0000000001092591
AUTHOR
Regina Mertz-kraus
Experimental alteration of granitic rocks: Implications for the evolution of geothermal brines in the Upper Rhine Graben, Germany
Abstract Geothermal energy exploitation in the Upper Rhine Graben (URG) chiefly has targeted faults and fractures within or connected with the crystalline basement, where hot fluids of c. 200 °C circulate at depths of c. 5 km. Formation fluids of the crystalline basement are highly saline, NaCl-dominated brines, whereas shallow crystalline basement water ( The trace element concentrations of the leachates are hereby related to the composition and stability of minerals in the rocks and can be directly linked to the proposed and observed dissolution processes at the different temperatures. In experiments with pure water at 70 °C, representing the recharge or infiltration conditions, water-roc…
A New LA ‐ ICP ‐ MS Method for Ti in Quartz: Implications and Application to High Pressure Rutile‐Quartz Veins from the Czech Erzgebirge
Experimental determination of the pressure and temperature controls on Ti solubility in quartz provides a calibration of the Ti-in-quartz (TitaniQ) geothermometer applicable to geological conditions up to ~ 20 kbar. We present a new method for determining 48Ti mass fractions in quartz by LA-ICP-MS at the 1 μg g−1 level, relevant to quartz in HP-LT terranes. We suggest that natural quartz such as the low-CL rims of the Bishop Tuff quartz (determined by EPMA; 41 ± 2 μg g−1 Ti, 2s) is more suitable than NIST reference glasses as a reference material for low Ti mass fractions because matrix effects are limited, Ca isobaric interferences are avoided, and polyatomic interferences at mass 48 are i…
Mn/Ca in shells of Arctica islandica (Baltic Sea) – A potential proxy for ocean hypoxia?
Oxygen depletion threatens an increasing number of shallow water environments, specifically habitats below the seasonal halocline in coastal settings of the Baltic Sea. To understand the natural variations of dissolved oxygen levels on seasonal and inter-annual time-scales prior to the instrumental era, high-resolution archives are urgently required. The present study evaluates the potential use of Mn/Ca values in shells of the bivalve, Arctica islandica to infer concentrations of past dissolved oxygen concentrations. This study is based on laser ablation – inductively coupled plasma – mass spectrometry (LA-ICP-MS) data of six contemporaneous specimens and demonstrates that background varia…
An experimental study of the role of partial melts of sediments versus mantle melts in the sources of potassic magmatism
Abstract Potassium-rich lavas with K/Na of >2 are common in orogenic and anorogenic intraplate magmatic provinces. However, in the primitive mantle, the concentration of Na exceeds that of K by 10 times. The source of K-rich lavas thus needs to be either K-enriched or Na-depleted to account for high K/Na ratios. The geochemical and isotopic compositions of high 87Sr/86Sr post-collisional lavas show that their mantle source contains a recycled crustal component. These highly K-enriched lavas with crustal like trace element patterns are termed “orogenic lamproites” and are compositionally distinct from K-rich “anorogenic lamproites” that show lower 87Sr/86Sr and a trace element pattern that r…
Insights from sodium into the impacts of elevated pCO2 and temperature on bivalve shell formation
Ocean acidification and warming are predicted to affect the ability of marine bivalves to build their shells, but little is known about the underlying mechanisms. Shell formation is an extremely complex process requiring a detailed understanding of biomineralization processes. Sodium incorporation into the shells would increase if bivalves rely on the exchange of Na+/H+ to maintain homeostasis for shell formation, thereby shedding new light on the acid-base and ionic regulation at the calcifying front. Here, we investigated the combined effects of seawater pH (8.1, 7.7 and 7.4) and temperature (16 and 22 °C) on the growth and sodium composition of the shells of the blue mussel, Mytilus edul…
Otolith fingerprints reveals potential pollution exposure of newly settled juvenile Sparus aurata
Abstract Coastal ecosystems are increasingly threatened by a wide range of human activities. Fish otolith chemistry, by creating a unique specific signature, can be used as a natural tag for determining life stage dispersal, spatial connectivity and population structure. In this study, we tested whether differences in otolith composition among juveniles of gilthead sea bream, Sparus aurata, could enable their proper allocation to polluted areas based on higher concentrations of elements related to contaminants. Otoliths were embedded, sectioned and analysed by LA-ICP-MS in line scan mode. Multivariate analysis confirmed clear separation between sites and elements. Samples from the site unde…
Melting phlogopite-rich MARID: Lamproites and the role of alkalis in olivine-liquid Ni-partitioning
Abstract In this study, we show how veined lithospheric mantle is involved in the genesis of ultrapotassic magmatism in cratonic settings. We conducted high pressure experiments to simulate vein + wall rock melting within the Earth's lithospheric mantle by reacting assemblages of harzburgite and phlogopite-rich hydrous mantle xenoliths. These comprised a mica-, amphibole-, rutile-, ilmenite-, diopside (MARID) assemblage at 3–5 GPa and 1325–1450 °C. Melting of the MARID assemblages results in infiltration of melt through the harzburgite, leading to its chemical alteration. At 3 and 4 GPa, melts are high in K2O (> 9 wt%) with K2O/Na2O > > 2 comparable to anorogenic lamproites. Higher pressure…
Vegetation and climate record from Abric Romaní (Capellades, northeast Iberia) during the Upper Pleistocene (MIS 5d−3)
This study addresses the pollen record of Abric Romani archaeological site and the climate evolution of the last interglacial and glacial stadials in the Iberian Peninsula. The new pollen record spans the interval from 110,000 to 55,000 years ago. In general, the glacial/stadial vegetation is characterized by a steppe and herbaceous communities indicating dry and cold climatic conditions, whereas the vegetation optimum of past interglacials can be described as pine-oaks with mediterranean forest indicating milder and moister climatic conditions. During the first half of the MIS 5a and the MIS 5c, the region was warmer, which is characterized by temperate forests. However, the existence of A…
Trace elements in olivine of ultramafic lamprophyres controlled by phlogopite-rich mineral assemblages in the mantle source
