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1.
One hundred and twenty‐five new lead isotopic analyses on galena, mainly from the Los Pedroches – Alcudia Valley area of southern Iberia, are presented. These data allow us to define four compositional groups in the 207Pb/206Pb versus 208Pb/206Pb and 207Pb/206Pb versus 206Pb/204Pb diagrams. Group I compositions are intermediate between those previously reported for southeastern and southwestern Iberian ore mineral locations. The compositions of Group II, the largest group, overlap with ore data from southwestern Spain. Groups III and IV have compositions that have never before been identified in this region and are comparable to those from the Sardinian Cu ores, which might explain the previously assumed exotic origin for local Bronze Age artefacts.  相似文献   

2.
The archaeological discovery of the Acqualadrone rostrum (an offensive naval weapon mounted on the prow at the waterline), off the Italian coast near Messina in 2008, has led to the need for scientific research in order to plan the conservation treatment of this artefact. The discovery is exceptional because of the presence of a wooden section from the original ship. This paper describes the physico‐chemical characterization of a metallic and two wooden samples by inductively coupled plasma – optical emission spectroscopy, inductively coupled plasma – mass spectrometry, Fourier transform infrared spectroscopy, 13C {1H} cross‐polarization magic angle spinning NMR spectroscopy, energy‐dispersive X‐ray spectroscopy, gas chromatography – mass spectrometry and X‐ray diffraction. The results reveal the use of leaded bronze (Cu, 70%; Pb, 20%; Sn, 10%) in the manufacturing process of the alloy and the use of lead whose isotopic composition is referable to either Spanish or Cypriot mines. The analysis of the results relating to the wooden samples indicates their different state of preservation and, at least in some places, the spreading of caulking on the wood, probably using a vegetable resin.  相似文献   

3.
High‐sulfidation vein gold deposits such as El Indio, Chile, formed in fracture arrays <1000 m beneath paleo‐solfatara in volcanic terranes. Stable isotope data have confirmed a predominance of magmatic vapor during the deposition of arsenic‐rich sulfide–sulfosalt assemblages in this deposit. These provide a unique opportunity to analyze the processes and products of high‐temperature volcanic gas expansion in fractures that form the otherwise inaccessible infrastructure deep inside equivalent present‐day fumaroles. We provide field emission scanning electron microscope and LA‐ICP‐MS micro‐analytical data for the wide range of heavy, semi‐metals and metalloids (arsenic, antimony, bismuth, tin, silver, gold, tellurium and selenium) in the complex pyrite‐enargite‐Fe‐tennantite assemblages from Copper Stage mineralization in the El Indio deposit. These data document the progressive fractionation of antimony and other heavy metals, such as bismuth, during crystallization from a sulfosalt melt that condensed from expanding vapor at about 15 MPa (150 bars) and >650°C following higher temperature vapor deposition of crystalline pyrite and enargite. The sulfosalt melt aggressively corroded the earlier enargite and pyrite and hosts clusters of distinctive euhedral quartz crystals. The crystallizing sulfosalt melt also trapped an abundance of vugs within which heavy metal sulfide and sulfosalt crystals grew together with K‐Al silicates and fluorapatite. These data and their geologic context suggest that, in high‐temperature fumaroles on modern active volcanoes, over 90% of the arsenic content of the primary magmatic vapor (perhaps 2000 mg kg?1) was precipitated subsurface as sulfosalt. Subsurface fractionation may also account for the range of exotic Pb‐Sn‐Bi‐Se sulfosalts observed in fumarole sublimates on active volcanoes such as Vulcano, Italy, as well as on extra‐terrestrial volcanoes such as Maxwell Montes, Venus.  相似文献   

4.
In this paper we present data to demonstrate the applicability of laser‐ablation MC–ICP–MS isotope analysis to archaeological artefacts, in this case Roman silver coins. The technique requires no chemical preparation, does minimal damage to the sample and yields external reproducibility that is better than conventional TIMS analysis; 207Pb/206Pb =±0.015% 2σ in comparison with 207Pb/206Pb =±0.04% 2σ, respectively. We show that Pb isotope compositions give isotope fingerprints to mints despite the likely reworking of the metal during coin production.  相似文献   

