Regina Mertz-Kraus

Linking coral river runoff proxies with climate variability, hydrology and land-use in Madagascar catchments

Understanding the linkages between coastal watersheds and adjacent coral reefs is expected to lead to better coral reef conservation strategies. Our study aims to examine the main predictors of environmental proxies recorded in near shore corals and therefore how linked near shore reefs are to the catchment physical processes. To achieve these, we developed models to simulate hydrology of two watersheds in Madagascar. We examined relationships between environmental proxies derived from massive Porites spp. coral cores (spectral luminescence and barium/calcium ratios), and corresponding time-series (1950-2006) data of hydrology, climate, land use and human population growth. Results suggest regional differences in the main environmental drivers of reef sedimentation: on annual time-scales, precipitation, river flow and sediment load explained the variability in coral proxies of river discharge for the northeast region, while El Niño-Southern Oscillation (ENSO) and temperature (air and sea surface) were the best predictors in the southwest region.

In situ 230Th-232Th-234U-238U analysis of silicate glasses and carbonates using laser ablation single-collector sector-field ICP-MS

We present a novel method for the determination of Th and U isotopic ratios by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) applicable to samples with U concentrations as low as 0.4 µg g−1. While previous in situ U-series determinations have used multi-collector (MC) ICP-MS, we use a single-collector sector-field ICP-MS connected to a 213 nm Nd:YAG laser. Precision and accuracy were determined for different matrices: NIST SRM 612, MPI-DING (T1-G, and ATHO-G) and USGS (BHVO-2G, NKT-1G, and BCR-2G) reference glasses, 91500 zircon, and a travertine. We used a laser beam with a diameter of 110 µm and tracks up to 1800 µm long in order to obtain adequate precision on samples with the lowest abundances of 230Th and 234U. We applied corrections for background, tailing of the 232Th, 235U and 238U beams on 230Th and 234U, instrumental mass discrimination, and elemental sensitivity. Mass discrimination and relative elemental sensitivities for Th and U are similar for igneous rock glasses, zircon, and calcium carbonate under the experimental conditions used; synthetic, transparent NIST SRM 612, however, yields different values. Therefore, we used BCR-2G (Th/U = 3.507 ± 0.018 (1 SE)) for calibration of relative elemental sensitivities. The internal precision of three line scans obtained for 230Th/238U, 234U/238U, and 230Th/232Th ratios varies between 0.1 and 2.8% (relative standard error, 1 RSE), limited by counting statistics on the minor isotopes. For repeated measurements of BCR-2G and the travertine, we obtained activity ratios (±2SD) of (230Th/238U) = 1.000 ± 0.006 and (234U/238U) = 0.994 ± 0.014, and (230Th/238U) = 1.493 ± 0.032 and (234U/238U) = 1.369 ± 0.011, respectively, concordant within 2% of TIMS values. This consistency indicates that LA-ICP-SF-MS is a suitable method for U-series analyses. Regarding future studies, it also provides the advantage of combining U–Th isotope ratio determinations with additional multi-element and isotope analyses, respectively, during a single line scan.

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., pH7.7) 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 the shells may shed new light on the mechanisms responsible for beneficial transgenerational acclimation. Irrespective of parental exposure, the amount of Na incorporated into shells increased with decreasing pH, implying active removal of excessive protons through the Na+/H+ exchanger which is known to depend on the Na+ gradient actively built up by the Na+/K+-ATPase as a driving force. However, the shells with a prior history of transgenerational exposure to low pH recorded significantly lower amounts of Na than those with no history of acidic exposure. It therefore seems very likely that the clams may implement less costly and more ATP-efficient ion regulatory mechanisms to maintain pH homeostasis in the calcifying fluid following transgenerational acclimation. Our results suggest that marine bivalves may have a greater capacity to acclimate or adapt to ocean acidification by the end of this century than currently understood.

