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Fish stocking occurs in aquatic systems for conservation purposes, to create or enhance recreational fisheries and to enhance wild-catch commercial fisheries. Identifying and quantifying the contribution of stocking efforts to wild populations is crucial to informing these management objectives. Provenance determination methods trade off accuracy, replicability, and costeffectiveness at fishery-relevant scales. We present and assess multiple methods for provenance determination using a case study of barramundi (Lates calcarifer) in the Dry Tropics region of northern Australia. A novel application of near-infrared spectroscopy (NIRS) is compared to two established methods for fish provenance, otolith microchemistry and genetic parentage analysis using microsatellites. The otolith microchemistry method was able to provide extremely high provenance resolution (>99% accuracy). The microsatellite parentage analysis method had a slightly lower overall accuracy (95%), likely as a result of genetic introgression in this region. Provenance determination using otolith NIRS had the lowest overall accuracy (76%). Once limitations regarding spectral noise, image resolution, and sample size are addressed, NIRS may have potential for costeffectively determining provenance in fish. Key words: barramundi, Lates calcarifer, provenance, natal origin, fish stocking, stock enhancement, otolith microchemistry, NIRS, microsatellite parentage analysis, Introduction Fish stocking occurs in aquatic systems around the world for conservation purposes, to create or enhance recreational fisheries and to enhance wild-catch commercial fisheries (Warren-Myers et al. 2018). Identifying [...]

This study aims to evaluate relationships between elemental signatures in calcite and the crystallographic orientation of its planes. The ability of calcite (a widespread calcium carbonate mineral) to entrap various trace and minor elements in its structure is the foundation of multiple methods (also called proxies) to reconstruct paleoenvironment conditions (e.g., temperature, pH, and marine chemistry). Although several element-to-calcium ratios (E/Ca) are routinely measured in marine carbonates and are widely used in paleoclimate studies, some of the controls on the incorporation of these elements are still unclear. Here, we examine the effect of crystallography on (E/Ca)calcite by growing thin layers of calcite on differently oriented Iceland Spar substrates immersed in modified seawater solution. Newly grown calcite layers were examined with Laser Ablation Inductivity–Coupled Plasma Mass Spectrometry (LA-ICP-MS), Backscattered Electron Imaging (BSE), and Energy Dispersive X-ray Spectroscopy (EDS). We propose that the crystallographic orientation might slightly influence the incorporation of lithium (Li), sodium (Na), magnesium (Mg), sulfur (S), and barium (Ba) into the studied calcite faces and have no impact on the incorporation of boron (B), potassium (K), and strontium (Sr) at least under the conditions of our experiment. [ABSTRACT FROM AUTHOR]

Coccolithophores are an important group of calcifying marine phytoplankton. Although coccolithophores are not silicified, some species exhibit a requirement for Si in the calcification process. These species also possess a novel protein (SITL) that resembles the SIT family of Si transporters found in diatoms. However, the nature of Si transport in coccolithophores is not yet known, making it difficult to determine the wider role of Si in coccolithophore biology. Here, we show that coccolithophore SITLs act as Na+‐coupled Si transporters when expressed in heterologous systems and exhibit similar characteristics to diatom SITs. We find that CbSITL from Coccolithus braarudii is transcriptionally regulated by Si availability and is expressed in environmental coccolithophore populations. However, the Si requirement of C. braarudii and other coccolithophores is very low, with transport rates of exogenous Si below the level of detection in sensitive assays of Si transport. As coccoliths contain only low levels of Si, we propose that Si acts to support the calcification process, rather than forming a structural component of the coccolith itself. Si is therefore acting as a micronutrient in coccolithophores and natural populations are only likely to experience Si limitation in circumstances where dissolved silicon (DSi) is depleted to extreme levels. [ABSTRACT FROM AUTHOR]

An invasive foraminiferan is recorded for the first time in an Australian estuary. Trochammina hadai, originally described as endemic from Japan and subsequently found to be alien in coastal waters of California and Brazil, has been identified in estuarine sediment in the vicinity of Bunbury Port in Western Australia. Species determination is based on morphological, molecular and ecological similarities to the Japanese type. The species has not been recorded in other estuaries in Australia. Bunbury Port is a major exporter of woodchip to Japan and the introduction of T. hadai may have come from ballast water out of shallow-draught woodchip vessels. Small sediment samples of estuarine mud obtained at water depths of ~5 m contain abundant T. hadai (on average,0.4 mm in adult diameter) that are easily recognised in microscopic view of the sediment surface by their bright reddish-brown colour. The collection of sediment samples from the estuarine floor and ballast water, and the examination of these for foraminifers, may provide a useful indicator in estuaries for the possible presence of other exotic species, particularly in the vicinity of ports. [ABSTRACT FROM AUTHOR]