Abstract Carbonate-rich ultramafic lamprophyres (aillikites) and associated rocks characteristically occur during the early stages of thinning and rifting of cratonic mantle lithosphere, prior to the eruption of melilitites, nephelinites and alkali basalts. It is accepted that they require volatile-rich melting conditions, and the presence of phlogopite and carbonate in the source, but the exact source rock assemblages are debated. Melts similar to carbonate-rich ultramafic lamprophyres (aillikites) have been produced by melting of peridotites in the presence of CO2 and H2O, whereas isotopes and trace elements appear to favor distinct phlogopite-bearing rocks. Olivine macrocrysts in ailliki…
Chemical evolution of ore-forming brines – Basement leaching, metal provenance, and the redox link between barren and ore-bearing hydrothermal veins. A case study from the Schwarzwald mining district in SW-Germany
Abstract Six mineralogically exemplary barren and mineralized hydrothermal veins (with Pb and Zn ores) of Jurassic-Cretaceous and Cenozoic age in the Schwarzwald mining district, SW Germany were chosen to shed light on the origin of their mineralogical diversity. The selection of the veins was guided by the fact that they represent the largest number of veins in the region, are very well known mineralogically and geochemically, and they provide nice examples of barren and mineralized veins of similar age. Fluid inclusion data from the individual veins overlap implying their diverse mineralogy is not caused by different fluid compositions participating during fluid mixing. LA-ICPMS data of s…
U-Pb monazite ages from the Pakistan Himalaya record pre-Himalayan Ordovician orogeny and Permian continental breakup
The Greater Himalayan Sequence in India and Nepal records crustal thickening processes that took place during and following the onset of India-Asia collision (ca. 54–50 Ma). These resulted in late Eocene–early Miocene kyanite- and sillimanite-grade regional metamorphism, and Oligocene–Miocene crustal anatexis, which formed migmatites and leucogranites. We present new U-Pb monazite data for kyanite- and sillimanite-grade gneisses of the Neoproterozoic to Cambrian Tanawal Formation in the Pakistan Himalaya, which have metamorphic ages of 482.4 ± 7.9 Ma and 464.5 ± 4.0 Ma, respectively. These ages, together with along-strike equivalent rocks in the Lesser Himalaya of India and Nepal, help to d…
Controls on strontium and barium incorporation into freshwater bivalve shells ( Corbicula fluminea )
Abstract Trace elements of bivalve shells can potentially serve as proxies of environmental change. However, to reconstruct past environments using the geochemical properties of the shells and determine the degree to which the element levels are biologically influenced, it is essential to experimentally determine the relationship between environmental variables and the element composition of the shells. To disentangle possible controls on the incorporation of strontium and barium into freshwater bivalve shells, we conducted controlled laboratory experiments using the extremely salinity and temperature tolerant Asian clam, Corbicula fluminea as a model species. Bivalves were reared for five …
Non-Matrix-Matched Calibration for the Multi-Element Analysis of Geological and Environmental Samples Using 200 nm Femtosecond LA-ICP-MS: A Comparison with Nanosecond Lasers
LA-ICP-MS is one of the most promising techniques for in situ analysis of geological and environmental samples. However, there are some limitations with respect to measurement accuracy, in particular for volatile and siderophile/chalcophile elements, when using non-matrix-matched calibration. We therefore investigated matrix-related effects with a new 200 nm femtosecond (fs) laser ablation system (NWRFemto200) using reference materials with different matrices and spot sizes from 10 to 55 μm. We also performed similar experiments with two nanosecond (ns) lasers, a 193 nm excimer (ESI NWR 193) and a 213 nm Nd:YAG (NWR UP-213) laser. The ion intensity of the 200 nm fs laser ablation was much l…
Spatial variations in Ba/Cashell fingerprints of Glycymeris pilosa along the eastern Adriatic Sea
Abstract The long living Glycymeris pilosa bivalve is an interesting target species for the sclerochronological research in the Mediterranean Sea. In this study, Ba/Cashell and Mg/Cashell variations were studied along the coast of the eastern Adriatic Sea. Specimens were collected alive by SCUBA and skin diving during several occasions in 2014, 2015 and 2016 from five sites including Pag, Pasman Channel, Cetina, Živogosce and Drace. Element-to-Cashell ratios were measured by LA-ICP-MS in line scan mode in three specimens of each site, ranging in age from 7 to 21. In addition, chemical analysis was conducted on three ontogenetically older specimens (68-97 years-old) from Drace. Mg/Cashell an…
XRF and LA-ICP-MS studies of gold and silver artefacts from a 12–13th century CE tumulus in Senegal: Implications for the medieval African gold trade
Abstract Silver and gold artefacts from a 12–13th c. CE tumulus in Senegal were recently analysed by means of XRF and LA-ICP-MS. The identification of major, minor and trace elements allowed gaining a rare insight into the composition of precious metals circulating in that part of Africa in medieval times. The results show that all objects were made of polymetallic alloys. Comparisons with analyses from other West African as well as North African and European silver and gold artefacts suggest that the metal from the studied objects most probably originate from outside West Africa. At least in the case of the gold artefacts, this is quite surprising, as we expected to come across pure West A…
Carbonates from the ancient world's longest aqueduct:A testament of Byzantine water management
The fourth‐ and fifth‐century aqueduct system of Constantinople is, at 426 km, the longest water supply line of the ancient world. Carbonate deposits in the aqueduct system provide an archive of both archaeological developments and palaeo‐environmental conditions during the depositional period. The 246‐km‐long aqueduct line from the fourth century used springs from a small aquifer, whereas a 180‐km‐long fifth‐century extension to the west tapped a larger aquifer. Although historical records testify at least 700 years of aqueduct activity, carbonate deposits in the aqueduct system display less than 27 years of operation. This implies that the entire system must have been cleaned of carbonate…
Assessment of Five Monazite Reference Materials for U-Th/Pb Dating Using Laser-Ablation ICP-MS
Monazite is a common accessory phosphate mineral that occurs under a wide range of pressure and temperature conditions in sedimentary, metamorphic and igneous rocks. Monazite contains high amounts of Th and U, rendering single monazite grains suitable for in-situ U-Th/Pb dating using laser ablation inductively-coupled mass spectrometry (LA-ICP-MS). Two key aspects of monazite dating that are critical for accurate age data with maximum precision are (i) optimized instrumental conditions to minimize analytical scatter and (ii) a well characterized reference material to ensure the accuracy of the obtained aged. Here, we analyzed five monazite reference materials (USGS 44069, 94-222, MAdel, Moa…