Thallium geochemistry in the metamorphic Lengenbach sulfide deposit, Switzerland: Thallium-isotope fractionation in a sulfide melt

Abstract 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 Lengenbach metals. (2) LA-ICP-MS analyses of micas from the Lengenbach deposit and surrounding country rocks between the deposit and the Pizzo Cervandone to trace potential metal-bearing fluid pathways. We found that Tl isotope compositions expressed as ε205Tl values in all investigated samples range from -4.1 ± 0.5 to +1.9 ± 0.5. The whole variation can be seen in the Lengenbach deposit alone, which hence records considerable fractionation even during high-temperature processes involving a sulfide melt. This large range of ε205Tl is thought to be caused by nuclear volume-dependent fractionation. Interestingly, the common fahlores at Lengenbach behave differently from all other investigated sulfosalts: based on their heavy isotopic composition together with a low As/S-ratio, they do not seem to be crystallized from the sulfide melt, but are interpreted to have formed from hydrothermal fluids enriched in the heavy Tl isotopes. Although As mobilization in the gneisses and dolomites surrounding the Lengenbach deposit is evident based on secondary arsenites, no traces of such a country rock fluid could be found in fissure micas at Lengenbach. Hence, considerations involving K/Rb, Rb/Tl, As/S, and Pb/Tl ratios in the sulfides and micas imply that the element enrichment in the Lengenbach deposit is either pre-Alpine or related to peak metamorphism, but occurred definitely before mica growth at Lengenbach.

Density banding in corals: barcodes of past and current climate change

The predicted sea surface temperature (SST) rise over the next decades is likely hazardous to coral health because precipitation of the calcareous skeleton depends primarily on SST. Temperature modulates vertical growth and density of the skeleton with seasonal SST changes resulting in an alternation of high-density and low-density bands (HDB and LDB). Notably, growth rates and the timing of the HDBs and LDBs relative to the seasons differ on a global scale within geographic regions. In this contribution, we use combined information of skeletal density and seasonally resolved oxygen isotope SST estimates from massive Porites from a Late Miocene (9 Ma) reef in the eastern Mediterranean Sea (Crete, Greece) to understand reef vulnerability over short and geological periods of time. Three types of HDB–SST relationships have been found: (1) coincidence of HDB with summer, (2) winter or (3) autumn and spring. The latter doubles HDBs in a year and implies maximum calcification is coupled to the taxon-specific optimum SST during the transitional seasons and reduced at its respective critical winter and summer SSTs. Modeling with a nonlinear temperature–calcification relationship reproduces the climate barcode of density bands. The model should be relevant for other poikilothermic carbonate producers in reefs and platforms and has implications for judging geographic distributions and causes of extinctions of corals, benthic carbonate communities and entire carbonate systems. With regard to the causes underlying expansion and demise of carbonate platforms and reefs in geological history, we expect the model predictions to help for a deeper understanding of biotic responses during hyperthermals or coolings and possibly also for identifying regions in the modern ocean where corals are endangered or taking advantage of global warming.

TERMITE: An R script for fast reduction of laser ablation inductively coupled plasma mass spectrometry data and its application to trace element measurements: TERMITE: An R script for reduction of LA-ICPMS data

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 materials with different matrices for calibration of LA-ICPMS data are implemented, and additional reference materials can be added by the user. TERMITE also provides an optional outlier test, and the results are provided graphically (as a pdf file) as well as numerically (as a csv file). RESULTS As an example, we apply TERMITE to a speleothem sample and compare the results with those obtained using the commercial software GLITTER. The two programs give similar results. TERMITE is particularly useful for samples that are homogeneous with respect to their major element composition (in particular for the element used as an internal standard) and when many measurements are performed using the same analytical parameters. In this case, data evaluation using TERMITE is much faster than with all other available software, and the concentrations of more than 100 single spot measurements can be calculated in less than a minute. CONCLUSIONS TERMITE is an open-source software for the reduction of LA-ICPMS data, which is particularly useful for the fast, reproducible evaluation of large datasets of samples that are homogeneous with respect to their major element composition. Copyright

Morphological and chemical evolution of corundum (ruby and sapphire): Crystal ontogeny reconstructed by EMPA, LA-ICP-MS, and Cr3+ Raman mapping

Abstract 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 Cr3+ photoluminescence mapping. Results traced the development of corundum crystals and the evolution of their chemistry and morphology, and helped to clarify the geological processes within particular deposits. These variations of corundum morphology are directly correlated with Cr and Fe contents and varying P-T conditions that prevailed during crystal growth. Dipyramidal habits combined with white color in corundum from two deposits in the Mangari area in Kenya have Cr concentrations of ~200–700 μg/g in crystals that grew under high P-T conditions. Prismatic habit of bright red ruby crystals was linked to Cr concentrations of ≥1500 μg/g in samples from Luc Yen (Vietnam) and Mangari (Kenya), formed under lower P-T. Concentrations of Cr between 700–1500 μg/g are associated with pink color and combinations of different habits (dipyramidal, prismatic, or dipyramidal-prismatic) in these samples. Contents of Fe ~700 μg/g and Cr ~1200 μg/g in sapphire crystals from the Morogoro area of Tanzania caused pink color that correlated with dipyramidal habit and elongation along the c axis. Rhombohedral habit and blue-violet color were observed at Cr ~600 μg/g and Fe ≥2000 μg/g in sapphires from Andranondambo in Madagascar, formed during the final stage of contact metamorphism.

