North Atlantic control on precipitation pattern in the eastern Mediterranean/Black Sea region during the last glacial

Based on proxy records from western Black Sea cores, we provide a comprehensive study of climate change during the last glacial maximum and late-glacial period in the Black Sea region. For the first time we present a record of relative changes in precipitation for NW Anatolia based on variations in the terrigenous supply expressed as detrital carbonate concentration. The good correspondence between reconstructed rainfall intensity in NW Anatolia and past western Mediterranean sea surface temperatures (SSTs) implies that during the glacial period the precipitation variability was controlled, like today, by Mediterranean cyclonic disturbances. Periods of reduced precipitation correlate well with low SSTs in the Mediterranean related to Heinrich events H1 and H2. Stable oxygen isotopes and lithological and mineralogical data point to a significant modification in the dominant freshwater/sediment source concomitant to the meltwater inflow after 16.4 cal ka BP. This change implies intensification of the northern sediment source and, with other records from the Mediterranean region, consistently suggests a reorganization of the atmospheric circulation pattern affecting the hydrology of the European continent. The early deglacial northward retreat of both atmospheric and oceanic polar fronts was responsible for the warming in the Mediterranean region, leading simultaneously to more humid conditions in central and northern Europe.     

Origin and formation pathways of kerogen-like organic matter in recent sediments off the Danube delta (northwestern Black Sea)

The chemical structure, source(s), and formation pathway(s) of kerogen-like organic matter (KL) were investigated in recent sediments from the northwestern Black Sea, off the Danube delta. Three sections from a sediment core collected at the mouth of the Sulina branch of the delta, under an oxic water column, were examined: S₀ (0–0.5 cm bsf), S₁₀ (10–13 cm bsf), and S₂₀ (20–25 cm bsf). The bulk geochemical features of these sediments (total organic carbon, organic C/N atomic ratio, δ¹³C_org) were determined. Thereafter, KL was isolated from the samples, as the insoluble residue obtained after HF/HCl treatment. KL chemical composition was investigated via spectroscopic (FTIR, solid state ¹³C and ¹⁵N NMR) and pyrolytic (Curie point pyrolysis–gas chromatography–mass spectrometry) methods, and the morphological features were examined by scanning and transmission electron microscopy. Similar morphological features and chemical composition were observed for the three KLs and they suggested that the selective preservation of land-plant derived material as well as of resistant aliphatic biomacromolecules (probably derived from cell walls of freshwater microalgae) was the main process involved in KL formation. Besides, some melanoidin-type macromolecules (formed via the degradation-recondensation of products mainly derived from proteinaceous material) and/or some encapsulated proteins also contributed to the KL chemical structure.     

Mg/Ca-paleothermometry in the western Mediterranean Sea on planktonic foraminifer species Globigerina bulloides: Constraints and implications

We generated a high-resolution SST_Mg/Ca record for the surface-dwelling planktonic foraminifera Globigerina bulloides from the core MD99-2346 collected in the Gulf of Lion, and compared it to that obtained using modern analogue techniques applied to fossil foraminiferal assemblages (SST_MAT). The two temperature records display similar patterns during the last 28,000 years but the SST_Mg/Ca estimates are several degrees warmer (∼ +4 °C) than SST_MAT. The temperature shift between SST_Mg/Ca and SST_MAT remained relatively constant over time. This seems to exclude a bias on the Mg/Ca record associated with salinity or secondary Mg-rich calcite encrustation on the foraminiferal tests during early diagenesis. Therefore, anomalously high Mg/Ca suggests either: (1) the empirical equation for G. bulloides of Elderfield and Ganssen (2000) is incorrect; or (2) there is a specific Mediterranean genotypes of G. bulloides for which a specific Mg/Ca-temperature calibration is needed.     