Late Quaternary slip rates for the southern Elsinore fault in the Coyote Mountains, southern California from analysis of alluvial fan landforms and clast provenance, soils, and U-series ages of pedogenic carbonate
Abstract Offset alluvial fans along the Elsinore fault in the south-central Coyote Mountains were studied to resolve an average late Quaternary slip rate for this major western strand of the San Andreas fault system in southern California. Alluvial fans and their offsets were mapped using high-resolution DEMs combined with field observations of fan-surface morphology and the character of the soils developed in each fan remnant. Clast assemblage data was used to determine the source of each alluvial fan upstream of the fault, and U-series dating of pedogenic carbonate was used to estimate minimum ages of the alluvial fan surfaces. Forty U-Th dates on pedogenic carbonate confirm the utility o…
Geodynamic setting of Upper Miocene to Quaternary alkaline basalts from Harrat al ‘Uwayrid (NW Saudi Arabia): Constraints from K Ar dating, chemical and Sr-Nd-Pb isotope compositions, and petrological modeling
Highlights • Volcanic activity of Harrat Uwayrid (NW Arabia) lasted from 8.2 to 0.3 Ma. • Alkali olivine basalts are followed by basanites, tephrites and tephriphonolites. • Sr-Nd-Pb isotopic ratios of all volcanic rocks suggest a PREMA source. • Different degrees of partial melting of amphibole-garnet-spinel lherzolite • Lithospheric mantle source rather than asthenosphere or plume-type mantle Abstract The volcanic field of Harrat ar Rahah-’Uwayrid (NW Saudi Arabia) consists of an older plateau basalt sequence that overlies Cambrian sandstone and younger cinder cones with smaller flows that are concentrated in the central part of this field. Petrographic and whole rock geochemical data ind…
Two-Stage Origin of K-Enrichment in Ultrapotassic Magmatism Simulated by Melting of Experimentally Metasomatized Mantle
The generation of strongly potassic melts in the mantle requires the presence of phlogopite in the melting assemblage, while isotopic and trace element analyses of ultrapotassic rocks frequently indicate the involvement of subducted crustal lithologies in the source. However, phlogopite-free experiments that focus on melting of sedimentary rocks and subsequent hybridization with mantle rocks at pressures of 1&ndash
Kinematics and U-Pb zircon ages of the sole metamorphics of the Marmaris Ophiolite, Lycian Nappes, Southwest Turkey
In the eastern Mediterranean, the Lycian Nappes are found in the structurally uppermost position in the Anatolide-Tauride belt related to the closure of the Neotethys. In Western Turkey, the Marmaris Ophiolite with the metamorphic sole occupies the uppermost tectonic position in the Lycian belt. The metamorphic sole is represented by discontinuous tectonic slices composed of amphibolites, phyllites, micashists and quartzo-feldspathic micaschists. Zircons from the micashists and quartzo-feldspathic micaschists display dark cores and rims. The cores yield ages between 229 and 175 Ma, inner rims yield ages between 153 and 143 Ma and the outer rims show a concordia age of 96.7 ± 0.79 Ma. In ter…
Ancient xenocrystic zircon in young volcanic rocks of the southern Lesser Antilles island arc
Abstract The Lesser Antilles arc is one of the best global examples in which to examine the effects of the involvement of subducted sediment and crustal assimilation in the generation of arc crust. Most of the zircon recovered in our study of igneous and volcaniclastic rocks from Grenada and Carriacou (part of the Grenadines chain) is younger than 2 Ma. Within some late Paleogene to Neogene (~ 34–0.2 Ma) lavas and volcaniclastic sediments however, there are Paleozoic to Paleoarchean (~ 250–3469 Ma) xenocrysts, and Late Jurassic to Precambrian zircon (~ 158–2667 Ma) are found in beach and river sands. The trace element characteristics of zircon clearly differentiate between different types o…
Unionid shells (Hyriopsis cumingii) record manganese cycling at the sediment-water interface in a shallow eutrophic lake in China (Lake Taihu)
Abstract Aquatic eutrophication is becoming a serious environmental problem throughout the world. The utility of bivalves as bio-filters to improve water quality and reduce algal blooms has been widely acknowledged, but the potential usefulness of bivalve shells as retrospective monitors of eutrophication-induced environmental change has received little attention. Here, we present the first multi-year, high-resolution Mn/Ca shell records of the freshwater mussel, Hyriopsis cumingii (Lea, 1852) from a shallow eutrophic lake (Lake Taihu, China). Mn/Ca shell time-series of the two studied shells exhibit a high degree of synchrony after being placed in a precise temporal context by means of gro…
Trace and minor element records in aragonitic bivalve shells as environmental proxies
Abstract Investigation of the geochemical composition of bivalve shells can provide information on changes in the marine environment occurring during the lifespan of an organism. Three species, locally abundant in the Adriatic Sea, were chosen in this study, namely Glycymeris pilosa, Callista chione, and Venus verrucosa. Of these, G. pilosa has the longest lifespan, exceeding 50 years, and therefore presents a potential archive of decadal climate variability. The other two species, C. chione and V. verrucosa, are commercially important. Samples were collected alive by SCUBA diving in the North Adriatic Sea, near Barbariga, Istria. Major growth increments in these shells form on an annual ba…
NanoSr - A New Carbonate Microanalytical Reference Material for In Situ Strontium Isotope Analysis
The in situ measurement of Sr isotopes in carbonates by MC‐ICP‐MS is limited by the availability of suitable microanalytical reference materials (RMs), which match the samples of interest. Whereas several well‐characterised carbonate reference materials for Sr mass fractions > 1000 µg g−1 are available, there is a lack of well‐characterised carbonate microanalytical RMs with lower Sr mass fractions. Here, we present a new synthetic carbonate nanopowder RM with a Sr mass fraction of ca. 500 µg g−1 suitable for microanalytical Sr isotope research (‘NanoSr’). NanoSr was analysed by both solution‐based and in situ techniques. Element mass fractions were determined using EPMA (Ca mass fraction),…
Speleothem δ13C record suggests enhanced spring/summer drought in south-eastern Spain between 9.7 and 7.8 ka – A circum-Western Mediterranean anomaly?