An understanding of population demographics and life history processes is integral to the rehabilitation of fish populations. In Australia's highly modified Murray–Darling Basin, native fish are imperilled and fish deaths in the Darling River in 2018–19 highlighted their vulnerability. Golden perch (Macquaria ambigua) is a long-lived percichthyid that was conspicuous in the fish kills. To guide population rehabilitation in the Darling River, pre-fish kill age structure, provenance and movement of golden perch were explored using otolith microstructure and chemistry (87Sr/86Sr). Across the Lower and Mid-Darling River, recruitment was episodic, with dominant cohorts associated with years characterised by elevated discharge. There was substantial variability in age structure, recruitment source and movement patterns between the Lower and Mid-Darling River. In the Mid-Darling River, tributaries were an important recruitment source, whereas in the Lower Darling fish predominantly originated in the Darling River itself. Downstream movement of juveniles, upstream migration of adults and return movements to natal locations were important drivers of population structure. Restoring resilient golden perch populations in the Darling River will be reliant on mitigating barriers to movement, promoting a connected mosaic of recruitment sources and reinstating the hydrological and hydraulic factors associated with spawning, recruitment and dispersal. Globally, increasing water resource development and climate change will necessitate such integrated approaches to the management of long-lived migratory riverine fishes. To inform rehabilitation following catastrophic fish kills in the Darling River, otoliths (fish ear stones) were used to understand pre-fish kill population structure, provenance and movement of golden perch. Throughout the Darling River, golden perch recruitment was associated with periods of elevated flow, but there were regional differences in age structure and variation in recruitment source and movement. Mitigating barriers to movement and restoring river flows associated with spawning, recruitment and dispersal are key considerations for population rehabilitation. [ABSTRACT FROM AUTHOR]

Understanding the spatial and temporal scales over which key population processes occur is fundamental to effective fisheries management, especially when informing recovery actions following extreme events. In 2018–19, hypoxia-induced fish kills occurred in the lower Darling River, south-eastern Australia. We collected carcasses of three potamodromous species that perished during these events to reconstruct their lifetime movements and identify potential recovery mechanisms. Golden perch Macquaria ambigua , Murray cod Maccullochella peelii and silver perch Bidyanus bidyanus otolith 87Sr/86Sr profiles were compared with water 87Sr/86Sr ratios to better understand natal provenance and movement history, and to identify the scale at which migration influences population processes. Golden perch were predominantly locally spawned (Darling River), although we found some evidence of emigration into the nearby Murray River early in life and return movements into the Darling River. Murray cod were mainly locally spawned and thereafter lifelong residents, with some evidence of stocking supplementing populations. Silver perch were mostly immigrants, with the Murray River (>500 km away) the principal source of fish. For recovery of native fish populations to be effective in the Darling River, recovery actions are required that incorporate knowledge on the relevant spatial and temporal scales over which life history processes occur. Otoliths were used to retrospectively determine lifetime movements of golden perch, Murray cod and silver perch that died in fish kills in the lower Darling River in 2018–19. Movement between the Murray and Darling rivers appears important for population function of golden perch and silver perch, but not Murray cod, emphasising the need for complementary local and regional-scale recovery efforts. [ABSTRACT FROM AUTHOR]

Palaeoclimate variability must be constrained to predict the nature and impacts of future climate change in the Eastern Mediterranean. Here, we present a late Holocene high‐resolution multiproxy data set from Kocain Cave, the first of its kind from SW Turkey. Regional fluctuations in effective‐moisture are recorded by variations in magnesium, strontium, phosphorous and carbon isotopes, with oxygen isotopes reacting to changes in precipitation and effective‐moisture. The new record shows a double‐peak of arid conditions at 1150 and 800 BCE, a wet period 330–460 CE followed by a rapid shift to dry conditions 460–830 CE, and a dry/wet Medieval Climate Anomaly/Little Ice Age pattern. Large discrepancies exist between Turkish records and the Kocain record, which shares more similarities with other Eastern Mediterranean coastal records. Heterogeneity of regional climate and palaeoclimate proxy records are emphasized. Plain Language Summary: Records of past climate are essential in the Eastern Mediterranean to understand regional impacts of modern climate change. In combination with archeology, these allow us to examine climatic impacts on people in the past to help us prepare for the future. Here, we examine a stalagmite (Ko‐1) from Kocain Cave, southwest Turkey, which contains information about past climate change in its chemistry. Measurements of trace‐metals and carbon isotope ratios record the amount of water entering the cave, oxygen isotope ratios record rainfall amount. Measurements of uranium are used to date the climate changes. Earthquakes that damaged nearby cities and caused tsunamis changed the angle of the stalagmite, providing more evidence for dating the sample. The Kocain Cave record shows climatic conditions changed frequently in southwest Turkey. Important are dry conditions 1150 and 800 BCE, wet conditions 330–460 CE followed by a rapid shift to dry conditions 460–830 CE, and a dry/wet Medieval Climate Anomaly/Little Ice Age pattern. These climate changes were different to records from elsewhere in Turkey and matched better with coastal records from Greece and Lebanon/Israel. The complex nature of past climate is emphasized due to varied climatic regions in Turkey and the many impacts on each record. Key Points: Stalagmite Ko‐1 record of effective‐moisture from SW Turkey stresses spatial and temporal heterogeneity of Turkish climateClimate changes share more similarities with other Eastern Mediterranean coastal regions, than central or northern TurkeyHeterogeneity of modern climate and proxy records highlight the complexity of historical comparisons [ABSTRACT FROM AUTHOR]