Chronology of the Mediterranean sea-level highstand during the Last Interglacial: a critical review of the U/Th-dated deposits

Relative sea-level (RSL) evolution during Marine Isotopic Stage (MIS) 5 in the Mediterranean basin is still not fully understood despite a plethora of morphological, stratigraphic and geochronological studies carried out on highstand deposits of this area. In this review we assembled a database of 323 U/Th-dated samples (e.g. corals, molluscs, speleothems) which were used to chronologically constrain RSL evolution within MIS 5. The application of strict geochemical criteria to the U/Th samples indicates that only ~33% of data available for the Mediterranean Sea can be considered ‘reliable’. Most of these data (~65%) refer to the MIS 5e highstand, while only ~17% could be related to the MIS 5a. No attribution to MIS 5c can be unequivocally supported. Nevertheless, the resulting framework does not allow us to define a satisfactory RSL trend during the MIS 5e highstand and subsequent MIS 5 substages. Overall, the proposed selection of reliable/unreliable data would be useful for detecting areas where MIS 5 substage attributions are not supported by confident U/Th chronological data and thus the related reconstructions need to be revised. In this regard, the resulting framework calls for a reappraisal and re-examination of the Mediterranean records with advanced geochronological methodologies.     

Porphyry Cu–Au mineralisation associated with a multi-phase intrusion, and related replacement fronts in limestones in an island arc setting near the Gümü hane village (Artvin) in the Eastern Black Sea Province (Turkey)

The Gümü hane area near Artvin is highly characteristic due to a significant hydrothermal alteration zone genetically associated with a microdiorite stock and its late-stage derivatives in the form of porphyry plugs that intruded into all the pre-Middle Eocene lithologies. The porphyry intrusion is multi-stage, intermediate to felsic in composition, and divided into pre-ore feldspar porphyries and quartz–feldspar porphyries, syn-ore feldspar–amphibole porphyries, and post-ore feldspar porphyries. Sericitic alteration is dominant, but K-silicate alteration is also observed and is characterised mainly by secondary feldspars, biotites, quartz, anhydrite, magnetite and pyrite veinlets. The central part of the alteration and the porphyry system where syn-ore feldspar–amphibole porphyry outcrops coincides with intense quartz stock-working with anomalous but uneconomical Cu and Au values. In this zone, pyrite is ubiquitous and is accompanied by chalcopyrite and lesser sphalerite, sulphosalts, molybdenite, bornite and magnetite. Chemical analyses of surface and drill core samples show that overall Au and Cu values are around 0.5 ppm and 0.3%, respectively, and that they are in the ranges of 1–2 ppm and 0.3–0.4%, respectively, in the densest stock-work zones.Multi-phase intrusion of porphyries into Late Cretaceous limestone also caused replacement fronts along re-crystallised limestone and porphyry contacts. This type of mineralisation is enriched in Mn, Zn, Cu, Au and Ba, and contains on average 4.7% MnO, 3.2% FeO, 3.1% Zn, 0.95% Cu, 0.3% Pb, 200 ppb Au, 900 ppm Bi and 660 ppm Ba, present in Fe- and Mn-oxides, pyrite, chalcopyrite, sphalerite and lesser bornite, sulphosalts and gold. Supergene oxidation is well developed in these zones.Hydrothermal alteration mass change calculations reflect an intimate relationship between the two types of mineralisation. The lithologies near mineralised fronts are highly depleted in MnO and Zn, and the intensity of depletion is reduced away from the contact into the porphyry. The leached elements are added to the re-crystallised limestone block in which MnO and Zn show an 81-fold and 472-fold increase, respectively, over the least altered limestone. Au and Cu are enriched along the contact both in the porphyry and in the limestone, implying that they may have been derived either from other lithologies in the vicinity or the magma itself.     