5.
Lead and strontium isotope analyses were performed by thermal ionization mass spectrometry (TIMS) on Roman to Byzantine iron artefacts and iron ores from the territory of ancient Sagalassos (south‐west Turkey), to evaluate Pb and Sr isotopes for provenance determination of ores for local iron production. It can be demonstrated that for early Roman artefacts and hematite iron ore processed in early Roman times from Sagalassos proper, as well as for magnetite placer sands and early Byzantine raw iron from the territory of the city, Sr isotopes are much less ambiguous than Pb isotopes in providing clearly coherent signatures for ore and related iron objects. Late Roman iron objects were produced from iron ores that as yet remain unidentified. Early Byzantine iron artefacts display more scatter in both their Pb and Sr isotope signatures, indicating that many different ore sources may have been used. Our study demonstrates that iron objects can be precisely analysed for their Sr isotopic composition, which, compared to Pb isotopes, appears to be a much more powerful tool for distinguishing between chronological groups and determining the provenance of raw materials.  相似文献   

6.
Z. AL‐SAA'D 《Archaeometry》2000,42(2):385-397
Chemical and lead isotope analyses were utilized to determine the composition, technology and origin of a collection of Islamic copper‐based objects found in Jordan. The atomic absorption spectrometry results show that the objects were made of different types of copper‐base alloys that contain various amounts of zinc, tin and lead. The use of brass, highly leaded brass and quaternary alloys of Cu‐Zn‐Sn‐Pb in the manufacture of everyday, household objects strongly points to Islamic traditions. The lead isotope compositions of the objects match very well that of the copper ore mined from the Dolomite‐Limestone‐Shale unit of the Arabah copper mines.  相似文献   

7.
The mineralized fracture system that underlay paleo‐fumarole field at Chinkuashih, Taiwan has been exposed by copper–gold mining to depths of about 550 m below the paleo‐surface. Its mineralogy and systematic variations in metal and semimetal (Fe, Cu, As, Sb, Bi, Hg, Cd, Sn, Zn, Pb, Se, Te, Au, Ag) concentrations provide insights into the chemical responses of a magmatic‐vapor phase as it expands through fracture arrays to the surface and discharges as fumaroles associated with more extensive solfatara. At Chinkuashih, following initial sealing of the fractures by silica‐alunite alteration, brittle failure reestablished discharge from an underlying reservoir of magmatic vapor. Crystalline pyrite was deposited first in the fractures and was succeeded and replaced by ‘enargite’ (Cu3(As,Sb)S4) as sulfosalt encrustations (‘sublimate’) on fracture surfaces and in extensional cracks. Subsequent recrystallization resulted in complex exsolution intergrowths with antimony fractionation to the evolving crystal–vapor interface. Heavy metal fractionation between sulfosalt and vapor enriched the vapor phase in heavy metals that subsequently precipitated as complex Bi–Hg–Sn sulfosalts in discrete areas (paleo‐fumaroles) close to the paleo‐surface in a manner analogous to modern‐day fumaroles on active volcanoes such as Vulcano, Italy. As in similar paleo‐fumaroles (e.g., El Indio, Chile and Lepanto, Philippines), the most characteristic reaction sequence is the partial replacement of the early pyrite by enargite and Fe‐tennantite. It is proposed that this reaction tracks the decrease in the pressure of the underlying magmatic‐vapor reservoir because of the sustained discharge of vapor to the surface.  相似文献   

8.
The mineralogy, petrography and major‐ and trace‐element composition of iron ores from Elba Island (Tuscany, Italy), one of the most important iron sources in the Mediterranean area since the first millennium bc , revealed that hematite‐rich ores display prominent enrichments in W and Sn (up to 4950 μg g?1 and 8400 μg g?1, respectively). These two elements are hosted by tiny grains of W–Sn mineral phases (ferberite, scheelite and cassiterite) that are disseminated throughout the hematite matrix. A comparison with iron ores from many Italian and European localities (most of which were exploited in ancient times) suggests the uniqueness of the geochemical pattern of Elba Island hematite‐rich ores (i.e., high W and Sn, low Mo and low Cu, Pb and Zn). We suggest that this geochemical signature may represent a new provenance marker not only for discarded ore at smelting/smithing sites, but, possibly, also for metallurgical slag and smelted metal produced in the chaîne opératoire of the iron process.  相似文献   

9.
The reliable identification of fakes consisting of bronze often presents problems, because traditional methods such as stylistic studies, optical microscopy, chemical analysis or X‐ray diffraction of the corrosion may not be conclusive. We present a method that is based on the comparison of the tin isotope ratios 122Sn/116Sn and 117Sn/119Sn in the metal and in the adherent corrosion layer. An artificial patina is usually generated within a short time period. It has been observed that such a procedure leads to a depletion of the light tin isotopes in the corrosion layer, while in naturally corroded authentic archaeological objects no isotopic fractionation has been detected. The method has also been applied to archaeological objects and it could be confirmed, among other examples, that the famous ‘Sky Disc of Nebra’ is authentic.  相似文献   