Foraminifera are a group of mostly marine protists with high taxonomic diversity. Species identification is often complex, as both morphological and molecular approaches can be challenging due to a lack of unique characters and reference sequences. An integrative approach combining state of the art morphological and molecular tools is therefore promising. In this study, we analysed large benthic Foraminifera of the genus Amphisorus from Western Australia and Indonesia. Based on previous findings on high morphological variability observed in the Soritidae and the discontinuous distribution of Amphisorus along the coast of western Australia, we expected to find multiple morphologically and genetically unique Amphisorus types. In order to gain detailed insights into the diversity of Amphisorus, we applied micro CT scanning and shotgun metagenomic sequencing. We identified four distinct morphotypes of Amphisorus, two each in Australia and Indonesia, and showed that each morphotype is a distinct genotype. Furthermore, metagenomics revealed the presence of three dinoflagellate symbiont clades. The most common symbiont was Fugacium Fr5, and we could show that its genotypes were mostly specific to Amphisorus morphotypes. Finally, we assembled the microbial taxa associated with the two Western Australian morphotypes, and analysed their microbial community composition. Even though each Amphisorus morphotype harboured distinct bacterial communities, sampling location had a stronger influence on bacterial community composition, and we infer that the prokaryotic community is primarily shaped by the microhabitat rather than host identity. The integrated approach combining analyses of host morphology and genetics, dinoflagellate symbionts, and associated microbes leads to the conclusion that we identified distinct, yet undescribed taxa of Amphisorus. We argue that the combination of morphological and molecular methods provides unprecedented insights into the diversity of foraminifera, which paves the way for a deeper understanding of their biodiversity, and facilitates future taxonomic and ecological work. [ABSTRACT FROM AUTHOR]

Rationale: Magnesium is one of the most abundant elements in the earth's crust and in seawater. Fractionation of its stable isotopes has been shown to be a useful indicator of many geological, chemical, and biological processes. For example, biogenic carbonates display an 5 range of d26Mg values, which is attributed to variable degrees of biological control on Mg ions during biomineralisation. Understanding this biological control is essential for developing proxies based on biogenic carbonates. Methods: In this work, we present a new approach of measuring Mg isotopes in biogenic carbonates using Laser Ablation Multi-Collector Inductively Coupled Plasma Mass Spectrometry (LA-MC-ICPMS). Results: Our results show that this microanalytical approach provides relatively fast, high spatial resolution (<0.2 µm) measurements with high precision and accuracy down to 0.2? (2SE). To achieve high levels of precision and accuracy, baseline interferences need to be monitored and a carbonate standard with a relatively low trace metal composition similar to biogenic carbonates should be used. We also demonstrate that the matrix effect on Mg isotopes in carbonates with low Fe and Mn is limited to less than 0.2? fractionation under different laser parameters and low oxide condition (<0.3% ThO/Th). Conclusions: Our newly developed LA-MC-ICPMS method and its applications to biogenic carbonates show significant advantages provided by the microanalytical approach in understanding complex processes of biomineralisation in marine calcifiers. [ABSTRACT FROM AUTHOR]

Emiliania huxleyi cells were grown in artificial seawater of different Li and Ca concentrations and coccolith Li/Ca ratios determined. Coccolith Li/Ca ratios were positively correlated to seawater Li/Ca ratios only if the seawater Li concentration was changed, not if the seawater Ca concentration was changed. This Li partitioning pattern of E. huxleyi was previously also observed in the benthic foraminifer Amphistegina lessonii and inorganically precipitated calcite. We argue that Li partitioning in both E. huxleyi and A. lessonii is dominated by a coupled transmembrane transport of Li and Ca from seawater to the site of calcification. We present a refined version of a recently proposed transmembrane transport model for Li and Ca. The model assumes that Li and Ca enter the cell via Ca channels, the Li flux being dependent on the Ca flux. While the original model features a linear function to describe the experimental data, our refined version uses a power function, changing the stoichiometry of Li and Ca. The version presented here accurately predicts the observed dependence of DLi on seawater Li/Ca ratios. Our data demonstrate that minor element partitioning in calcifying organisms is partly mediated by biological processes even if the partitioning behavior of the calcifying organism is indistinguishable from that of inorganically precipitated calcium carbonate. Plain Language Summary: Marine shell‐forming organisms such as the minute, but abundant, coccolithophores (single‐celled phytoplankton) and foraminifera (single‐celled zooplankton) are not only ecologically important but also contribute significantly to the global carbonate sink. Minor elements (e.g., Sr and Li) trapped in biogenic carbonate sediments provide a window into past environmental conditions such as temperature, which is relevant for climate change. An understanding of elemental incorporation processes is required in order to correctly translate these minor element signatures into past environmental data. Here we conducted culture experiments with the coccolithophore Emiliania huxleyi to determine its Li incorporation behavior. We compare our results with previously published data on the foraminifer Amphistegina lessonii and data on synthetic calcite. The Li incorporation behavior of biogenic calcites is surprisingly similar to that of synthetic calcite. This is usually taken to mean that Li incorporation into shells should proceed inorganically. By contrast, we conclude that minor element incorporation processes in marine shell‐forming organisms always include biological processes. This is relevant to past climate reconstructions because it excludes any interpretation of minor element signatures in fossil shells based on inorganic processes only. Key Points: The Li partitioning pattern of E. huxleyi resembles that of A. lessonii and inorganic calciteLi partitioning in E. huxleyi is dominated by a coupled transmembrane transport of Li and CaThe vital effect is ubiquitous in calcifying organisms, even if it appears to be absent [ABSTRACT FROM AUTHOR]