South-eastern Spain is one of the driest regions in Europe and thus, prone to drought. Terrestrial climate records covering the late Glacial and Holocene from this area are sparse. Here, we present a flowstone record from Cueva Victoria, south-eastern Spain, which covers the late Glacial (15 ka) to the mid-Holocene (7 ka) including the Younger Dryas (YD). Between the onset of the Bølling/Allerød (B/A) and the early Holocene, flowstone δ18O values progressively decrease in accordance with sea-surface temperatures in the Alboran Sea, indicating an increase in precipitation in south-eastern Spain and a supra-regional signal of North Atlantic temperature change. At the same time, decreasing δ13…
Development of a Matrix-Matched Sphalerite Reference Material (MUL-ZnS-1) for Calibration of In Situ Trace Element Measurements by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry
Sphalerite (ZnS) is an abundant ore mineral and an important carrier of elements such as Ge, Ga and In used in high-technology applications. In situ measurements of trace elements in natural sphalerite samples using LA-ICP-MS are hampered by a lack of homogenous matrix-matched sulfide reference materials available for calibration. The preparation of the MUL-ZnS1 calibration material containing the trace elements V, Cr, Mn, Co, Ni, Cu, Ga, Ge, As, Se, Mo, Ag, Cd, In, Sn, Sb, Tl and Pb besides Zn, Fe and S is reported. Commercially available ZnS, FeS, CdS products were used as the major components, whereas the trace elements were added by doping with single-element ICP-MS standard solutions a…
U-Pb Zircon Geochronology Of The Paleogene - Neogene Volcanism In The Nw Anatolia: Its Implications For The Late Mesozoic-Cenozoic Geodynamic Evolution Of The Aegean
The northern Aegean region was shaped by subduction, obduction, collision, and post-collisional extension processes. Two areas in this region, the Rhodope-Thrace-Biga Peninsula to the west and Armutlu-Almacik- Nallihan (the Central Sakarya) to the east, are characterized by extensive Eocene to Miocene post-collisional magmatic associations. We suggest that comparison of the Cenozoic magmatic events of these two regions may provide insights into the Late Mesozoic to Cenozoic tectonic evolution of the Aegean. With this aim, we present an improved Cenozoic stratigraphy of the Biga Peninsula derived from a new comprehensive set of U-Pb zircon age data obtained from the Eocene to Miocene volcani…
Variation of olivine composition in the volcanic rocks in the Songliao basin, NE China: lithosphere control on the origin of the K-rich intraplate mafic lavas
Abstract Lithospheric thickness and the heterogeneity of the mantle lithosphere are two major parameters that play a role in determining the final composition of the mafic melts and their minerals. The Songliao basin in northeast China represents an ideal natural laboratory to study the effect of these two parameters on early Pliocene to Holocene K-rich mafic lavas (K2O > 4 wt.%; K2O/Na2O > 1). A series of Cenozoic volcanic edifices (Erkeshan, Wudalianchi, Keluo and Xiaogulihe) are tentatively divided into three groups (Group 1 — thin, Group 2 — middle, and Group 3 — thick) according to the lithosphere thickness. They are located in the northern region of the Songliao basin extending in a n…
Peri-Gondwanan Ordovician arc magmatism in southeastern Ireland and the Isle of Man: Constraints on the timing of Caledonian deformation in Ganderia
The timing of and tectonic controls on Ordovician magmatism and deformation within accreted terranes are key elements in reconstructing the generation of the Caledonian-Appalachian orogen. This pap ...
