat transported from the entire system towards the surface. By means of a detailed mass and balance of the aquifer and considering the soil CO₂ fluxes measured from the main gas emission of the region, we computed a total CO₂ discharge of about 7.8 × 10⁹ mol a^?1 for the whole Narni‐Amelia system. Finally, considering the enthalpy difference between infiltrating water and water discharged by the springs, we computed an advective heat transfer related to groundwater flow of 410 ± 50 MW.     

THE CHARACTERIZATION OF WATERLOGGED ARCHAEOLOGICAL WOOD: THE THREE ROMAN SHIPS FOUND IN NAPLES (ITALY)*

Three apparently well‐preserved shipwrecks dating back to Roman times were brought to light near Piazza Municipio in Naples (Italy), during the excavation for the construction of Line 1 of the subway. The shipwrecks were covered by marine sand and silt, below the water table. In order to establish the nature and the extent of wood degradation and, therefore, determine how best to preserve the shipwrecks, a diagnostic investigation was carried out. The study involved the identification of wood species, chemical characterization of the residue component and physical and micro‐morphological characterization.     

WHITE,VEINED MARBLE FROM ROMAN AMMAIA (PORTUGAL): PROVENANCE AND USE

A multimethod approach using petrography and strontium (Sr) isotopic analysis was applied to determine the geological source of 17 marble artefacts from the Roman town of Ammaia (Portugal). All samples are calcitic, with dolomite, quartz and muscovite as accessory minerals. The marbles are characteristically medium‐grained with a maximum grain size (MGS) between 0.98 mm and 1.82 mm, have a heteroblastic texture, and have curved to embayed calcite grain boundaries. ⁸⁷Sr/⁸⁶Sr values of marble leachates range from 0.708488 to 0.708639. Comparison with Hispanic and Mediterranean marbles suggests the Estremoz Anticline as the most likely source for the Ammaia marble, especially for architectural marble. This hypothesis is supported by the geographical proximity of the Estremoz marble district and the long and expensive overland transport required for other marbles to reach Ammaia.     

THE FIRST ARCHAEOMETRIC CHARACTERIZATION OF ROMAN MILLSTONES FOUND IN THE AQUILEIA ARCHAEOLOGICAL SITE (UDINE,ITALY)*

An archaeometric study of all the Roman millstones preserved today in the National Archaeological Museum of Aquileia, the ancient capital of the X Regio Augustea –‘Venetia et Histria’ located on the Friuli plain (northeastern Italy), has been recently envisaged to define their geological–geographical provenance. We present here the results of the first step of the research, which is aimed at characterizing all of the definitely allochthonous lithologies. In order to carry out petrography on thin‐section and geochemical analyses, 10 small samples were picked out directly from Pompeian‐style millstones (catilli and/or metae) and rotary querns. Five different lithologies originating in various Italian regions were recognized: eight samples consist of pale‐ and dark‐grey lavas from the Venetian Volcanic Province, Vulsini Volcanic District (Latium), Etna Volcano and Pantelleria island (Sicily), whereas two samples were shown to be made of green garnet‐bearing schists (pietra ollare) from the Western Italian Alps. The presence of Alpine pietra ollare in northeastern Italy, used to produce pots and food containers, was established for numerous classical findings at Roman and Middle Age sites, but the analysed items represent the first evidence for the utilization of this kind of stone to produce mills during the Roman epoch.     

ON THE WHITE AND COLOURED MARBLES OF THE ROMAN TOWN OF CUICUL (DJEMILA,ALGERIA)

This paper reports the results of an archaeometric study of the local and imported marbles found in the Roman town of Cuicul (now Djemila, Algeria), a research project funded by the Sixth Framework Programme of the European Union. Of the few imported coloured lithotypes that have been found, four are of Greek origin and one was imported from Asia Minor. In addition, two other classical Roman coloured stones found on the site are probably of local North African origin (most likely one from Numidia and one from Algeria). With regard to the grey and white marbles employed in the statuary and architecture, petrographic study in thin section and the δ¹³C and δ¹⁸O isotopic data emphasize the frequent use of the local fine‐grained lithotype from Filfila (Skikda) together with imported Greek lithotypes (i.e., Pentelic marble, the dolomitic variety of Thasian marble, and Parian marble from Lakkoi) as well as different varieties of the so‐called ‘greco scritto’, whose provenance in some cases still remains uncertain. In fact, the petrographic and geochemical features of the marbles do not always match those known for the classical ‘greco scritto’ from the quarry of Cap de Garde, near Annaba (Algeria).     