In this study, we report the chemical composition of early carbonate cement precipitates in carbonate hardgrounds to understand the geochemical signature of near‐surface carbonate mineral precipitation. As carbonate hardgrounds lithify at or near the sediment‐water interface, they acquire cements that may be minimally evolved from paleoseawater. Using a suite of chemical measurements, we explore the potential of carbonate hardground cements as paleoenvironmental proxies. Trace metal and isotopic ratios, including some rare earth elements, Mg/Ca, manganese, and strontium concentrations, δ18O, δ13C, and 87Sr/86Sr, were analyzed in the carbonate cements from 17 Phanerozoic carbonate hardgrounds. The sensitivity of the geochemical signal to alteration depends on the geochemical analysis in question and the environmental water‐rock ratio. Of these samples, only our modern sample has measurements consistent with primary precipitation from seawater; all other samples precipitated from chemically evolved seawater or were influenced by meteoric water, even if only minimally changed. The more recent samples from the Cenozoic had seawater 87Sr/86Sr. The Mesozoic samples, in contrast, did not preserve seawater 87Sr/86Sr, even though the Mg/Ca, δ18O, and δ13C values were consistent with precipitation from seawater. Finally, the Paleozoic samples preserved expected seawater 87Sr/86Sr, though rare earth element and δ18O suggest primary precipitation was from evolved seawater. Additionally, we place our results in the context of open versus closed system precipitation using transects of the Mg/Ca ratios across individual cements. Overall, we stress that one geochemical measurement provides only a partial record of fluid composition, but multiple measurements allow a potential understanding of the seawater geochemical signal. Plain Language Summary: All potential archives for reconstructing ancient seawater chemistry have complicating factors, be it biological modification or secondary alteration. This study investigates a promising alternative, carbonate hardground cements. As carbonate hardgrounds form relatively quickly and in equilibrium with seawater, if a sample has remained unaltered, it should retain the primary seawater chemistry. We evaluate 17 samples from across the Phanerozoic, compiling trace element concentrations and isotopic ratios to determine if a sample has undergone significant diagenesis. Overall, no ancient sample satisfies all criteria, but the suite of measurements allows for an evaluation framework for future samples. Key Points: Carbonate hardground cements may capture primary seawater chemistryCarbon, oxygen, and strontium isotopes, combined with Mg/Ca and rare earth element abundances, can indicate primary geochemical signalsCement chemical evolution can indicate open versus closed system behavior [ABSTRACT FROM AUTHOR]

The ratio of boron to calcium (B/Ca) in a subset of foraminifera has been shown to covary with seawater carbonate chemistry, making this geochemical signature a promising proxy for carbon cycle science. Some studies suggest complications with the B/Ca proxy in photosymbiont‐bearing planktonic foraminifera, while relatively few studies have investigated B/Ca in species that lack large dinoflagellate symbionts. For the first time, we use a sediment trap time series to evaluate B/Ca of subtropical and subpolar planktonic foraminifera species that are asymbiotic (Globigerina bulloides and Neogloboquadrina incompta) and a species that hosts small intrashell photosymbionts (Neogloboquadrina dutertrei). We find that B/Ca measurements across size fractions indicate overall little to no size‐dependent uptake of boron that has previously been reported in some symbiont‐bearing foraminifera. Neogloboquadrina incompta and N. dutertrei B/Ca are strongly correlated with calcite saturation, pH, and carbonate ion concentration, which is in good agreement with the limited number of published core top results. While G. bulloides B/Ca trends with seasonal fluctuations in carbonate chemistry, during discrete periods considerable B/Ca offsets occur when a cryptic G. bulloides species is known to be seasonally present within the region. We confirm presence and significant B/Ca offset between cryptic species by individual LA‐ICP‐MS analyses. This finding calls into question the use of traditional morphological classification to lump what might be genetically distinct species for geochemical analyses. Our overall results highlight the utility of G. bulloides, N. incompta, and N. dutertrei B/Ca while bringing to light new considerations regarding divergent geochemistry of cryptic species. Key Points: Analyzed populations of Neogloboquadrina foraminifera show no size‐dependent offsets in B/Ca and significant correlations with carbonate system variablesB/Ca of individual G. bulloides analyzed by LA‐ICP‐MS indicates that local cryptic species have significant B/Ca offsetsDivergent geochemistry of cryptic species calls into question the use of traditional species classification for B/Ca analysis [ABSTRACT FROM AUTHOR]