10.
Pulsed thermography has been applied to the quantitative characterization of the insertions of two ancient bronzes, the Boxer at Rest and the Hellenistic Prince. The analysis of the thermographic signal time dependence performed by a specifically developed model enabled the evaluation of the insertions’ thickness and of elements which could provide indications about the procedure followed for their insertion. This could be achieved by exploiting a semi-empirical relation establishing the thermal diffusivity dependence on the total effective weighted concentration of Sn and Pb atoms obtained from the analysis of the values determined on samples containing different concentrations of Sn and Pb.  相似文献   

11.
The historical Norberg mining district in central Sweden with its shallow, easily accessible iron ores figures prominently in the earliest documents from the 14th century concerning mining or metallurgy. This 1000-km2 district is considered to be one of the first areas in Sweden exploited for iron ores and, in fact, Europe’s oldest known blast furnace, Lapphyttan, is located in the Norberg district about 10 km from the mines in the village of Norberg (Norbergsby). Earlier archaeological excavations suggest the furnace was in operation as early as the 11th or 12th century (870 and 930 14C yr BP), and a number of other sites in the district have been dated to the 13th–15th centuries. Here, we have analyzed two lake sediment records (Kalven and Noren) from the village of Norberg and a peat record from Lapphyttan. The Lapphyttan peat record was radiocarbon dated, whereas the sediment from Kalven is annually laminated, which provides a fairly precise chronology. Our pollen data indicate that land use in the area began gradually as forest grazing by at least c. AD 1050, with indications of more widespread forest disturbance and cultivation from c. 1180 at Lapphyttan and 1250 at Kalven. Based on 206Pb/207Pb isotope ratios in Kalven’s varved sediment record, there is an indication of mining or metallurgy in the area c. 960, but likely not in immediate connection to our sites. Evidence of mining and metallurgy increases gradually from c. 1180 when there is a decline in 206Pb/207Pb ratios and an increase in charcoal particles at Lapphyttan, followed by increasing inputs of lithogenic elements in Noren’s sediment record indicating soil disturbance, which we attribute to the onset of mining the iron ore bodies surrounding Noren. From AD 1295 onwards evidence of mining and metallurgy are ubiquitous, and activities accelerate especially during the late 15th century; the maximum influence of Bergslagen ore lead (i.e., the minimum in 206Pb/207Pb isotope ratios) in both Kalven and Noren occurs c. 1490–1500, when also varve properties change in Kalven and in Noren sharp increases occur in the concentrations of a range of other ore-related metals (e.g., arsenic, cadmium, copper, iron, lead, mercury and zinc). From the 15th century onwards mining and metallurgy are the dominant feature of the sediment records.  相似文献   

12.
N. H. GALE 《Archaeometry》1997,39(1):71-82
A recent suggestion that some ancient metallurgical processes might give rise to large changes (> 0.5%) in the isotopic composition of tin gave hope that it might be possible to identify ancient bronze samples which had undergone recycling and mixing processes. This paper describes a method for the analysis of the isotopic composition of tin by thermal ionization mass spectrometry and applies it to analyse a number of ancient bronzes and tin metal objects from the Bronze Age Mediterranean. No observable isotopic fractionation of tin was found above $0.1% in the ratio122 Sn/116. Consequently, either recycling of bronze in the Late Bronze Age Mediterranean was not so common as supposed, or the isotopic composition of tin is not fractionated by anthropogenic metallurgical processes to the extent predicted by the Bradford group.  相似文献   