Ba/Ca ratios in shells of Arctica islandica —Potential environmental proxy and crossdating tool
Abstract Ba/Ca shell time-series of marine bivalves typically show flat background levels which are interrupted by erratic sharp peaks. Evidence from the literature indicates that background Ba/Ca shell ratios broadly reflect salinity conditions. However, the causes for the Ba/Ca shell peaks are still controversial and widely debated although many researchers link these changes to primary productivity, freshwater input or spawning events. The most striking feature is that the Ba/Ca shell peaks are highly synchronous in contemporaneous specimens from the same population. For the first time, we studied Ba/Ca shell in mature and ontogenetically old (up to 251 year-old) specimens of the long-li…
Tarbellastraea (Scleractinia): A new stable isotope archive for Late Miocene paleoenvironments in the Mediterranean
Abstract Geochemical proxy records of sea surface temperature (SST) or sea surface salinity (SSS) variability on intra- and interannual time-scales in corals from geological periods older than Pleistocene are extremely rare due to pervasive diagenetic alteration of coralline aragonite. Very recently, however, stable isotope data (δ18O, δ13C) from specimens of Porites of Late Miocene age (10 Ma) have been shown to preserve original environmental signatures. In this paper we describe new finds of the zooxanthellate corals Porites and Tarbellastraea in exceptional aragonite preservation from the island of Crete in sediments of Tortonian (∼ 9 Ma) and Early Messinian (∼ 7 Ma) age. Systematic, co…
Western Mediterranean Climate Response to Dansgaard/Oeschger Events: New Insights From Speleothem Records
The climate of the western Mediterranean was characterized by a strong precipitation gradient during the Holocene driven by atmospheric circulation patterns. The scarcity of terrestrial paleoclimate archives has precluded exploring this hydroclimate pattern during Marine Isotope Stages 5 to 3. Here we present stable carbon and oxygen isotope records from three flowstones from southeast Iberia, which show that Dansgaard/Oeschger events were associated with more humid conditions. This is in agreement with other records from the Iberian Peninsula, the Mediterranean, and western Europe, which all responded in a similar way to millennial‐scale climate variability in Greenland. This general incre…
Hydroclimate variability of western Thailand during the last 1400 years
Mainland Southeast Asia is located on the moisture transport route of the Indian summer monsoon (ISM) where hydroclimate records from speleothems have rarely been investigated. Here, we present a new multi-proxy (δ18O and δ13C values, trace element concentrations, and grayscale values) data set of stalagmite KPC1 from Khao Prae cave in western Thailand spanning the last 1400 years (500–1900 CE; the Common Era). These multi-proxy data reveal a high variability between the wet and dry periods during 500–850 CE and 1150–1300 CE, stable climate conditions during 850–1150 CE, and overall dry conditions since 1300 CE. The δ13C values, trace elements concentrations, and grayscale values show cente…
Thallium geochemistry in the metamorphic Lengenbach sulfide deposit, Switzerland: Thallium-isotope fractionation in a sulfide melt
The Lengenbach (Switzerland) Pb-As-Tl-Zn deposit was formed from a sulfide melt at about 500 °C during Alpine metamorphism, but details on its formation and especially the source of the metals are still under debate. In this study we present two sample sets to address these questions: 1. MC-ICP-MS analyses of thallium isotopes in sulfides, sulfosalts, and melt inclusions from the Alpine metamorphic Lengenbach deposit in the Binn Valley of Switzerland, the non-metamorphic Wiesloch Mississippi Valley-type deposit in Southern Germany, and the Cu- and As-rich mineralization at Pizzo Cervandone about 2 km SW of the Lengenbach deposit, which has been discussed as potential source of the Lengenbac…
Calcification response of reef corals to seasonal upwelling in the northern Arabian Sea (Masirah Island, Oman)
Tropical shallow-water reefs are the most diverse ecosystems in the ocean. Their persistence rests upon adequate calcification rates of the reef building biota, such as reef corals. Coral calcification is favoured in oligotrophic environments with high seawater saturation states of aragonite (Ωsw), which leads to an increased vulnerability to anthropogenic ocean acidification and eutrophication. Here we present Porites calcification records from the northern Arabian Sea upwelling zone and investigate the coral calcification response to low Ωsw and high nutrient concentrations due to seasonal upwelling. The calcification rate was determined from the product of skeletal extension rate and bul…
The giant inoceramid Platyceramus platinus as a high-resolution paleoclimate archive for the Late Cretaceous of the Western Interior Seaway
Abstract Platyceramus platinus was a giant inoceramid bivalve that inhabited the outer shelf environments of the Western Interior Seaway (WIS) in North America. With axial heights typically exceeding 1 m, the shells of this species potentially serve as a unique high-resolution geochemical proxy archive for Late Cretaceous paleoclimate. Here we present the first sclerochronological investigation of P. platinus shells to evaluate the usefulness of this species as an archive of short-term (e.g., seasonal to inter-annual) paleoenvironmental variability. We analyzed the growth patterns, the stable oxygen (δ18O) and carbon (δ13C) isotope values of well-preserved P. platinus shell fragments from t…
TERMITE: AnRscript for fast reduction of laser ablation inductively coupled plasma mass spectrometry data and its application to trace element measurements
RATIONALE High spatial resolution Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS) determination of trace element concentrations is of great interest for geological and environmental studies. Data reduction is a very important aspect of LA-ICP-MS, and several commercial programs for handling LA-ICPMS trace element data are available. Each of these software packages has its specific advantages and disadvantages. METHODS Here we present TERMITE, an R script for the reduction of LA-ICPMS data, which can reduce both spot and line scan measurements. Several parameters can be adjusted by the user, who does not necessarily need prior knowledge in R. Currently, ten reference m…
Paleoclimate variability during the Blake geomagnetic excursion (MIS 5d) deduced from a speleothem record