Present-day ocean deoxygenation has major implications for marine ecosystems and biogeochemical cycling in the oceans. Chromium isotopes are used as a proxy to infer changes in past oceanic redox state. Chromium isotopes in carbonates, including the prime proxy carrier foraminifera, were initially thought to record the seawater composition during crystallisation. However, the uptake of Cr into foraminiferal tests and carbonates is still poorly understood and recent studies question this assumption. We assess whether Cr in foraminiferal calcite is taken up during biomineralisation, has a post-depositional origin or is a combination of the two. Laser Ablation-MC-ICP-MS analyses and NanoSIMS imaging of individual tests were used to characterise the distribution of Cr in both planktic and benthic foraminifera. Foraminifera in sediment core-top samples have up to two orders of magnitude more Cr than sediment trap, plankton net, and culture samples. In cultured specimens, Cr is incorporated in foraminiferal tests at low concentrations (0.04–0.13 ppm) with a distribution coefficient of ∼250 ± 43 (2SE) which is an upper estimate due to substantial loss of dissolved Cr during the experiment. Part of the Cr signal in sedimentary foraminifera may be primary, but this primary signal is likely often overprinted by the uptake of Cr from bottom and pore waters. In sediment samples, there is no significant isotopic offset between individual species and bulk foraminiferal calcite from the same size fraction. The >500 μm fraction has a heavier isotopic composition than the smaller 250–500 μm fraction with an offset of −0.3 to −0.5‰ due to an increase in surface area to volume. We propose that Cr in foraminifera is predominantly post-depositional and records bottom/pore water signals. This is contrary to current interpretations of the foraminiferal Cr isotope proxy as a surface seawater redox proxy. • Chromium is distributed across the whole foraminiferal shell. • Post-depositional addition of Cr is the main uptake mechanism in foraminifera. • There is no interspecies isotope fractionation between equisized foraminifera. • Isotopic compositional changes are related to foraminiferal test size. [ABSTRACT FROM AUTHOR]

Ocean acidification poses a serious threat to marine calcifying organisms, yet experimental and field studies have found highly diverse responses among species and environments. Our understanding of the underlying drivers of differential responses to ocean acidification is currently limited by difficulties in directly observing and quantifying the mechanisms of bio‐calcification. Here, we present Raman spectroscopy techniques for characterizing the skeletal mineralogy and calcifying fluid chemistry of marine calcifying organisms such as corals, coralline algae, foraminifera, and fish (carbonate otoliths). First, our in vivo Raman technique is the ideal tool for investigating non‐classical mineralization pathways. This includes calcification by amorphous particle attachment, which has recently been controversially suggested as a mechanism by which corals resist the negative effects of ocean acidification. Second, high‐resolution ex vivo Raman mapping reveals complex banding structures in the mineralogy of marine calcifiers, and provides a tool to quantify calcification responses to environmental variability on various timescales from days to years. We describe the new insights into marine bio‐calcification that our techniques have already uncovered, and we consider the wide range of questions regarding calcifier responses to global change that can now be proposed and addressed with these new Raman spectroscopy tools. [ABSTRACT FROM AUTHOR]

The boron isotope compositions (δ11B) of biogenic carbonates have proven to be an invaluable tool for investigating changes in ocean carbonate chemistry, especially the impacts of declining seawater pH due to rising levels of atmospheric CO2. Accurate, high precision boron isotopic measurements, however, remain analytically challenging with conventional approaches being extremely time consuming and labour intensive. Here we present a new analytical approach for high precision accurate measurements of boron isotope compositions in biogenic carbonates. We show that a laser ablation MC-ICPMS system equipped with 1013 Ω amplifiers provides a powerful tool for determining micro-scale δ11B values with an internal precision of ≤0.15‰ (2SD) and a total long-term accuracy of better than 0.22‰, which is equivalent to or better than those of conventional solution-based methods. This accuracy is achieved by careful subtraction of baseline interference around the masses of 10B and 11B, which arises from matrix-specific scattered Ca, C, and O ions. We also report detailed protocols for time-response corrections of transient signals in biogenic carbonates, essential for high precision boron isotopic measurements when using 1013 Ω amplifiers. The overall veracity of our laser ablation MC-ICPMS method is further demonstrated by the isotopic variability observed at macro- (mm) and micro-scales (μm) in both calcite and aragonite biogenic minerals. An aragonite deep-sea coral, Desmophyllum dianthus, is shown to preserve large (up to 6‰) variations in δ11B accompanied by near synchronous changes in B/Ca. This variability is excessive compared to that expected for the relatively stable carbonate ion system of deep-ocean water and is therefore attributed to isotopic and elemental fractionation of B during coral biomineralisation. In contrast, cyclic 2.5‰ variability is found in the sclerosponge Ceratoporella nicholsoni, which can be directly linked to seasonal changes in seawater pH. These examples highlight the power of laser ablation MC-ICPMS and its ability to accurately and precisely recover small environmental signals in boron isotopes. We thus show that these significant improvements in both the internal precision and now long-term accuracy and reproducibility of laser ablation MC-ICPMS, together with its microscale analytical capabilities and relatively rapid ease of operation, have the potential to revolutionise the study of boron isotope systematics in biogenic carbonates. [ABSTRACT FROM AUTHOR]

