Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Mayfield, K. K., Eisenhauer, A., Santiago Ramos, D. P., Higgins, J. A., Horner, T. J., Auro, M., Magna, T., Moosdorf, N., Charette, M. A., Gonneea, M. E., Brady, C. E., Komar, N., Peucker-Ehrenbrink, B., & Paytan, A. Groundwater discharge impacts marine isotope budgets of Li, Mg, Ca, Sr, and Ba. Nature Communications, 12(1), (2021): 148-020-20248-3, doi:10.1038/s41467-020-20248-3.

Description: Groundwater-derived solute fluxes to the ocean have long been assumed static and subordinate to riverine fluxes, if not neglected entirely, in marine isotope budgets. Here we present concentration and isotope data for Li, Mg, Ca, Sr, and Ba in coastal groundwaters to constrain the importance of groundwater discharge in mediating the magnitude and isotopic composition of terrestrially derived solute fluxes to the ocean. Data were extrapolated globally using three independent volumetric estimates of groundwater discharge to coastal waters, from which we estimate that groundwater-derived solute fluxes represent, at a minimum, 5% of riverine fluxes for Li, Mg, Ca, Sr, and Ba. The isotopic compositions of the groundwater-derived Mg, Ca, and Sr fluxes are distinct from global riverine averages, while Li and Ba fluxes are isotopically indistinguishable from rivers. These differences reflect a strong dependence on coastal lithology that should be considered a priority for parameterization in Earth-system models.

Description: We thank A. Beck, H. Dulai, I. Santos, C. Benitez-Nelson, W. Moore, A. Martin, and H. Windom for sample access. We also thank A. Kolevica, A. Heuser, H. Pryer, J. Middleton, R. Franks, F. Lon, N. Slater, and O. Šebek for their laboratory and analytical assistance. This material is based upon research supported by the National Science Foundation Graduate Research Fellowship Program and an internship provided through the U.S. Geological Survey Graduate Research Internship Program (GRIP). This research was also supported by grants from: the German Academic Exchange Service (DAAD), Northern California chapter of the Achievement Rewards for College Scientists Foundation, International Association of GeoChemistry, Geological Society of America, Northern California Geological Society, Myers Trust, Friends of Long Marine Lab, and UC MEXUS (to K.K.M.). We acknowledge funding from EU-ITN Horizon project 643084 (to A.E. and T.M.) and NSF grant Award Number 1259440 (to A.P.). We also acknowledge funding from NSF grant award number OCE-1736949 (to T.J.H.). Any use of trade, firm or product names is for descriptive purposes only and does not imply endorsement by the U.S. Government.

Description: Anthropogenic impacts are perturbing the global nitrogen cycle via warming effects and pollutant sources such as chemical fertilizers and burning of fossil fuels. Understanding controls on past nitrogen inventories might improve predictions for future global biogeochemical cycling. Here we show the quantitative reconstruction of deglacial bottom water nitrate concentrations from intermediate depths of the Peruvian upwelling region, using foraminiferal pore density. Deglacial nitrate concentrations correlate strongly with downcore δ13C, consistent with modern water column observations in the intermediate Pacific, facilitating the use of δ13C records as a paleo-nitrate-proxy at intermediate depths and suggesting that the carbon and nitrogen cycles were closely coupled throughout the last deglaciation in the Peruvian upwelling region. Combining the pore density and intermediate Pacific δ13C records shows an elevated nitrate inventory of 〉10% during the Last Glacial Maximum relative to the Holocene, consistent with a δ13C-based and δ15N-based 3D ocean biogeochemical model and previous box modeling studies.