Temporal variation in the geometry of a strike–slip fault zone: Examples from the Dead Sea Transform

The location of the active fault strands along the Dead Sea Transform fault zone (DST) changed through time. In the western margins of Dead Sea basin, the early activity began a few kilometers west of the preset shores and moved toward the center of the basin in four stages. Similar centerward migration of faulting is apparent in the Hula Valley north of the Sea of Galilee as well as in the Negev and the Sinai Peninsula. In the Arava Valley, seismic surveys reveal a series of buried inactive basins whereas the current active strand is on their eastern margins. In the central Arava the centerward migration of activity was followed by outward migration with Pleistocene faulting along NNE-trending faults nearly 50 km west of the center. Largely the faulting along the DST, which began in the early–middle Miocene over a wide zone of up to 50 km, became localized by the end of the Miocene. The subsidence of fault-controlled basins, which were active in the early stage, stopped at the end of the Miocene. Later during the Plio-Pleistocene new faults were formed in the Negev west of the main transform. They indicate that another cycle has begun with the widening of the fault zone. It is suggested that the localization of faulting goes on as long as there is no change in the stress field. The stresses change because the geometry of the plates must change as they move, and consequently the localization stage ends. The fault zone is rearranged, becomes wide, and a new localization stage begins as slip accumulates. It is hypothesized that alternating periods of widening and narrowing correlate to changes of the plate boundaries, manifest in different Euler poles.     

Reassessment of HF/HNO3 Decomposition Capability in the High‐Pressure Digestion of Felsic Rocks for Multi‐Element Determination by ICP‐MS

Complete dissolution is essential to obtain accurate analytical results for geological samples. Felsic rocks are known to be very difficult to dissolve because of the presence of refractory minerals such as zircon. In this study, we undertook a systematic evaluation of the effect of the HF/HNO₃ ratio, digestion time, digestion temperature, digested test portion mass and the presence of insoluble fluorides on analytical results for the felsic rock GSP‐2 using high‐pressure HF and HF/HNO₃ digestion. Digestion in mixtures of HF and HNO₃ acids is a commonly used method of dissolution for geological samples. However, our results clearly indicate that adding HNO₃ inhibited the digestion capabilities of HF for refractory minerals such as zircon. It took 8–12 hr for Zr to be completely recovered in GSP‐2 at 190 °C, whereas it needed about 36 and 72 hr at 160 and 140 °C, respectively. White precipitates were observed in the final solution for test portion mass > 100 mg, irrespective of which of the five different digestion solutions was used (1 ml HF, 2 ml HF, 1 ml HF + 0.5 ml HNO₃, 1 ml HF + 1 ml HNO₃ and 1.5 ml HF + 1.5 ml HNO₃). Environmental scanning electron microscopy showed that these precipitates were mainly composed of AlF₃. Instead of further HCl, HNO₃ or HClO₄ attack, we propose that using ultra‐fine samples and a small sample size is a good way to avoid the formation of insoluble residues (e.g., fluorides). To further investigate the precision and accuracy of the proposed method (using HF alone as the digestion solution during the first acid attack step), a suite of silicate rock reference materials was analysed. Most of the results were found to be in reasonable agreement with the reference values, with a relative error of < 10%.     

U–Pb ages of Neoarchean granitoids from the Black Hills, South Dakota, USA: implications for crustal evolution in the Archean Wyoming province

