ALBERT

Description: Highlights • Improved understanding of the behaviour of instrumental mass fractionation (IMF). • The effect of matrix elements on IMF is largely associated with plasma conditions that can be quantified with the NAI. • Matrix effects can be systematically and significantly attenuated by tuning of instrumental operating parameters. • A matrix tolerance plasma state is defined for stable barium isotope analysis. • The suggested analytical protocol is expected to be applicable to other stable isotope measurements with MC-ICP-MS. Abstract Stable barium isotope measurements with multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) remain an analytical challenge and can be considerably affected by the presence of matrix elements, even when applying double spiking. Therefore significant efforts were invested in previous studies to develop efficient barium purification methods. However, due to the high variability in matrix/barium ratios for diverse sample matrices, potential matrix effects can still not be excluded. While a lot of effort has been invested into improving the chemical separation protocols, the impact of plasma conditions on the accuracy and precision of stable isotope measurements has rarely been considered. Here we present a systematic investigation of the relationship between plasma conditions, instrumental mass fractionation (IMF) and impurity (i.e. matrix) concentrations. The Normalised Ar Index (NAI) and Matrix-Ar Index (MA) are used to quantify MC-ICP-MS plasma conditions and plasma mass loading, respectively. Our results show that the effect of matrix elements on IMF is largely linked to plasma conditions (i.e. NAI) and behaves as a linear function of mass loading (i.e. MA). Accordingly, the matrix effects can be significantly attenuated by increasing the NAI thereby minimising the risk of plasma “over-loading”. The improved understanding of the behaviour of the matrix-induced IMF allows us to define a matrix tolerance plasma state for barium isotope analysis. The accuracy of this recommended method is further assessed by analyses of two well-studied reference materials, the GEOTRACES seawater reference sample SAFe D2 and the carbonate reference material JCp-1. We expect that the analytical protocol described in this study is applicable not only to barium isotope analysis, but also to a wide range of other stable isotope measurements with MC-ICP-MS.

Description: Boron isotope (δ11B) analysis using bulk foraminifera samples is a widely used method to reconstruct paleo sea water pH conditions. Although, these analyses exhibit high analytical precision, short term information is lost due to the pooling of tests with distinct and diverse boron isotope signatures resulting in average values for the time interval encompassed in the sample. Here we present and assess the analysis of δ11B of individual foraminifera by means of Laser Ablation Multi-Collector Inductively Coupled Plasma Mass Spectrometry (LA-MC-ICP-MS) to obtain seasonal variability patterns and to test the limits of precision of LA-MC-ICP-MS on the planktonic foraminifera Orbulina universa. The results show that relative seasonal differences (of ∼11 ‰) can be captured from either uncleaned or cleaned individual O. universa tests with an average precision of ±2.9 ‰ (2 SE). The δ11B variability among foraminifera representing the same season is on average 7.4 ‰ (2 SD) irrespective of cleaning state. With our approach, analyses on oxidatively cleaned O. universa do not require the use of a matrix matched standard to obtain B isotope values in the range of those expected for solution multi-specimen analyses from determining local pH. Our results are useful for considering the potential spread caused by foraminifera vital effects and for obtaining information of seasonal ranges of pH and possible bias related to seasonality hidden within conventional solution based δ11B analyses.

Description: Highlights • Holocene cold-water coral mound formation started non-synchronous in Belgica province. • Coral mounds and slope sediments record changes in intermediate water mass dynamics. • Increased turbulent bottom currents steered slope erosion and mound formation. • Internal waves at the ENAW-MOW boundary enhance energy supply and particle flux. • Transition zone between the ENAW-MOW shifted 250 m upslope during the last deglacial. Abstract Turbulent bottom currents significantly influence the formation of cold-water coral mounds and sedimentation processes on continental slopes. Combining records from coral mounds and adjacent slope sediments therefore provide an unprecedented palaeo-archive to understand past variations of intermediate water-mass dynamics. Here, we present coral ages from coral mounds of the Belgica province (Porcupine Seabight, NE Atlantic), which indicate a non-synchronous Holocene re-activation in mound formation suggested by a temporal offset of ∼2.7 kyr between the deep (start: ∼11.3 ka BP at 950 m depth) and shallow (start: ∼8.6 ka BP at 700 m depth) mounds. A similar depth-dependent pattern is revealed in the slope sediments close to these mounds that become progressively younger from 22.1 ka BP at 990 m to 12.2 ka BP at 740 m depth (based on core-top ages). We suggest that the observed changes are the consequence of enhanced bottom-water hydrodynamics, caused by internal waves associated to the re-invigoration of the Mediterranean Outflow Water (MOW) and the development of a transition zone (TZ) between the MOW and the overlying Eastern North Atlantic Water (ENAW), which established during the last deglacial. These highly energetic conditions induced erosion adjacent to the Belgica mounds and supported the re-initiation of mound formation by increasing food and sediment fluxes. The striking depth-dependent patterns are likely linked to a shift of the ENAW-MOW-TZ, moving the level of maximum energy ∼250 m upslope since the onset of the last deglaciation.