Description: Mid- to late-Holocene sea-level records from low-latitude regions serve as an important baseline of natural variability in sea level and global ice volume prior to the Anthropocene. Here, we reconstruct a high-resolution sea-level curve encompassing the last 6000 years based on a comprehensive study of coral microatolls, which are sensitive low-tide recorders. Our curve is based on microatolls from several islands in a single region and comprises a total of 82 sea-level index points. Assuming thermosteric contributions are negligible on millennial time scales, our results constrain global ice melting to be 1.5–2.5 m (sea-level equivalent) since ~5500 years before present. The reconstructed curve includes isolated rapid events of several decimetres within a few centuries, one of which is most likely related to loss from the Antarctic ice sheet mass around 5000 years before present. In contrast, the occurrence of large and flat microatolls indicates periods of significant sea-level stability lasting up to ~300 years.

Description: Acidification of the World’s oceans may directly impact reproduction, performance and shell formation of marine calcifying organisms. In addition, since shell production is costly and stress in general draws on an organism’s energy budget, shell growth and stability of bivalves should indirectly be affected by environmental stress. The aim of this study was to investigate whether a combination of warming and acidification leads to increased physiological stress (lipofuscin accumulation and mortality) and affects the performance [shell growth, shell breaking force, condition index (Ci)] of young Mytilus edulis and Arctica islandica from the Baltic Sea. We cultured the bivalves in a fully-crossed 2-factorial experimental setup (seawater (sw) pCO2 levels “low”, “medium” and “high” for both species, temperature levels 7.5, 10, 16, 20 and 25 °C for M. edulis and 7.5, 10 and 16 °C for A. islandica) for 13 weeks in summer. Mytilus edulis and A. islandica appeared to tolerate wide ranges of sw temperature and pCO2. Lipofuscin accumulation of M. edulis increased with temperature while the Ci decreased, but shell growth of the mussels only sharply decreased while its mortality increased between 20 and 25 °C. In A. islandica, lipofuscin accumulation increased with temperature, whereas the Ci, shell growth and shell breaking force decreased. The pCO2 treatment had only marginal effects on the measured parameters of both bivalve species. Shell growth of both bivalve species was not impaired by under-saturation of the sea water with respect to aragonite and calcite. Furthermore, independently of water temperatures shell breaking force of both species and shell growth of A. islandica remained unaffected by the applied elevated sw pCO2 for several months. Only at the highest temperature (25 °C), growth arrest of M. edulis was recorded at the high sw pCO2 treatment and the Ci of M. edulis was slightly higher at the medium sw pCO2 treatment than at the low and high sw pCO2 treatments. The only effect of elevated sw pCO2 on A. islandica was an increase in lipofuscin accumulation at the high sw pCO2 treatment compared to the medium sw pCO2 treatment. Our results show that, despite this robustness, growth of both M. edulis and A. islandica can be reduced if sw temperatures remain high for several weeks in summer. As large body size constitutes an escape from crab and sea star predation, this can make bivalves presumably more vulnerable to predation—with possible negative consequences on population growth. In M. edulis, but not in A. islandica, this effect is amplified by elevated sw pCO2. We follow that combined effects of elevated sw pCO2 and ocean warming might cause shifts in future Western Baltic Sea community structures and ecosystem services; however, only if predators or other interacting species do not suffer as strong from these stressors.

Description: Major changes in community structure and depositional relief of high-latitude coral communities in the southern Persian Gulf between marine isotope stage (MIS) 7 and the present day suggest that the area has become increasingly restricted. Corals and bivalves from outcrops on Kish Island, Iran, were identified in order to interpret the Late Pleistocene palaeoenvironmental setting. U/Th disequilibrium dating was used to constrain the ages of the stratigraphic units. During MIS 7, two coral-bearing sequences were deposited on what is now Kish Island. The lower sequence is dated as MIS 7.5 and changes laterally from an assemblage dominated by Cyphastrea sp. and Platygyra daedalea in the west to one characterized by branching Montipora in the east. By contrast, the upper sequence, dated as MIS 7.1, transitions from an assemblage dominated by platy Montipora in the west to a diverse assemblage of Platygyra and other faviids in the east. The assemblages of both sequences are within a marl matrix and bounded by thin lithified mollusc-rich layers. Corals and bivalves indicate that the sequences were deposited on gentle slopes in sheltered environments less than 20 m deep. The MIS 7 deposits may be classified as coral carpets or biostromes that developed a low-relief framework. During MIS 5, coral communities were no longer framework building and are now limited to an Acropora-rich layer of coral rubble that covers large parts of the island, and two small incipient reefs with sparse faviids. Similarities between the MIS 5 and modern nearshore coral communities suggest that the environmental conditions during MIS 5 were comparable to those of today. The late Pleistocene coral carpets and non-framework coral communities of the southern Persian Gulf may serve as models for coral biostromes in the fossil record, which formed under restricted environmental conditions such as elevated terrigenous input, high turbidity, and strong seasonal changes in temperature and/or salinity.