Decreasing CO2 partial pressure triggered Mg–Fe–Ca carbonate formation in ancient Martian crust preserved in the ALH84001 Meteorite

We retrace hydrogeochemical processes leading to the formation of Mg–Fe–Ca carbonate concretions (first distinct carbonate population, FDCP) in Martian meteorite ALH84001 by generic hydrogeochemical equilibrium and mass transfer modeling. Our simple conceptual models assume isochemical equilibration of orthopyroxenite minerals with pure water at varying water‐to‐rock ratios, temperatures and CO₂ partial pressures. Modeled scenarios include CO₂ partial pressures ranging from 10.1325 to 0.0001 MPa at water‐to‐rock ratios between 4380 and 43.8 mol mol^?1 and different temperatures (278, 303 and 348 K) and enable the precipitation of Mg–Fe–Ca solid solution carbonate. Modeled range and trend of carbonate compositional variation from magnesio‐siderite (core) to magnesite (rim), and the precipitation of amorphous SiO₂ and magnetite coupled to magnesite‐rich carbonate are similar to measured compositional variation. The results of this study suggest that the early Martian subsurface had been exposed to a dynamic gas pressure regime with decreasing CO₂ partial pressure at low temperatures (approximately 1.0133 to 0.0001 MPa at 278 K or 6 to 0.0001 MPa at 303 K). Moderate water‐to‐rock ratios of ca. 438 mol mol^?1 and isochemical weathering of orthopyroxenite are additional key prerequisites for the formation of secondary phase assemblages similar to ALH84001’s ‘FDCP’. Outbursts of water and CO_2(g) from confined ground water in fractured orthopyroxenite rocks below an unstable CO₂ hydrate‐containing cryosphere provide adequate environments on the early Martian surface.     

ANALYTICAL CHARACTERIZATION OF ROMAN PLASTERS OF THE ‘DOMUS FARINI’ IN MODENA*

The paper refers to the analytical characterization of Roman painted plasters dating back to the second century ad . The following techniques were used: optical microscopy (OM), scanning electron microscopy (SEM–EDS), micro‐Raman and Fourier transform infrared spectroscopies (µ‐Raman and FT–IR), X‐ray diffraction (XRPD), colorimetry and thermal analyses (TG/DTA). The investigation analysed the chemical composition and structure of the plasters, the chemical composition of the pigment layers, the use of binders and any chemical alteration of pigments as well as deterioration of the samples. Stratigraphic analysis of plasters allowed identification of their individual components, which proved helpful in finding out more about the mural painting technique employed.     

Roman Builders Facing the Risk of Disaster: Coupling Archaeological and Geochemical Analyses on a Section of the ‘Aqua Augusta’ (the Roman Serino Aqueduct,Southern Italy)

Four samples of carbonate sinters from two sites of the Roman Serino aqueduct were studied in order to better constrain the history of the aqueduct and to estimate to what extent natural hazards can be recorded in such deposits. Micromorphological observations, trace element, stable oxygen and carbon isotope analyses were performed on the samples. Together with new quantitative observations on the construction techniques of the aqueduct, our results highlight the imprint left by geological hazards on the Serino aqueduct. Damage, disruption, ground movement and a debris‐flow are evidenced.     

Origin of palaeo‐waters in the Ordovician carbonates in Tahe oilfield,Tarim Basin: constraints from fluid inclusions and Sr,C and O isotopes