Description: Highlights • Coral reef responses to slow-rate, low-amplitude, high-frequency sea-level changes. • Continuous reef development over the last 6000 years in optimal conditions. • Mid-late Holocene coral assemblages similar to their modern counterparts. • Facies distribution governed by variations in accommodation space. • Prominent role played by reef deposits in the formation and shaping of modern islands. Geological records of coastal system evolution during past higher and/or rising sea levels provide an important baseline for developing projections regarding the response of modern coastal systems to future sea-level rise. The mid-late Holocene corresponds to the most recent window into natural variability prior to the Anthropocene and involves slow-rate and low-amplitude sea-level changes that were mostly governed by a limited glacio-eustatic contribution, most likely sourced from Antarctica, and ‘glacial isostatic adjustment’ processes. This paper documents in unprecedented detail the response of coral reefs and coastal systems to changing accommodation space in relation to mid-late Holocene sea-level changes in French Polynesia. The sea-level curve that underpins this study has a global significance and documents a single short-lived sea-level highstand between 4.10 and 3.40 kyr BP. The amplitude of the highstand is less than one metre, within the range of the predicted sea level at the end of the current century. The reported relative sea-level changes are characterized by slow rates ranging from a few tens of millimetres per year to up to 2.5 mm/yr and by significant sea-level stability (stillstands) lasting more than a century and up to 250 years, defining a step-like pattern. Sea-level variability probably driven by climatic oscillations on interannual to millennial time scales is evidenced during the entire time window. The detailed reconstruction of reef development over the last 6000 years brings valuable information regarding coral reef dynamics and coastal processes during periods of higher sea level and wave energy regimes. The persistence of stable and optimal depositional environments over the last 6000 years is demonstrated by the constant overall composition and diversity of reef communities and the almost continuous development of coral microatolls. The facies distribution as well as the lateral extension and shift of facies belts have been governed by variations in accommodation space, which are controlled by relative sea-level changes and antecedent topography. The widespread development of mid-late Holocene reef deposits in coastal areas suggests that they have played a prominent role in global processes related to the formation and shaping of modern islands.

Description: Highlights • Dual geochemical approach using δ11B and B/Ca to evaluate coral calcifying fluids from West Maui, Hawai'i. • NMR analysis confirms boron is present as borate with no evidence of boric acid inclusion. • Increased pH up-regulation in corals exposed to high nutrient / low pH submarine groundwater discharge. • Calcifying fluid aragonite saturate state 9 to 10 times higher than ambient seawater. • Up-regulation as an internal coping mechanism to combat multiple stressors from land-based sources of pollution. Coral reefs and their ecosystems are threatened by both global stressors, including increasing sea-surface temperatures and ocean acidification (OA), and local stressors such as land-based sources of pollution that can magnify the effects of OA. Corals can physiologically control the chemistry of their internal calcifying fluids (CF) and can thereby regulate their calcification process. Specifically, increasing aragonite saturation state in the CF (ΩCF) may allow corals to calcify even under external low saturation conditions. Questions remain regarding the physiological processes that govern the CF chemistry and how they change in response to multiple stressors. To address this knowledge gap, the boron systematics (δ11B and B/Ca) were analyzed in tropical corals, Porites lobata, collected at submarine groundwater seeps impacted by the release of treated wastewater in west Maui, Hawai'i, to document the interactions between high nutrient / low pH seep water on CF carbonate chemistry. Results show substantial up-regulation of pH and dissolved inorganic carbon (DIC) with respect to seawater in P. lobata corals collected from within the wastewater impacted area at Kahekili Beach Park compared to the control site at Olowalu Beach. The ΩCF was 9 to 10 times higher than ambient seawater Ω, and 13 to 26% higher than in corals from the control site and from previously observed in tropical Porites spp. corals. Such elevated up-regulation suggests that corals exposed to nutrient-enriched, low pH effluent sustain CF supersaturated with respect to aragonite, possibly as an internal coping mechanism to combat multiple stressors from land-based sources of pollution. This elevated up-regulation has implications to coral vulnerability to future climate- and ocean-change scenarios.