In order to establish environmentally sustainable industries there is a need for high-resolution temporal and spatial monitoring of heavy metal pollutants even at low concentrations before they become hazardous for local ecosystems. Here we present single chamber records of Cu, Zn and Pb in shells of two benthic foraminifera species with different shell types from two shallow coastal stations in Israel: An area adjacent to an electrical power plant and desalination factory (Hadera) and an industrially free nature reserve (Nachsholim). Records of both foraminifera species show elevated metal concentrations in Hadera clearly identifying the footprint of the local industrial facilities. Moreover, short-term events of elevated Cu and Pb concentrations were detected by single chamber analyses. This study demonstrates the potential of using heavy metals anomalies in foraminiferal single chambers as a tool for detecting the industrial footprint of coastal facilities as well as short term events of elevated heavy metals. [ABSTRACT FROM AUTHOR]

Rationale: Boron isotope ratios (δ11B values) are used as a proxy for seawater paleo-pH, amongst several other applications. The analytical precision can be limited by the detection of low intensity ion beams from limited sample amounts. High-gain amplifiers offer improvements in signal/noise ratio and can be used to increase measurement precision and reduce sample amounts. Methods: 1013 ohm amplifier technology has previously been applied to several radiogenic systems, but has thus far not been applied to non-traditional stable isotopes. Here we apply 1013 ohm amplifier technology for the measurement of boron isotope ratios using solution mode MC-ICP-MS and laser ablation mode (LA-)MC-ICP-MS techniques. Precision is shown for reference materials as well as for low-volume foraminifera samples. Results: The baseline uncertainty for a 0.1 pA 10B+ ion beam is reduced to <0.1‰for a typical measurement period. The external precision is better than 0.2 ‰ (2SD) for δ11 B measurements for solution samples containing as little as 0.8 ng total boron. For in situ microanalyses with LA-MC-ICP-MS, the external precision of 11B/10B from an in-house calcite standard was 1 ‰ (2SD) for individual spot analyses, and 0.3‰for the mean of ≥10 replicate spot analyses. Conclusions: 1013 ohm amplifier technology is demonstrated to offer advantages for the determination of δ11B values by both MC-ICP-MS and LA-MC-ICP-MS for small samples of biogenic carbonates, such as foraminifera shells. 1013 ohm amplifier technology will also be of benefit to other non-traditional stable isotope measurements. [ABSTRACT FROM AUTHOR]

Experiments on the incorporation of trace elements into calcite were performed, and rare earth elements (REE) were used to mark the growth zones of individual crystals. Experiments were conducted at different pH (7.7 to 8.8) and temperatures (2 °C to 24.6 °C) in NH4Cl + CaCl2 solutions, where REE were rapidly consumed by growing calcite. LA-ICP-MS line-scans yielded the distribution of (REE/Ca)calcite within individual crystals in a manner consistent with the addition of REE into fluid. A sharp decrease of (REE/Ca)calcite toward the crystal edge suggests the fast depletion of (REE/Ca)fluid due to strong REE consumption by growing calcite. An attempt was made to estimate the lower limit of the partition coefficients between calcite and fluid using selected REE/Ca data within individual calcite crystals and the amount of REE added into fluid. [ABSTRACT FROM AUTHOR]

Shallow marine calcifiers play an important role as marine ecosystem engineers and in the global carbon cycle. Understanding their response to warming is essential to evaluate the fate of marine ecosystems under global change scenarios. A rare opportunity to test the effect of warming acting on natural ecosystems is by investigation of heat-polluted areas. Here, we study growth and calcification in benthic foraminifera that inhabit a thermally polluted coastal area in Israel, where they are exposed to elevated temperatures reaching up to ~42°C in summer. Live specimens of two known heat-tolerant species Lachlanella sp. 1 and Pararotalia calcariformata were collected over a period of 1 year from two stations, representing thermally polluted and undisturbed (control) shallow hard bottom habitats. Single-chamber element ratios of these specimens were obtained using laser ablation, and the Mg/Ca of the most recently grown final chambers were used to calculate their calcification temperatures. Our results provide the first direct field evidence that these foraminifera species not only persist at extreme warm temperatures but continue to calcify and grow. Species-specific Mg/Ca thermometry indicates that P. calcariformata precipitate their shells at temperatures as high as 40°C and Lachlanella sp. 1 at least up to 36°C, but both species show a threshold for calcification at cold temperatures: calcification in P. calcariformata only occurred above 22°C and in Lachlanella sp. 1 above 15°C. Our observations from the heat-polluted area indicate that under future warming scenarios, calcification in heat-tolerant foraminifera species will not be inhibited during summer, but instead the temperature window for their calcification will be expanded throughout much of the year. The observed inhibition of calcification at low temperatures indicates that the role of heat-tolerant foraminifera in carbonate production will most likely increase in future decades. [ABSTRACT FROM AUTHOR]