13.
The Trèves zinc–lead deposit is one of several Mississippi Valley‐type (MVT) deposits in the Cévennes region of southern France. Fluid inclusion studies show that the ore was deposited at temperatures between approximately 80 and 150°C from a brine that derived its salinity mainly from the evaporation of seawater past halite saturation. Lead isotope studies suggest that the metals were extracted from local basement rocks. Sulfur isotope data and studies of organic matter indicate that the reduced sulfur in the ores was derived from the reduction of Mesozoic marine sulfate by thermochemical sulfate reduction or bacterially mediated processes at a different time or place from ore deposition. The large range of δ34S values determined for the minerals in the deposit (12.2–19.2‰ for barite, 3.8–13.8‰ for sphalerite and galena, and 8.7 to ?21.2‰ for pyrite), are best explained by the mixing of fluids containing different sources of sulfur. Geochemical reaction path calculations, based on quantitative fluid inclusion data and constrained by field observations, were used to evaluate possible precipitation mechanisms. The most important precipitation mechanism was probably the mixing of fluids containing different metal and reduced sulfur contents. Cooling, dilution, and changes in pH of the ore fluid probably played a minor role in the precipitation of ores. The optimum results that produced the most metal sulfide deposition with the least amount of fluid was the mixing of a fluid containing low amounts of reduced sulfur with a sulfur‐rich, metal poor fluid. In this scenario, large amounts of sphalerite and galena are precipitated, together with smaller quantities of pyrite precipitated and dolomite dissolved. The relative amounts of metal precipitated and dolomite dissolved in this scenario agree with field observations that show only minor dolomite dissolution during ore deposition. The modeling results demonstrate the important control of the reduced sulfur concentration on the Zn and Pb transport capacity of the ore fluid and the volumes of fluid required to form the deposit. The studies of the Trèves ores provide insights into the ore‐forming processes of a typical MVT deposit in the Cévennes region. However, the extent to which these processes can be extrapolated to other MVT deposits in the Cévennes region is problematic. Nevertheless, the evidence for the extensive migration of fluids in the basement and sedimentary cover rocks in the Cévennes region suggests that the ore forming processes for the Trèves deposit must be considered equally viable possibilities for the numerous fault‐controlled and mineralogically similar MVT deposits in the Cévennes region.  相似文献   

14.
The kinetics of thermochemical sulfate reduction (TSR) were studied in experiments at 205–250°C, with determination of both sulfate and sulfide at intervals during the runs of up to 430 h. Analysis of the data indicates the reaction to have first‐order kinetics, and extrapolating these data, plus data from the literature, to 150°C gives a range of possible rate constants from 100 to 10?4 year?1. Although the rate law has not been well established, a reasonable estimate allows calculation of the amount of sulfide ore formed as a function of flow conditions and time. It is here concluded that TSR could happen during the formation of Mississippi Valley‐type ore deposits, subject to several caveats.  相似文献   

15.
In the North Aegean Domain, Thassos Island contains a Plio‐Pleistocene basin controlled by a large‐scale flat‐ramp extensional system with a potential décollement located at depth within a marble unit. Numerous mineralizations associated with normal faults of Plio‐Pleistocene age are the sign of fluid circulation during extension. Two main generations of fluid flow are recognized, related to Plio‐Pleistocene extension. A first circulation under high‐temperature conditions (about 100–200°C) resulted in dolomitization of marbles near the base of the Plio‐Pleistocene basin. The dolomites are characterized by low δ18O values (down to 11‰ versus Standard Mean Ocean Water). Some cataclastic deformation affected the dolomites. Hydrothermal quartz that crystallized in extension veins above a blind ramp also has low δ18O values (about 13‰). This shows that high‐temperature fluids moved up from the décollement level toward the surface. A second downward circulation of continental waters at near‐surface temperature is documented by calcite veins in fault zones and at the base of the Plio‐Pleistocene basin. These veins have O isotope values relatively constant at about 23–25‰ and C isotope values intermediate between the high δ13C value of the carbonate host rock (about 1–3‰ versus Peedee Belemnite) and the low δ13C value of soil‐derived carbon (?10‰). The calcites associated with the oxidative remobilization of primary sulphide Zn–Pb mineralization of Thassos carbonates have comparable O and C isotope compositions. Hot fluids, within the 100–200°C temperature range, have likely contributed to the weakening of the lower marble unit of Thassos and, thus, to the process of décollement.  相似文献   

16.
The possibility of lead isotope fractionation in ancient lead production is examined. Kinetic theory relating to isotopic fractionation in non-equilibrium evaporation is considered and the feasibility of the alteration of lead isotope abundance ratios in ore roasting and smelting is assessed. Previous experimental work is shown to have been inconclusive and conclusions are drawn on the need for further research to quantify the possible extent of fractionation in practice.  相似文献   

17.
Lead isotope analysis has been applied to the investigation of some Roman objects found in the town of Pompeii, consisting mostly of fistulae from the Augustan water supply system. The results of the analyses have produced ratios between 18.10 and 18.66 for 206Pb/204Pb, between 15.63 and 15.72 for 207Pb/204Pb and between 38.21 and 38.98 for 208Pb/204Pb. These data point to a fairly complex origin for the lead artefacts, probably involving several successive meltings and recyclings of a rather heterogeneous lead supply. The spread of lead isotope ratios can only be reconciled with a multiplicity of end‐members, at least three, but very probably more. There is one certain Sardinian ore, other indistinguishable Hercynian ores of Sardinia and/or Spain, and several different Alpine Mesozoic‐Tertiary mineralizations of the Mediterranean basin (Spain, Greece, Tuscany).  相似文献   