Zircons in basement rocks from the eastern Wyoming province (Black Hills, South Dakota, USA) have been analyzed by ion microprobe (SHRIMP) in order to determine precise ages of Archean tectonomagmatic events. In the northern Black Hills (NBH) near Nemo, Phanerozoic and Proterozoic (meta)sedimentary rocks are nonconformably underlain by Archean biotite–feldspar gneiss (BFG) and Little Elk gneissic granite (LEG), both of which intrude older schists. The Archean granitoid gneisses exhibit a pervasive NW–SE-trending fabric, whereas an earlier NE–SW-trending fabric occurs sporadically only in the BFG, which is intruded by the somewhat younger LEG. Zircon crystals obtained from the LEG and BFG exhibit double terminations, oscillatory zoning, and Th/U ratios of 0.6±0.3—thereby confirming a magmatic origin for both lithologies. In situ analysis of the most U–Pb concordant domains yields equivalent ²⁰⁷Pb/²⁰⁶Pb ages (upper intercept, U–Pb concordia) of 2559±6 and 2563±6 Ma (both ±2σ) for the LEG and BFG, respectively, which constrains a late Neoarchean age for sequential pulses of magmatism in the NBH. Unzoned (in BSE) patches of 2560 Ma zircon commonly truncate coeval zonation in the same crystals with no change in Th/U ratio, suggesting that deuteric, fluid-assisted recrystallization accompanied post-magmatic cooling. A xenocrystic core of magmatic zircon observed in one LEG zircon yields a concordant age of 2894±6 Ma (±2σ). This xenocryst represents the oldest crustal material reported thus far in the Black Hills. Whether this older zircon originated as unmelted residue of 2900 Ma crust that potentially underlies the Black Hills or as detritus derived from 2900 Ma crustal sources in the Wyoming province cannot be discerned. In the southern Black Hills (SBH), the peraluminous granite at Bear Mountain (BMG) of previously unknown age intrudes biotite–plagioclase schist. Zircon crystals from the BMG are highly metamict and altered, but locally preserve small domains suitable for in situ analysis. A U–Pb concordia upper intercept age of 2596±11 Ma (±2σ) obtained for zircon confirms both the late Neoarchean magmatic age of the BMG and a minimum age for the schist it intrudes. Taken together, these data indicate that the Neoarchean basement granitoids were emplaced at 2590–2600 Ma (SBH) and 2560 Ma (NBH), most likely in response to subduction associated with plate convergence (final assembly of supercontinent Kenorland?). In contrast, thin rims present on some LEG–BFG zircons exhibit strong U–Pb discordance, high common Pb, and low Th/U ratios—suggesting growth or modification under hydrothermal conditions, as previously suggested for similar zircons from SE Wyoming. The LEG–BFG zircon rims yield a nominal upper intercept date of 1940–2180 Ma, which may represent a composite of multiple rifting events known to have affected the Nemo area between 2480 and 1960 Ma. Together, these observations confirm the existence of a Paleoproterozoic rift margin along the easternmost Wyoming craton. Moreover, the 2480–1960 Ma time frame inferred for rifting in the Black Hills (Nemo area) corresponds closely to a 2450–2100 Ma time frame previously inferred for the fragmentation of supercontinent Kenorland.     

Three‐dimensional seismic characterization of a complex sediment drift in the South China Sea: Evidence for unsteady flow regime

This study describes a previously unobserved reflection seismic configuration comprising a honeycomb planform and a repeated erosion/infill cross‐section, based on high‐resolution three‐dimensional/two‐dimensional seismic data and bathymetric data. The honeycomb structures cover an area of more than 5000 km² and are developed within the Late Miocene to recent deep‐water sediments of the north‐western South China Sea. Linear erosional troughs up to 10 km long and 1 km wide are widely developed in this area, are intimately related to the particular seismic configuration and interpreted to represent a new type of sediment drift that is caused by unsteady bottom current regimes operating since the Late Miocene. The unsteady bottom current regimes are suggested to be triggered by irregular seabed morphologies. Considerable sea‐floor topography was generated as a direct result of tectonic movements in the area since the Late Miocene, and this topography then influenced the pathways of strong bottom currents. This study highlights that: (i) an unsteady bottom current regime can be laterally extensive and persist for millions of years; (ii) structurally controlled sea‐floor relief plays an important role in controlling the depositional pattern; and (iii) the bottom currents were active since the Late Miocene, flowing from the south‐east through the Xisha–Guangle Gateway and crossing the honeycomb structure zone. This study documents a new style of drift and will help to improve current knowledge of palaeoceanography and understanding of the South China Sea deep‐water circulation which is at present still poorly understood.     