Abstract: Partial or selective dissolution of planktonic foraminiferal tests on the seafloor has been shown to alter original test Mg/Ca compositions and thus may limit the accuracy of Mg/Ca-based thermometry for reconstructions of past sea surface temperatures. We have employed laser ablation ICPMS to determine the extent of dissolution-caused changes in Mg/Ca distribution across individual chamber walls of the planktonic foraminifera Globigerinoides sacculifer and Orbulina universa. G. sacculifer samples collected from a core-top depth transect in the NE Indian Ocean and laboratory dissolution experiments show little if any evidence of preferential removal of Mg-rich calcite layers by progressive dissolution of the tests. We attribute the absence of selective dissolution to the banded distribution of Mg across the chamber walls of these foraminiferal species and to the minimal presence of calcite crusts with relatively low-Mg composition on the outer surfaces of tests. Mg/Ca microanalyses of G. sacculifer from core-top samples further indicate that for samples collected above the calcite lysocline the effect of postdepositional dissolution on Mg/Ca sample mean values is minimal and within the uncertainty of Mg/Ca thermometry (i.e. ±0.4mmol/mol; ±0.8°C at ∼28°C). Comparison with previously published results for G. sacculifer supports these observations. Simple modelling of G. sacculifer test dissolution indicates that selective removal of calcite with high-Mg/Ca values from within the final chamber of G. sacculifer test appears insufficient to cause the ∼10% decrease in Mg/Ca values observed above calcite lysocline. These changes in test composition might be related to development/removal as a function of Δ[CO3 2−] of a thin diagenetic surface coating which has a relatively high-Mg/Ca composition (i.e. 20–25mmol/mol). [Copyright &y& Elsevier]

The work presented sought to determine the effects of Mg/Ca ratios in solution have on Mg partitioning (KMg) between precipitated abiotic low-Mg calcite and solution. Experiments were set up so that Mg/Ca in precipitated abiotic calcite would match the Mg/Ca in planktonic foraminifera. This research intended to investigate the effect of Mg/Ca(Fluid) on KMg when the molar value of Mg/Ca(Fluid) was below 0.5, which is below the previously reported Mg/Ca range. The values of pH, salinity, and aqueous Mg/Ca were monitored during calcite precipitation, and Mg/Ca of calcite was determined at the end of experiments. Partition coefficients of Mg were evaluated as a ratio of Mg/Ca in calcite to the averaged ratio of aqueous Mg/Ca for each experiment. [ABSTRACT FROM AUTHOR]

The Mg/Ca composition of calcium carbonate tests (shells) secreted by planktonic foraminifera is increasingly being employed to estimate past seawater temperatures and reconstruct paleocean and climate records spanning hundreds of thousands of years. We show, using two high-resolution microanalysis techniques, that the final chamber of the planktonic foraminifera Orbulina universa typically comprises between three and six paired, low and high Mg, growth bands. The number and spacing of these bands is consistent with a diurnal origin, modulated by changing pH within the foraminiferal microenvironment due to the day–night, photosynthesis–respiration cycle of algal symbionts. The amplitude of Mg/Ca variation within individual tests and across many daily growth bands cannot be accounted for by seawater temperature in the shallow, euphotic zone habitat of O. universa. Our results indicate the Mg/Ca composition of calcite precipitated by O. universa in nature is strongly influenced by diurnal changes in the biological activity of algal symbionts and the host foraminifer. This brings into question the fundamental premise often made in applying Mg/Ca palaeoseawater thermometry, that the Mg/Ca composition of foraminiferal calcite is determined by seawater temperature, and whether the Mg/Ca composition of other planktonic species that are more widely used for palaeoseawater thermometry are subject to similar influences. [Copyright &y& Elsevier]

The occurrence of carbonatites in oceanic settings is very rare if compared with their continental counterpart, having been reported only in Cape Verde and Canary Islands. This paper provides an overview of the main geochemical characteristics of oceanic carbonatites, around which many debates still exist regarding their petrogenesis. We present new data on trace elements in minerals and whole-rock, together with the first noble gases isotopic study (He, Ne, Ar) in apatite, calcite, and clinopyroxene from Fuerteventura carbonatites (Canary Islands). Trace elements show a similar trend as Cape Verde carbonatites, almost tracing the same patterns on multi-element and REE abundance diagrams. 3He/4He isotopic ratios of Fuerteventura carbonatites reflect a shallow (sub-continental lithospheric mantle, SCLM) He signature in their petrogenesis, and they clearly differ from Cape Verde carbonatites, i.e., fluids from a deep and low degassed mantle with a primitive plume-derived He signature are involved in their petrogenesis. [ABSTRACT FROM AUTHOR]