TERMITE-An R script for fast reduction of LA-ICPMS 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 materials with different matrices for calibration of LA-ICPMS data are implemented, and additional reference materials can be added by the user. TERMITE also provides an optional outlier test, and the results are provided graphically (as a pdf file) as well as numerically (as a csv file). RESULTS As an example, we apply TERMITE to a speleothem sample and compare the results with those obtained using the commercial software GLITTER. The two programs give similar results. TERMITE is particularly useful for samples that are homogeneous with respect to their major element composition (in particular for the element used as an internal standard) and when many measurements are performed using the same analytical parameters. In this case, data evaluation using TERMITE is much faster than with all other available software, and the concentrations of more than 100 single spot measurements can be calculated in less than a minute. CONCLUSIONS TERMITE is an open-source software for the reduction of LA-ICPMS data, which is particularly useful for the fast, reproducible evaluation of large datasets of samples that are homogeneous with respect to their major element composition. Copyright

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. islandica shells is vitally or/and environmentally affected, A. islandica specimens were reared for three months under different water temperatures (3, 8 and 13 °C) and food concentrations (low, medium and high). Concentrations of Mg, Sr, Na, and Ba were measured in the newly formed shell portions by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The microstructures of the shells were analyzed by Scanning Electron Microscopy (SEM). Shell growth and condition index of each specimen were calculated at the end of the experimental period. Findings indicate that no significant variation in the morphometric characteristics of the microstructures were formed at different water temperatures or different food concentrations. Shell carbonate that formed at lowest food concentration usually incorporated the highest amounts of Mg, Sr and Ba relative to Ca+2 (except for Na) and was consistent with the slowest shell growth and lowest condition index at the end of the experiment. These results seem to indicate that, under food limitation, the ability of A. islandica to discriminate element impurities during shell formation decreases. Moreover, all trace element-to‑calcium ratios were significantly affected by shell growth rate. Therefore, physiological processes seem to dominate the control on element incorporation into A. islandica shells.

Origin, age, and significance of deep-seated granulite-facies migmatites in the Barrow zones of Scotland, Cairn Leuchan, Glen Muick area

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 recorded by lower-sillimanite zone (Sill+Ms) units located only a few kilometres away to the southeast at Glen Girnock, indicating the presence of a significant thermal and barometric high exposed within the Scottish Dalradian and supporting previous suppositions of a potential tectonic break between the two regions. U–Pb zircon geochronology performed on these mafic migmatites produced ages of c. 540–470 Ma from grains with both igneous and metamorphic morphological characteristics. Their basaltic protoliths likely formed during a period of volcanism dated at ∼570 Ma, associated with passive-margin extension prior to the onset of Iapetus Ocean closure, and high-grade metamorphism and partial melting is interpreted to have taken place at around 470 Ma, synchronous with sillimanite-grade metamorphism recorded elsewhere in the Dalradian. These high-grade Cairn Leuchan lithologies are interpreted as representing a fragment of Grampian Terrane lower crust that This article has been accepted for publication and undergone full peer review but has not been through the copyediting, typesetting, pagination and proofreading process, which may lead to differences between this version and the Version of Record. Please cite this article as doi: 10.1111/jmg.12428 This article is protected by copyright. All rights reserved. A cc ep te d A rt ic le was exhumed via displacement along a steeply dipping tectonic discontinuity related to the Portsoy–Duchray Hill Lineament, and are not pre-Caledonian Mesoproterozoic basement, as suggested by some previous studies. Veins within some mafic migmatites in the Cairn Leuchan area, composed almost entirely (>80%) of garnet, with minor quartz, plagioclase, amphibole, and clinopyroxene, are interconnected with leucosomes and are interpreted to represent former garnet-bearing melt segregations that have been locally drained of almost all melt. Thus, mafic components of the lower crust, currently underlying relatively lower-grade metasediments exposed to the southeast, may represent a potential source rock for widely documented, post-orogenic felsic plutons, sills, and dykes that occur throughout the Grampian Terrane.