Description: Ocean environmental conditions can be inferred from the chemical composition of bamboo coral skeletons. The high magnesium calcite internodes of these long-living octocorals may therefore represent a potential archive for seawater properties such as salinity or temperature where instrumental time series are absent. To extend these time series into the past using a natural archive the principles of temperature and salinity signal incorporation into cold-water coral skeletal material need to be investigated. Since skeletal Na and S concentrations have been proposed as environmental proxies, we mapped the spatial distribution and concentration of these elements in two Atlantic specimens of Keratoisis grayi (family Isididae). These measurements were conducted with an electron microprobe applying a spatial resolution of 4 μm. The mean apparent distribution coefficient of Na/Ca for the two samples was within 2.5 and 2.8*10−4, while that of S shows a similar depletion relative to seawater with 3.8 and 3.6*10−3. The two elements show an inverse correlation in bamboo coral skeletons. The mean apparent distribution coefficient of Na is similar to that of abiotic calcites. This similarity can be interpreted as the absence of significant vital effects for skeletal Na/Ca. Hence it corroborates the idea that the average skeletal composition of bamboo corals holds the potential to record past seawater conditions. In contrast, it appears unlikely that the spatial variations of the element distribution of seemingly simultaneously precipitated material along growth rings are exclusively controlled by environmental factors. We further exclude Rayleigh fractionation, ion-specific pumping, and Ca/proton exchange as the driver of Na and S distribution in bamboo corals. Instead, we adapt a calcification model originally proposed for scleractinians to bamboo corals. This model can explain the observed distribution of Na and S in the skeleton by a combination of Ca/proton pumping, bicarbonate active transport, and the formation of an organic skeletal matrix. The adapted model can further be used to predict the theoretical behaviour of other elements and disentangle vital effects from external factors influencing compositional features. It is therefore a useful tool for future studies on the potential of bamboo corals as environmental archives.

Description: Highlights • European legislation resulted in significant reduction in shell-bound lead. • Intertidal muricid represents a suitable archive for lead pollution. • Shell-bound copper and zinc not related to environmental concentrations. Heavy metals in coastal waters are a great environmental concern in the North Sea since the middle of the 20th century. Regulatory efforts have led to a significant reduction in atmospheric and water-transported heavy metals. Still, high concentrations of these in sediments remain a risk for ecosystems, requiring close monitoring. Here, we investigated the applicability of Nucella lapillus museum collections as a tool for targeted tracking of chronic anthropogenic heavy metal pollution. We analysed the concentration ratios of the common heavy metals Cu, Cd, Pb, and Zn in relation to Ca in N. lapillus shells collected from the Dutch and Belgian intertidal zone over the last 130 years. We found that shell Cu/Ca and Zn/Ca concentration ratios remained remarkably constant, whereas Pb/Ca concentration trends were closely aligned with emissions of leaded petrol in Europe. Our results suggest that N. lapillus provides a suitable Pb pollution archive of the intertidal zone.

Description: Ocean environmental conditions can be inferred from the chemical composition of bamboo coral skeletons. The high magnesium calcite internodes of these long-living octocorals may therefore represent a potential archive for seawater properties such as salinity or temperature where instrumental time series are absent. To extend these time series into the past using a natural archive the principles of temperature and salinity signal incorporation into cold-water coral skeletal material need to be investigated. Since skeletal Na and S concentrations have been proposed as environmental proxies, we mapped the spatial distribution and concentration of these elements in two Atlantic specimens of Keratoisis grayi (family Isididae). These measurements were conducted with an electron microprobe applying a spatial resolution of 4 μm. The mean apparent distribution coefficient of Na/Ca for the two samples was within 2.5 and 2.8*10−4, while that of S shows a similar depletion relative to seawater with 3.8 and 3.6*10−3. The two elements show an inverse correlation in bamboo coral skeletons. The mean apparent distribution coefficient of Na is similar to that of abiotic calcites. This similarity can be interpreted as the absence of significant vital effects for skeletal Na/Ca. Hence it corroborates the idea that the average skeletal composition of bamboo corals holds the potential to record past seawater conditions. In contrast, it appears unlikely that the spatial variations of the element distribution of seemingly simultaneously precipitated material along growth rings are exclusively controlled by environmental factors. We further exclude Rayleigh fractionation, ion-specific pumping, and Ca/proton exchange as the driver of Na and S distribution in bamboo corals. Instead, we adapt a calcification model originally proposed for scleractinians to bamboo corals. This model can explain the observed distribution of Na and S in the skeleton by a combination of Ca/proton pumping, bicarbonate active transport, and the formation of an organic skeletal matrix. The adapted model can further be used to predict the theoretical behaviour of other elements and disentangle vital effects from external factors influencing compositional features. It is therefore a useful tool for future studies on the potential of bamboo corals as environmental archives.