To evaluate possible connections between climate and the Earth's magnetic field, we examine paleoclimate proxies in a stalagmite (PA-8) recording the Blake excursion (∼112–∼116.4 ka) from Cobre cave (N Spain). Trace element, δ13C, δ18O, δ234U, fluorescent lamination, growth rate, and paleomagnetic records were synchronized using a floating lamina-counted chronology constrained by U–Th dates, providing a high-resolution multi-proxy paleoclimate record for MIS 5d. The alpine cave setting and the combination of proxies contributed to improve the confidence of the paleoclimatic interpretation. Periods of relatively warm and humid climate likely favored forest development and resulted in high sp…
Environmental and biological factors influencing trace elemental and microstructural properties of Arctica islandica shells
Long-term and high-resolution environmental proxy data are crucial to contextualize current climate change. The extremely long-lived bivalve, Arctica islandica, , is one of the most widely used paleoclimate archives of the northern Atlantic because of its fine temporal resolution. However, the interpretation of environmental histories from microstructures and elemental impurities of A. islandica, shells is still a challenge. Vital effects (metabolic rate, ontogenetic age, and growth rate) can modify the way in which physiochemical changes of the ambient environment are recorded by the shells. To quantify the degree to which microstructural properties and element incorporation into A. island…
Characterisation of Apatites as Potential Uranium Reference Materials for Fission-track Dating by LA-ICP-MS
We report homogeneity tests on large natural apatite crystals to evaluate their potential as U reference materials for apatite fission-track (AFT) thermochronology by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The homogeneity tests include the measurements of major element concentrations by electron probe microanalysis (EPMA), whereas for U concentration, isotope dilution (ID) ICP-MS and laser ablation (LA) ICP-MS were employed. Two apatite crystals are potential reference materials for LA-ICP-MS analysis: a 1 cm3 fraction of a Durango crystal (7.5 μg g−1 U) and a 1 cm3 Mud Tank crystal (6.9 μg g−1 U). The relative standard deviation (1 RSD) of the U concentrat…
Reproducibility of trace element time-series (Na/Ca, Mg/Ca, Mn/Ca, Sr/Ca, and Ba/Ca) within and between specimens of the bivalve Arctica islandica – A LA-ICP-MS line scan study
Abstract Trace element time-series in bivalve mollusk shells and other (biogenic) materials can potentially serve as environmental proxies. Yet, the applicability of element-to-calcium ratios is often challenging, because non-environmental factors such as vital effects distort or mask environmental signals. If a trace element time-series is driven by an environmental factor, it should be reproducible within and between coeval specimens of the same species. In the present study, we tested whether time-series of trace element-to-calcium ratios can be reproduced within and between coeval specimens of the bivalve Arctica islandica and thus whether an external signal is encoded in the temporal v…
Late Miocene sea surface salinity variability and paleoclimate conditions in the Eastern Mediterranean inferred from coral aragonite δ18O
Abstract Coral skeletons are archives of chemical proxies which enable paleoenvironmental reconstructions to be made at subannual resolution. Stable oxygen isotope ( δ 18 O) ratios of these archives reflect sea surface temperature (SST) as well as the δ 18 O composition of ambient seawater. The δ 18 O seawater composition is not only controlled by global ice build-up, but river discharge and the hydrological balance of evaporation and precipitation, all influencing sea surface salinity (SSS), also play an important role in marginal seas. New sub-annually resolved coral δ 18 O data were measured and evaluated together with published data from reef coral communities of Late Miocene age from C…
Evidence of warm and humid interstadials in central Europe during early MIS 3 revealed by a multi-proxy speleothem record
Marine Isotope Stage 3 (MIS 3, 57-27 ka) was characterised by numerous rapid climate oscillations (i.e., Dansgaard-Oeschger (D/O-) events), which are reflected in various climate archives. So far, MIS 3 speleothem records from central Europe have mainly been restricted to caves located beneath temperate Alpine glaciers or close to the Atlantic Ocean. Thus, MIS 3 seemed to be too cold and dry to enable speleothem growth north of the Alps in central Europe. Here we present a new speleothem record from Bunker Cave, Germany, which shows two distinct growth phases from 52.0 (+0.8, -0.5) to 50.9 (+0.6, -1.3) ka and 473 (+1.0, -0.6) to 42.8 (+/- 0.9) ka, rejecting this hypothesis. These two growth…
Strontium/lithium ratio in aragonitic shells of Cerastoderma edule (Bivalvia) — A new potential temperature proxy for brackish environments
Abstract Quantitative reconstruction of water temperature from shells of bivalve mollusks is still a very challenging task. For example, in highly variable environments such as intertidal zones, shell oxygen isotope values can only provide reliable temperature estimates if the δ18Owater signature during the time of growth is known. Furthermore, trace element-to-calcium ratios such as Sr/Ca or Mg/Ca often do not serve as reliable paleothermometers, because their incorporation into bivalve shells is known to be strongly biologically controlled. Here, we present a potential novel temperature proxy which is based on the Sr/Lishell ratio of the intertidal bivalve Cerastoderma edule. Up to 81% of…
FeMnOx-1: A new microanalytical reference material for the investigation of Mn–Fe rich geological samples
Suitable Mn-Fe rich microanalytical reference materials (MRMs) as calibration material for laser ablation-inductively coupled plasma mass spectrometry (LA-ICPMS) have not been available. The United States Geological Survey (USGS) in collaboration with the Max Planck Institute for Chemistry has prepared a synthetic MRM, FeMnOx-1, with elevated mass fractions of MnO (25 g/100 g), Fe2O3 (8.5 g/100 g) and high mass fractions of 25 trace elements varying between 200 and 5000 mg/kg. This new MRM has been designed as calibration material for a wide range of different Mn-Fe deposits, such as desert/rock varnish, ocean crusts and nodules as well as Mn accumulations in soils and lakes. Small-scale an…
Supplement_Budsky – Supplemental material for Speleothem δ13C record suggests enhanced spring/summer drought in south-eastern Spain between 9.7 and 7.8 ka – A circum-Western Mediterranean anomaly?