Petrographic features, isotopes, and trace elements were determined, and fluid inclusions were analyzed on fracture‐filling, karst‐filling and interparticle calcite cement from the Ordovician carbonates in Tahe oilfield, Tarim basin, NW China. The aim was to assess the origin and evolution of palaeo‐waters in the carbonates. The initial water was seawater diluted by meteoric water, as indicated by bright cathodoluminescence (CL) in low‐temperature calcite. The palaeoseawater was further buried to temperatures from 57 to 110°C, nonluminescent calcite precipitated during the Silurian to middle Devonian. Infiltration of meteoric water of late Devonian age into the carbonate rocks was recorded in the first generation of fracture‐ and karst‐filling dull red CL calcite with temperatures from <50°C to 83°C, low salinities (<9.0 wt%), high Mn contents and high ⁸⁶Sr/⁸⁷Sr ratios from 0.7090 to 0.7099. During the early Permian, ⁸⁷Sr‐rich hydrothermal water may have entered the carbonate rocks, from which precipitated a second generation of fracture‐filling and interparticle calcite and barite cements with salinities greater than 22.4 wt%, and temperatures from 120°C to 180°C. The hydrothermal water may have collected isotopically light CO₂ (possibly of TSR‐origin) during upward migration, resulting in hydrothermal calcite and the present‐day oilfield water having δ¹³C values from ?4.3 to ?13.8‰ and showing negative relationships of ⁸⁷Sr/⁸⁶Sr ratios to δ¹³C and δ¹⁸O values. However, higher temperatures (up to 187°C) and much lower salinities (down to 0.5 wt%) measured from some karst‐filling, giant, nonluminescent calcite crystals may suggest that hydrothermal water was deeply recycled, reduced (Fe‐bearing) meteoric water heated in deeper strata, or water generated from TSR during hydrothermal water activity. Mixing of hydrothermal and local basinal water (or diagenetically altered connate water) with meteoric waters of late Permian age and/or later may have resulted in large variations in salinity of the present oilfield waters with the lowest salinity formation waters in the palaeohighs.     

OXYGEN AND CARBON ISOTOPE ANALYSIS OF HUMAN TOOTH ENAMEL FROM THE NEW KINGDOM SITE OF TOMBOS IN NUBIA

This study examines the feasibility of using oxygen isotope analysis of tooth carbonate to identify immigrants from the New Kingdom site of Tombos in Nubia (n = 30). In comparison with published data, the results (δ¹⁸O_ca,VSMOW = 31.4‰) imply a substantial presence of immigrants. However, further analysis of these data strongly suggests the need to consider hydrological and cultural factors such as the contribution of aquifer waters to the Nile, use of groundwater sources, and differences in handling and storage of water. The carbon isotope analysis, in conjunction with published ⁸⁷Sr/⁸⁶Sr data, provides additional support for the presence of immigrants at Tombos.     

Response of Alum Rock springs to the October 30, 2007 Alum Rock earthquake and implications for the origin of increased discharge after earthquakes

The origins of increased stream flow and spring discharge following earthquakes have been the subject of controversy, in large part because there are many models to explain observations and few measurements suitable for distinguishing between hypotheses. On October 30, 2007 a magnitude 5.5 earthquake occurred near the Alum Rock springs, California, USA. Within a day we documented a several‐fold increase in discharge. Over the following year, we have monitored a gradual return towards pre‐earthquake properties, but for the largest springs there appears to be a permanent increase in discharge. The Alum Rock springs discharge waters that are a mixture between modern (shallow) meteoric water and old (deep) connate waters expelled by regional transpression. After the earthquake, there was a small and temporary decrease in the fraction of connate water in the largest springs. Accompanying this geochemical change was a small (1–2°C) temperature decrease. Combined with the rapid response, this implies that the increased discharge has a shallow origin. Increased discharge at these springs occurs both for earthquakes that cause static volumetric expansion and for those that cause contraction, supporting models in which dynamic strains are responsible for the subsurface changes that cause flow to increase. We make a quantitative comparison between the observed changes and model predictions for three types of models: (i) a permanent increase in permeability; (ii) an increase in permeability followed by a gradual decrease to its pre‐earthquake value; and (iii) an increase of hydraulic head in the groundwater system discharging at the springs. We show that models in which the permeability of the fracture system feeding the springs increases after the earthquake are in general consistent with the changes in discharge. The postseismic decrease in discharge could either reflect the groundwater system adjusting to the new, higher permeability or a gradual return of permeability to pre‐earthquake values; the available data do not allow us to distinguish between these two scenarios. However, the response of these springs to another earthquake will provide critical constraints on the changes that occur in the subsurface and should permit a test of all three types of models.     