Application of 1013 Ω Amplifiers in Low‐Signal Plasma‐Source Isotope Ratio Measurements by MC‐ICP‐MS: A Case Study with Pt Isotopes

Recent developments in amplifier hardware enable low‐noise measurements of exceedingly small ion beams in isotope ratio analysis, yielding higher precision from smaller samples than ever before. To date, these amplifiers have largely been employed in thermal ionisation instruments, with few applications using plasma‐source (i.e., MC‐ICP‐MS) instruments. Here, we demonstrate the utility of these new generation 10¹³ Ω amplifiers in MC‐ICP‐MS, employing Pt isotopes as a case study, a system that could greatly benefit from the promised advances. The data demonstrate that for samples with low Pt abundance, for a modest increase in uncertainties, the amount of sample required can be reduced by a factor of 50–100. This technique thereby opens up new possibilities for analysis of samples that have low Pt mass fractions or were otherwise impossible to obtain in sufficient quantities.     

Ore Genesis for Stratiform Ore Bodies of the Dongfengnanshan Copper Polymetallic Deposit in the Yanbian Area, NE China：Constraints from LA-ICP-MS in situ Trace Elements and Sulfide S–Pb Isotopes

The Dongfengnanshan Cu polymetallic deposit is one representative deposit of the Tianbaoshan ore district in the Yanbian area, northeast(NE) China. There occur two types of ore bodies in this deposit, the stratiform ore bodies and veintype ones, controlled by the Early Permian strata and the Late Hercynian diorite intrusion, respectively. Due to the ambiguous genetic type of the stratiform ore bodies, there has been controversy on the relationship between them and veintype ore bodies. To determine the genetic type of stratiform ore bodies, laser ablation inductively coupled plasma mass spectrometry(LA-ICP-MS) in situ trace elements and S–Pb isotope analysis have been carried on the sulfides in the stratiform ore bodies. Compared with that in skarn, Mississippi Valley-type(MVT), and epithermal deposits, sphalerite samples in the stratiform ore bodies of the Dongfengnanshan deposit are significantly enriched in Fe, Mn, and In, while depleted in Ga, Ge, and Cd, which is similar to the sphalerite in volcanic-associated massive sulfide(VMS) deposits. Co/Ni ratio of pyrrhotites in the stratiform ore bodies is similar to that in VMS-type deposits. The concentrations of Zn and Cd of chalcopyrites are similar to those of recrystallized VMS-type deposits. These characteristics also reflect the intermediate ore-forming temperature of the stratiform ore bodies in this deposit. Sulfur isotope compositions of sulfides are similar to those of VMS-type deposits, reflecting that sulfur originated from the Permian Miaoling Formation. Lead isotope compositions indicate mixed-source for lead. Moreover, the comparison of the Dongfengnanshan stratiform ore bodies with some VMStype deposits in China and abroad, on the trace elements and S–Pb isotope characteristics of the sulfides reveals that the stratiform ore bodies of the Dongfengnanshan deposit belong to the VMS-type, and have closely genetic relationship with the early Permian marine volcanic sedimentary rocks.     

Predictive mapping for copper–gold magmatic-hydrothermal systems in NW Argentina: Use of a regional-scale GIS, application of an expert-guided data-driven approach, and comparison with results from a continental-scale GIS