• Foraminifera incorporate Zn and Pb in their calcite shells proportionate to seawater. • No species-specific or temperature effect on metal incorporation is observed. • Heavy metal concentrations can be measured by laser-ablation of individual chambers. • Such single-chamber analyses could record short-term pollution events. The establishment of sustainable coastal industries requires better temporal and spatial monitoring of heavy metal (HM) pollutants, even at low concentrations and during pulse-release events, before their accumulation becomes hazardous for local ecosystems or for the use of seawater in desalination (for drinking water). Foraminifera, unicellular marine organism, build their shells by sequential addition of chambers made of calcite, which contains impurities reflecting the composition of the growth medium. Therefore, the chemical composition of each chamber reflects HM in the ambient water at the time of calcification. To test the applicability of single-chamber analyses of foraminifera shells as a tool for HM monitoring in seawater, we conducted culturing experiments to calibrate the relationship of zinc and lead in foraminiferal shells and the ambient seawater. Two species of the cosmopolitan genus Amphistegina were cultured under a range of concentrations of both metals and two temperatures. We show that concentrations of zinc and lead in shells increase linearly with metal concentration in seawater with no difference between species and no effect of temperature. Our experiments further show that the concentrations in seawater can be directly inferred from concentrations in the shells at least up to the levels representing chronic pollution for both metals (68 ug/L for Zn and 8 ug/L for Pb). Combined with their high abundances in all marine environments and good preservation of their shells in sediments, our results demonstrate that foraminifera represent a powerful natural recording system offering high spatial and temporal resolution, allowing the establishment of historical baselines and detection of confined or short-term events of HM release, which could escape traditional monitoring methods. [ABSTRACT FROM AUTHOR]

Glacial–interglacial deep Indo-Pacific carbonate ion concentration ([ CO 3 2 − ]) changes were mainly driven by two mechanisms that operated on different timescales: 1) a long-term increase during glaciation caused by a carbonate deposition reduction on shelves (i.e., the coral reef hypothesis), and 2) transient carbonate compensation responses to deep ocean carbon storage changes. To investigate these mechanisms, we have used benthic foraminiferal B/Ca to reconstruct deep-water [ CO 3 2 − ] in cores from the deep Indian and Equatorial Pacific Oceans during the past five glacial cycles. Based on our reconstructions, we suggest that the shelf-to-basin shift of carbonate deposition raised deep-water [ CO 3 2 − ], on average, by 7.3 ± 0.5 (SE) μmol/kg during glaciations. Oceanic carbon reorganisations during major climatic transitions caused deep-water [ CO 3 2 − ] deviations away from the long-term trend, and carbonate compensation processes subsequently acted to restore the ocean carbonate system to new steady state conditions. Deep-water [ CO 3 2 − ] showed similar patterns to sediment carbonate content (%CaCO 3 ) records on glacial–interglacial timescales, suggesting that past seafloor %CaCO 3 variations were dominated by deep-water carbonate preservation changes at our studied sites. [ABSTRACT FROM AUTHOR]

Abstract: The boron isotopic and chemical content of carbonates (expressed as δ11B and B/Ca ratios) have been proposed as proxies for seawater carbonate system parameters. Thermodynamic and kinetic effects on δ11B and B partitioning are not yet fully constrained, underscoring the importance of exploring possible effects of growth rate on boron incorporation in synthetic calcium carbonate minerals, which is the focus of this study. Secondary Ion Mass Spectrometry (SIMS) measurements of B/Ca and δ11B were performed on single crystal of calcite synthesized by diffusion of CO2 under controlled conditions from a solution of NH4Cl–CaCl2 doped with boron. Growth rates of calcite (V, nm/s) within crystals grown isothermally at 24.6°C were monitored by sequentially spiking calcite-precipitating fluids with rare earth element (REE) dopants. The REE were analyzed with SIMS at spots that match those locations where B/Ca and δ11B ratios were measured. Values for the boron Nernst partition coefficient, defined as D B =B(calcite)/B(fluid), increase from 0.5 (pHNBS =8.15) to 0.9 (pH=8.00) with values of V increasing from 0.04 to 0.13nm/s. For δ11B behavior, it was not possible to draw conclusive results due to the analytical error (2.2‰; 2σ). pH effects on D B during calcite precipitation, associated with an increase in pH from 8.00 to 8.15, appear to be masked by the competing effects of changing V. We conclude that over the range of growth rates and other conditions investigated in this study, growth rate effects on B partitioning need to be accounted for when using B/Ca ratios in biogenic calcite as a proxy for seawater carbonate system parameters. [Copyright &y& Elsevier]