Diagenesis of the Amposta offshore oil reservoir (Amposta Marino C2 well,Lower Cretaceous,Valencia Trough,Spain)

Samples from the Amposta Marino C2 well (Amposta oil field) have been investigated in order to understand the origin of fractures and porosity and to reconstruct the fluid flow history of the basin prior, during and after oil migration. Three main types of fracture systems and four types of calcite cements have been identified. Fracture types A and B are totally filled by calcite cement 1 (CC1) and 2 (CC2), respectively; fracture type A corresponds to pre‐Alpine structures, while type B is attributed to fractures developed during the Alpine compression (late Eocene‐early Oligocene). The oxygen, carbon and strontium isotope compositions of CC2 are close to those of the host‐rock, suggesting a high degree of fluid‐rock interaction, and therefore a relatively closed palaeohydrogeological system. Fracture type C, developed during the Neogene extension and enlarged by subaerial exposure, tend to be filled with reddish (CS3r) and greenish (CS3g) microspar calcite sediment and blocky calcite cement type 4 (CC4), and postdated by kaolinite, pyrite, barite and oil. The CS3 generation records lower oxygen and carbon isotopic compositions and higher ⁸⁷Sr/⁸⁶Sr ratios than the host‐limestones. These CS3 karstic infillings recrystallized early within evolved‐meteoric waters having very little interaction with the host‐rock. Blocky calcite cement type 4 (CC4 generation) has the lowest oxygen isotope ratio and the most radiogenic ⁸⁷Sr/⁸⁶Sr values, indicating low fluid‐rock interaction. The increasingly open palaeohydrogeological system was dominated by migration of hot brines with elevated oxygen isotope ratios into the buried karstic system. The main oil emplacement in the Amposta reservoir occurred after the CC4 event, closely related to the Neogene extensional fractures. Corrosion of CC4 (blocky calcite cement type 4) occurred prior to (or during) petroleum charge, possibly related to kaolinite precipitation from relatively acidic fluids. Barite and pyrite precipitation occurred after this corrosion. The sulphur source associated with the late precipitation of pyrite was likely related to isotopically light sulphur expelled, e.g. as sulphide, from the petroleum source rock (Ascla Fm). Geofluids (2010) 10 , 314–333     

MARINE RESOURCES IN THE MESOLITHIC AND NEOLITHIC AT THE GROTTA DELL’UZZO (SICILY): EVIDENCE FROM ISOTOPE ANALYSES OF MARINE SHELLS*

Oxygen isotopes in shell carbonate samples from the marine rocky‐shore intertidal gastropod Monodonta turbinata (Born) are investigated in both modern analogue specimens and in archaeological specimens from the Grotta dell’Uzzo (Sicily). Variations in shell edge values of δ¹⁸O in living specimens collected monthly over two years are closely correlated with monthly seawater temperatures measured at the time of collection, showing that the species can be used for palaeoseasonality studies. Analyses of shell edge δ¹⁸O values in archaeological specimens, from Mesolithic through to early Neolithic phases at the Grotta dell’Uzzo, enabled the inference of various seasons of collection of shellfish and how such seasonality varies between the different phases of occupation. Interesting similarities and differences exist between the seasons of marine shellfish exploitation and the seasons inferred from the vertebrate zooarchaeological assemblages. A major inference drawn from the analyses and discussion is that the exploitation of all marine resources (fish and shellfish) increased in the later Mesolithic and early Neolithic periods.     

THE CHARACTERIZATION OF PAINTS AND WATERPROOFING MATERIALS FROM THE SHIPWRECKS FOUND AT THE ARCHAEOLOGICAL SITE OF THE ETRUSCAN AND ROMAN HARBOUR OF PISA (ITALY)*

This work presents the results of a diagnostic survey on the shipwrecks from the archaeological site of the ancient harbour of San Rossore (Pisa, Italy). The original waterproofing, caulking and painting materials were characterized by Fourier transform infrared spectroscopy (FTIR), gas chromatography – mass spectrometry (GC–MS), energy‐dispersive X‐ray microanalysis (EDX) and X‐ray diffraction (XRD). The major constituents of the waterproofing and caulking materials detected on the planks were tricyclic abietanes showing a high degree of aromatization. These compounds are indicative of a pitch obtained from the wood of trees of the Pinaceae family. The analysis of the organic components of the paint samples revealed diterpenoid acids characteristic of Pinaceae resins together with linear long‐chain alcohols and fatty acids, highlighting the presence of beeswax. Noticeably, the characteristic odd carbon number alkanes that are normally present in beeswax were not detected. The EDX and XRD analyses showed that hematite, calcite, cerussite and kaolinite were employed as pigments to paint the ships’ hulls.