Description: Continuous surface cores of cold-seep carbonates were recovered offshore Pacific Nicaragua and Costa Rica from 800 to 1,500-m water depths (Meteor 66/3) in order to decipher their evolution and methane enriched fluid emanation in contrasting geological settings. Cores from the mounds Iguana, Perezoso, Baula V and from the Jaco Scarp escarpment were used for a multi-method approach. For both settings aragonite was revealed as dominant authigenic carbonate phase in vein fillings and matrix cementation, followed by Mg-calcite as second most abundant. This common precipitation process of CaCO3 polymorphs could be ascribed as indirectly driven by chemical changes of the advecting pore water due to anaerobic oxidation of methane. A more direct influence of seep-related microbial activity on the authigenic mineral assemblage in both settings is probably reflected by the observed minor amounts of dolomite and a dolomite-like CaMg carbonate (MgCO3 ~ 42 %). δ13C data of Jaco Scarp samples are significantly lower (−43 to −56 ‰ PDB) than for mound samples (−22 to −36 ‰ PDB), indicating differences in fluid composition and origin. Noteworthy, δ18O values of Scarp samples correlate most closely with the ocean signature at their time of formation. Documenting the archive potential, a high resolution case study of a mound core implies at least 40 changes in fluid supply within a time interval of approximately 14 ky. As most striking difference, the age data indicate a late-stage downward-progressing cementation front for all three mound cap structures (approx. 2–5 cm/ky), but a significantly faster upward carbonate buildup in the bulging sediments on top of the scarp environment (approx. 120 cm/ky). The latter data set leads to the hypothesis of chemoherm carbonate emplacement in accord with reported sedimentation rates until decompression of the advective fluid system, probably caused by the Jaco Scarp landslide and dating this to approximately 13,000 years ago.

Description: delta Sr-88/86 values of standards and a variety of natural samples were measured by MC-ICP-MS using the double-spike (DS) method and compared to results obtained by the standard-sample-bracketing (SSB) method and to DS-TIMS measurements. The external reproducibility of the SRM987 measurements carried out by DS-MC-ICP-MS was 0.021 parts per thousand (1SD), slightly better than previously published DS-TIMS and SSB-MC-ICP-MS results. The value of the IAPSO seawater standard (0.388 +/- 0.018; 2SEM) agrees with the results of the current SSB and DS-TIMS measurements and with previously published values. Using these values a variance-weighted mean for seawater was calculated (0.387 +/- 0.002, 2SEM). Compared to measurements carried out by the SSB method, natural sample measurements by the DS method are more accurate and more precise. An excellent agreement between DS-MC-ICP-MS and DS-TIMS methods was demonstrated for delta Sr-88/86 determination in natural samples over a range of similar to 0.5 parts per thousand. The DS-TIMS delta Sr-88/86 results had a smaller standard error than the DS-MC-ICP-MS measurements but required a much longer acquisition time