Supplemental material, Supplement_Budsky for Speleothem δ13C record suggests enhanced spring/summer drought in south-eastern Spain between 9.7 and 7.8 ka – A circum-Western Mediterranean anomaly? by Alexander Budsky, Denis Scholz, Jasper A Wassenburg, Regina Mertz-Kraus, Christoph Spötl, Dana FC Riechelmann, Luis Gibert, Klaus Peter Jochum and Meinrat O Andreae in The Holocene
Detrital-zircon geochronology and provenance of the El Oro Metamorphic Complex, Ecuador: Geodynamic implications for the evolution of the western Gondwana margin
Abstract The El Oro Metamorphic Complex (EOMC) in SW Ecuador has been the subject of debate for several decades. While previous studies have focused on the metamorphic and deformation history of the complex to determine its geodynamic evolution, the pre-metamorphic history and its association to units in the north-central Andes remains poorly understood. Here we present a U-Pb detrital zircon provenance study to provide insights into the depositional history and the geodynamic setting of the EOMC. Our results imply that the southern portion of the EOMC (the Tahuin division) is composed of an older Palaeozoic (pre-Famatinian) sequence in the south (El Tigre unit; c. 525-510 Ma), and younger …
Carboniferous granites on the northern margin of Gondwana, Anatolide-Tauride Block, Turkey - Evidence for southward subduction of Paleotethys
Carboniferous metagranites with U-Pb zircon crystallization ages of 331-315 Ma crop out in the Afyon zone in the northern margin of the Anatolide-Tauride Block, which is commonly regarded as part of Gondwana during the Late Palaeozoic. They are peraluminous, calc-alkaline and are characterized by increase in Rb and Ba, decrease in Nb-Ta, and enrichment in Sr and high LILE/HFSE ratios compatible with a continental arc setting. The metagranites intrude a metasedimentary sequence of phyllite, metaquartzite and marble; both the Carboniferous metagranites and metasedimentary rocks are overlain unconformably by Lower Triassic metaconglomerates, metavolcanics and Upper Triassic to Cretaceous recry…
Sodium provides unique insights into transgenerational effects of ocean acidification on bivalve shell formation
Abstract Ocean acidification is likely to have profound impacts on marine bivalves, especially on their early life stages. Therefore, it is imperative to know whether and to what extent bivalves will be able to acclimate or adapt to an acidifying ocean over multiple generations. Here, we show that reduced seawater pH projected for the end of this century (i.e., pH 7.7) led to a significant decrease of shell production of newly settled juvenile Manila clams, Ruditapes philippinarum. However, juveniles from parents exposed to low pH grew significantly faster than those from parents grown at ambient pH, exhibiting a rapid transgenerational acclimation to an acidic environment. The sodium compo…
A 4000-year long Late Holocene climate record from Hermes Cave (Peloponnese, Greece)
The societal and cultural development during the Bronze Age and the subsequent Iron Age was enormous in Greece, however interrupted by two significant transformations around 4200 years b2k (Early Helladic II/III; b2k refers to years before 2000 CE) and 3200 years b2k (end of Late Helladic III). Artefacts and building remains provide some insights into the cultural evolution, but only little is known about environmental and climatic changes on a detailed temporal and spatial scale. Here we present a 4000-year long stalagmite record (GH17-05) from Hermes Cave, Greece, located on Mount Ziria in the close vicinity of the Late Bronze Age citadel of Mycenae and the Classical-Hellenistic polis of …
The aqueduct of Gerasa – Intra-annual palaeoenvironmental data from Roman Jordan using carbonate deposits
Abstract Calcium carbonate (CaCO3) deposits from Roman aqueducts are an innovative archive to obtain local high-resolution palaeoenvironmental and archaeological data in interdisciplinary studies. Deposits from one of the aqueducts of the Roman city of Gerasa provide a record of 59 years during the 1st to 3rd centuries CE, divided into three sequences separated by plaster layers. Annual carbonate layers show an alternation of sparite, formed in winter, and micrite, formed in summer. Brown bands at the base of many sparite layers probably correspond to large rainstorms in early winter. A fine lamination present in the brown bands may be diurnal in origin. Stable isotope and trace element dat…
LA-ICP-MS analyses on coral growth increments reveal heavy winter rain in the Eastern Mediterranean at 9 Ma
Abstract Sediment particles incorporated into coral skeletons reflect variation in composition and amount of suspended material in ambient water during coral growth. They can be used to identify periods of enhanced storm frequency and associated freshwater discharge. Tortonian (Late Miocene) Porites corals from Crete (Aegean Sea, Eastern Mediterranean) show pronounced annual density bands in X-ray photographs. δ18O compositional variability reflects the annual banding equivalent with a ~ 7 °C annual sea surface temperature (SST) cycle over a seven-year period. Fine sediment particles are concentrated in layers with skeletal porosity parallel to growth increments. Variations in the chemical …
Diagenetic stability of non-traditional stable isotope systems (Ca, Sr, Mg, Zn) in teeth – An in-vitro alteration experiment of biogenic apatite in isotopically enriched tracer solution
Stable isotope ratios and trace element concentrations of fossil bones and teeth are important geochemical proxies for the reconstruction of diet and past environment in archaeology and palaeontology. However, since diagenesis can significantly alter primary diet-related isotope signatures and elemental compositions, it is important to understand and quantify alteration processes. Here, we present the results of in-vitro alteration experiments of dental tissues from a modern African elephant molar reacted in aqueous solutions at 30 °C and 90 °C for 4 to 63 days. Dental cubes with ≈ 3 mm edge length, comprising both enamel and dentin, were placed into 2 mL of acidic aqueous sol…
Precise chronology of Polynesian temple construction and use for southeastern Maui, Hawaiian Islands determined by 230Th dating of corals
International audience; Emergent archaic states in pre-contact Hawai'i used a ritual control hierarchy implemented through a system of temples to manage production, extract tribute, and reinforce the legitimacy of the ruling elites. Based on a limited sample of precise 230Th dates from coral offerings on Maui Island temples it had been hypothesized that this temple system rapidly expanded during the period from A.D. 1580–1640. We tested this hypothesis by obtaining an expanded sample of 39 new 230Th coral dates from temples in Kahikinui District, and one sample from the summit of a cinder cone that likely had ritual significance. Combined with seven coral dates previously obtained, this yie…