18.
Numerical groundwater modeling was used to investigate the role of fluid flow associated with uplift of the Arkoma basin during the closing stages of the Ouachita orogeny in forming the Mississippi Valley‐type Zn–Pb ores of the Tri‐State district. The model hydrostratigraphy was flexurally compensated to account for the restoration of Pennsylvanian–Permian sediments removed since the close of the orogeny in estimating the regional paleotopographic gradient. Estimates of the amount of Pennsylvanian–Permian sediment that has been removed by erosion vary widely. A thick and a thin endmember case were considered, and in both cases topographydriven fluid flow was shown to have been an important mechanism for groundwater motion, with a lesser component contributed during the early stages of uplift by overpressuring created by compaction in the deep portion of the Arkoma basin. The Pennsylvanian–Permian sediments and underlying Western Interior Plains confining system acted as thick capping aquitards that caused slow rates of groundwater flow over much of the profile. As a result, meteoric water infiltration initiated during uplift was slow to flush saline formation waters, allowing MVT ore‐forming salinities to persist at Tri‐State on the order of at least 100 Myr. The slow groundwater flow rates also caused heat transport to occur primarily by conduction rather than advection. Despite this, MVT ore‐forming temperatures were still reached at Tri‐State for both endmember cases of Pennsylvanian–Permian aquitard thickness, though much more readily in the thick aquitard case. Faults within the Tri‐State district served as a regional fluid focusing mechanism and probably played a more important role in localizing mineralization than the window in the Ozark confining unit that occurs in the district. Fluids rising along these faults could have cooled by about 8–10°C and as much as another 0.3°C km?1 as they flowed laterally northward. This temperature change alone however would not have been sufficient to precipitate the total mass of metal sulfide ore occurring at Tri‐State.  相似文献   

19.
Results from soil chemical analysis have demonstrated enhanced concentrations of lead (Pb) associated with archaeological sites. However, interpretation of these Pb concentrations is difficult because of the multitude of possible Pb sources. This pilot study of an abandoned croft in Shetland suggests that Pb isotope ratios have the potential to identify sources of anthropogenic Pb. The results highlight two different Pb associations. The first includes hearth, house floor and house overburden soils, with end members of fuel materials and an unidentified material with a low (< 1.126) 206 Pb/ 207 Pb ratio. The second includes byre, kailyard (garden) and arable soils, with end members of hearth materials and local wind‐blown sand.  相似文献   

20.
Petrography, Eh‐pH calculations and the stable isotope composition of oxygen are used to interpret geochemical processes that occurred during iron oxide mineralization and dolomitization along the Menuha Ridge segment of the Paran Fault, southern Israel, adjacent to the Dead Sea Transform (DST). Iron mineralization is strongly localized in the fault zone as ferruginous lenses, whereas Fe dolomitization spreads laterally into the Cenomanian‐Turonian carbonate host rock as stratabound beds. The average oxygen isotope fractionation between syngenetic quartz and iron oxides in the ferruginous lenses gives a temperature of 50 ± 10°C and δ18O SMOW water = ?3.5‰; consistent with an origin from metalliferous groundwater flow in the sedimentary basin. Ferroan dolomite initially formed under strongly reducing conditions, but this was followed by oxidation and pseudomorphic replacement of the dolomite by a mesh of fine‐grained iron oxides (simple zoned dolomites). This cycle of ferroan dolomite formation and replacement by iron oxides was repeated in complex zoned dolomites. Dolomite oxygen isotope compositions fall into two groups: a high δ18O group corresponding to the simple zoned dolomites and non‐ferroan dolomites and a low δ18O group corresponding to the complex zoned dolomites. Water‐rock calculations suggest that the epignetic dolomites formed under fluid‐buffered conditions: the high δ18O group are indicated to have formed at temperatures of ca. 25°C for waters with δ18O = ?4 to 0‰; the low δ18O complex zoned dolomites at 50–75°C for waters with the same isotopic composition. A kinetic calculation for a complex zoned dolomite‐bearing bed indicates that dolomitization must have occurred at high values of the dolomite saturation index. This requirement for high Mg supersaturation and the indication that epigenetic dolomitization is more protracted in stratigraphically deeper formations located closer to the DST is consistent with models proposing that Mg‐rich solutions originated in the Dead Sea Rift.  相似文献   

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