Description: Strontium isotopes in various marine carbonates were determined using an “AXIOM” MC-ICP-MS in combination with a NewWave UP193 laser ablation unit. Using a modified measurement and data reduction strategy, an external reproducibility of 87Sr/86Sr ratios in carbonates of about 19 ppm (RSD) was achieved. For recent and sub-recent marine carbonates a mean radiogenic strontium isotope ratio 87Sr/86Sr of 0.709170 ± 0.000007 (2SE) was determined, which agrees well with the value of 0.7091741 ± 0.0000024 (2SE) reported for modern sea water (J. M. McArthur, D. Rio, F. Massari, D. Castrodi, T. R. Bailey, M. Thirlwall and S. Houghton, Palaeogeogr. Palaeoclimatol. Palaeoeco., 2006, 242(126), 2006). Compared to published laser-based methods, an improved accuracy and precision was achieved by applying a new data reduction protocol using the simultaneous responses of all isotopes measured. The latter is considered as a new principal approach for isotope ratio evaluation using LA-MC-ICP-MS. A major advantage of the presented method is the direct determination of the stable strontium isotope fractionation. Providing reproducible sample ablation, introduction into the plasma and stable plasma condition, this method excludes the efforts of a quantitative strontium recovery after ion chromatographic separation to avoid additional fractionation of the sample strontium due to chemical pre-treatment/separation (ion chromatography and solution preparation), and is therefore, together with the quicker sample preparation and spatially resolved analysis, advantageous when compared to published solution–nebulization bracketing-standard MC-ICP-MS methods for stable strontium isotope determination.

Description: A new in situ method using LA-MC-ICP-MS (193 nm excimer laser) for the determination of stable boron isotope ratios (δ11B) in carbonates was developed. Data were acquired via a standard sample standard bracketing procedure typically providing a reproducibility of 0.5‰ (SD) for samples containing 35 ppm of boron. A single ablation interval consumed about 5 µg of sample corresponding to about 0.2 ng of boron. The major finding was the similar instrumental fractionation behaviour of carbonates, soda-lime glass and sea salt with respect to boron isotopes. As no matrix induced offset was detectable between these distinct materials we propose the use of NIST glasses as internal standards for boron isotope ratio measurements via LA-MC-ICP-MS. This finding overcomes the problem of a missing matrix matched carbonate standard for in situ boron isotope studies. As a first application a set of coral samples from a culturing experiment was analysed. δ11B values range from 19.5 to 25‰ depending on the pH of the water used in the particular treatment. This is in good agreement with the results of earlier studies.

Description: Thorium- and uranium isotopes were measured in a diagenetic manganese nodule from the Peru basin applying alpha- and thermal ionization mass spectrometry (TIMS). Alpha-counting of 62 samples was carried out with a depth resolution of 0.4 mm to gain a high-resolution230Thexcess profile. In addition, 17 samples were measured with TIMS to obtain precise isotope concentrations and isotope ratios. We got values of 0.06–0.59 ppb (230Th), 0.43–1.40 ppm (232Th), 0.09–0.49 ppb (234U) and 1.66–8.24 ppm (238U). The uranium activity ratio in the uppermost samples (1–6 mm) and in two further sections in the nodule at 12.5±1.0 mm and 27.3–33.5 mm comes close to the present ocean water value of 1.144±0.004. In two other sections of the nodule, this ratio is significantly higher, probably reflecting incorporation of diagenetic uranium. The upper 25 mm section of the Mn nodule shows a relatively smooth exponential decrease in the230Thexcess concentration (TIMS). The slope of the best fit yields a growth rate of 110 mm/Ma up to 24.5 mm depth. The section from 25 to 30.3 mm depth shows constant230Thexcess concentrations probably due to growth rates even faster than those in the top section of the nodule. From 33 to 50 mm depth, the growth rate is approximately 60 mm/Ma. Two layers in the nodule with distinct laminations (11–15 and 28–33 mm depth) probably formed during the transition from isotopic stage 8 to 7 and in stage 5e, respectively. The Mn/Fe ratio shows higher values during interglacials 5 and 7, and lower ones during glacials 4 and 6. A comparison of our data with data from adjacent sediment cores suggests (a) a variable supply of hydrothermal Mn to sediments and Mn nodules of the Peru basin or (b) suboxic conditions at the water sediment interface during periods with lower Mn/Fe ratios.