Geographic Information Systems (GISs) are very useful tools for managing, checking, and organizing spatial information–from many sources and of many types–in thematic layers. Processing of these data enables exploration-oriented GISs to produce potential and predictive maps for a given commodity, which constitute documents of real use in decision-making. Integration of all information in a single reference system enables a better understanding of the parameters controlling a region's metallogeny, in terms of both time and space. But what scale should be used for developing a mineral exploration GIS? Should preference be given to systems with high spatial resolutions (scale < 1:500,000), or to more general systems with scales of around 1:1,500,000 or 1:2,000,000? Will the gain be worthwhile relative to the additional work generated by compilation at a higher scale? In order to make greater use of previous predictive studies performed on gold-rich epithermal and porphyry systems at the scale of the entire Andes, an expert-guided data-driven approach is now applied to a regional-scale GIS of NW Argentina, between the Puna and the Sierrras Pampeanas, where known deposits like Bajo de la Alumbrera, Agua Rica, and others, account for a metal potential of over 10 Mt Cu and 750 t Au. In developing this new predictive map, three criteria that were likely to be connected to the mineralizing event were selected and quantified: (i) lithostratigraphy, because of its role as a favourable environment for the development of mineralization, based on its physico-chemical properties; (ii) lithostratigraphic contacts, based on the rheological properties of the formations in contact; and (iii) the orientation of structural discontinuities, which channel source magmas and encourage the circulation of hydrothermal fluids. Assigning a score enables classification of the favourabilities calculated for each of the criteria considered. This approach is employed here to check and standardize the statistical results obtained by methods such as Weight of Evidence Modelling or an algebraic approach. For each criterion, four classes were distinguished: very favourable: score = 3; favourable: score = 2; slightly favourable: score = 1; and unfavourable: score = 0. The predictive map is obtained by adding the scores for the three favourable criteria defined above.The regional-scale work identified 20 anomalous envelopes with cumulative scores greater than 5. They correspond to mining areas that are active (e.g., Bajo de la Alumbrera), under development (e.g., Agua Rica), or abandoned (e.g., La Mejicana), or to new areas (e.g., the Vicuña Pampa Volcanic Complex). Structural analysis of the region, integrating the orientation of the favourable envelopes, suggests that the mineralizing fluids were emplaced under extensional conditions, sub-parallel to the principal directions of shortening: (i) WNW–ESE, found along the southern edge of the Puna; and (ii) E–W, seen in the Sierra de Famatina. It appears that a regional-scale information system is a tool that is well suited to the definition of areas for mineral prospecting, and to the study and confirmation of metallotects usable for mineral exploration.Comparison with work conducted on the basis of a 1:2,000,000 geological compilation shows that the principal mining districts can indeed be found at continental scale. On the other hand, the lack of detail inherent at a scale of 1:2,000,000 may lead to inaccuracies, in particular fictitious favourabilities assigned to formations that are genetically unrelated to the mineralization, but that contain, for example, small Tertiary intrusive bodies that cannot be recorded at this scale. This comparison therefore shows that the use of a continental-scale GIS is effective, and well suited to the definition of prospective areas at a strategic level.     

Enigmatic sedimentary–volcanic successions in the central European Variscides: a Cambrian/Early Ordovician age for the Wojcieszów Limestone (Kaczawa Mountains,SW Poland) indicated by SHRIMP dating of volcanic zircons

Metamorphosed volcanic and sedimentary successions in the central European Variscides are, in many areas, poorly biostratigraphically constrained, making palaeotectonic interpretations uncertain. In such instances, geochronological data are crucial. Sensitive high resolution ion microprobe (SHRIMP) dating of volcanic zircons from a quartz–white mica schist (interpreted as deformed metavolcaniclastic/epiclastic rock) within the stratigraphically controversial Wojcieszów Limestone of the Kaczawa Mountains (Sudetes, SW Poland), near to the eastern termination of the European Variscides, has yielded an age of 498 ± 5 Ma (2σ error), corresponding to late Cambrian to early Ordovician magmatism in that area and constraining the depositional age of the limestones. The new SHRIMP data are not consistent with the recent revision of the age of the Wojcieszów Limestone based on Foraminifera findings that ascribed them to a Late Ordovician—Silurian or even younger interval. They are though, consistent with sparse macrofossil data and strongly support earlier interpretations of the lower part of the Kaczawa Mountains succession as a Cambrian–Early Ordovician extensional basin‐fill with associated initial rift volcanic rocks, likely emplaced during the breakup of Gondwana. Copyright © 2008 John Wiley & Sons, Ltd.