Morphological and chemical evolution of corundum (ruby and sapphire): Crystal ontogeny reconstructed by EMPA, LA-ICP-MS, and Cr3+Raman mapping
The term “ ontogeny ,” which is commonly used in biology, was introduced into the Earth sciences in 1961 to include the genesis and evolution of single crystals and crystal aggregates. The term encompasses nucleation , growth , alteration , and destruction . We present results of studies concerning the ontogeny of natural corundum (rubies and sapphires), and the chemical and morphological evolution of corundum crystals from deposits in Africa (Kenya, Tanzania, Madagascar) and Southeast Asia (Vietnam). Trace-element compositions indicative for different corundum habits were determined by rim-to-rim LA-ICP-MS and electron microprobe analyses. Raman spectroscopy was applied for Cr 3+ photolumi…
Origin, age, and significance of deep-seated granulite-facies migmatites in the Barrow zones of Scotland, Cairn Leuchan, Glen Muick area
Funding for this work was provided by the Johannes-Gutenberg University of Mainz. Petrological modelling of granulite‐facies mafic and semipelitic migmatites from Cairn Leuchan, northeast Scotland, has provided new constraints on the pressure (P) and temperature (T) conditions of high‐grade metamorphism in the type‐locality Barrow zones.Phase diagrams constructed in the Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O2 system have constrained the P–T conditions of peak metamorphism in the Glen Muick region of the upper‐sillimanite zone (Sill+Kfs) to have been at least ~840 ◦C at ~9 kbar (high‐pressure granulite facies). These conditions are approximately ~120 ◦C and ~3 kbar higher than those reco…
Carbonate deposits from the ancient aqueduct of Béziers, France — A high-resolution palaeoenvironmental archive for the Roman Empire
Abstract Carbonate deposits from a Roman aqueduct in Beziers, southern France, record environmental conditions during the late first century C.E. These deposits formed in a steep section of the aqueduct with a high flow velocity, which caused rapid deposition of up to 11 mm of calcite per year over a period of 22–24 years. The microstructure, trace element and stable isotope composition show that regular deposition was interrupted by high-discharge events, probably in response to heavy rainfall during autumn and winter, transporting colloidally- and particle-bound elements and depositing calcite with elevated δ 18 O values. Individual autumn high-discharge events coincide with abrupt decrea…
Strontium Uptake and Intra-Population 87Sr/86Sr Variability of Bones and Teeth—Controlled Feeding Experiments With Rodents (Rattus norvegicus, Cavia porcellus)
Strontium isotopes in biogenic apatite, especially enamel, are widely employed to determine provenance and track migration in palaeontology and archaeology. Body tissues record the 87Sr/86Sr of bioavailable Sr of ingested food and water. To identify non-local individuals, knowledge of the 87Sr/86Sr of a non-migratory population is required. However, varying factors such as tissue turnover rates, feeding selectivity, Sr content, digestibility of food, and the ingestion of mineral dust can influence body tissue 87Sr/86Sr. To evaluate the Sr contribution of diet and water to mammalian hard tissues 87Sr/86Sr, controlled feeding studies are necessary. Here we present 87Sr/86Sr from controlled fe…
Melting and dynamic metasomatism of mixed harzburgite + glimmerite mantle source: Implications for the genesis of orogenic potassic magmas
Abstract Tectonically young, orogenic settings are commonly the sites of post-collisional silica-rich ultrapotassic magmas with extreme K2O-contents of up to 9 wt% and K2O/Na2O > 2. Many experimental studies investigating the generation of these melts have concentrated on melting of homogenous phlogopite bearing peridotites, whereas geochemical signatures indicate the involvement of at least two types of source rocks: ultra-depleted and K and trace elements-enriched ones. We report the results of melting experiments at 1–2 GPa of mixed glimmerite and harzburgite, in which these rock types make up two halves each capsule. Melting begins in the glimmerite, and its metasomatic effects on the h…
Nutrients attenuate the negative effect of ocean acidification on reef coral calcification in the Arabian Sea upwelling zone (Masirah Island, Oman)
Tropical shallow-water reefs are the most diverse ecosystem in the ocean. Its persistence rests upon adequate calcification rates of the reef building biota, such as reef corals. Optimum calcification rates of reef corals occur in oligotrophic environments with high seawater saturation states of aragonite (Ωsw), which leads to increased vulnerability to anthropogenic ocean acidification and eutrophication. The calcification response of reef corals to this changing environment is largely unknown, however. Here, we present annually and sub-annually resolved records of calcification rates (n = 3) of the coral Porites from the nutrient rich and low Ωsw Arabian Sea upwe…
Sodium provides unique insights into transgenerational effects of ocean acidification on bivalve shell formation
Ocean acidification is likely to have profound impacts on marine bivalves, especially on their early life stages. Therefore, it is imperative to know whether and to what extent bivalves will be able to acclimate or adapt to an acidifying ocean over multiple generations. Here, we show that reduced seawater pH projected for the end of this century (i.e., pH 7.7) led to a significant decrease of shell production of newly settled juvenile Manila clams, Ruditapes philippinarum. However, juveniles from parents exposed to low pH grew significantly faster than those from parents grown at ambient pH, exhibiting a rapid transgenerational acclimation to an acidic environment. The sodium composition of…
Insights fromsodium into the impacts of elevated pCO2 and temperature on bivalve shell formation
Ocean acidification and warming are predicted to affect the ability of marine bivalves to build their shells, but little is known about the underlying mechanisms. Shell formation is an extremely complex process requiring a detailed understanding of biomineralization processes. Sodium incorporation into the shells would increase if bivalves rely on the exchange of Na+/H+ to maintain homeostasis for shell formation, thereby shedding new light on the acid-base and ionic regulation at the calcifying front. Here, we investigated the combined effects of seawater pH (8.1, 7.7 and 7.4) and temperature (16 and 22 °C) on the growth and sodium composition of the shells of the blue mussel, Mytilus edul…