Climate-driven sea level anomalies modulate coastal groundwater dynamics and discharge

Author Posting. © American Geophysical Union, 2013. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 40 (2013): 2701–2706, doi:10.1002/grl.50192.To better understand the physical drivers of submarine groundwater discharge (SGD) in the coastal ocean, we conducted a detailed field and modeling study within an unconfined coastal aquifer system. We monitored the hydraulic gradient across the coastal aquifer and movement of the mixing zone over multiple years. At our study site, sea level dominated over groundwater head as the largest contributor to variability in the hydraulic gradient and therefore SGD. Model results indicate the seawater recirculation component of SGD was enhanced during summer while the terrestrial component dominated during winter due to seasonal changes in sea level driven by a combination of long period solar tides, temperature and winds. In one year, sea level remained elevated year round due to a combination of ENSO and NAO climate modes. Hence, predicted changes in regional climate variability driven sea level may impact future rates of SGD and biogeochemical cycling within coastal aquifers.This work is a result of research sponsored by the NSF Chemical Oceanography program (OCE- 0425061 to M.C. and A.M. and OCE-0751525 to M.C.) and an NDSEG graduate fellowship (to M.G.).2013-12-0

Relationship between water and aragonite barium concentrations in aquaria reared juvenile corals

This paper is not subject to U.S. copyright. The definitive version was published in Geochimica et Cosmochimica Acta 209 (2017): 123-134, doi:10.1016/j.gca.2017.04.006.Coral barium to calcium (Ba/Ca) ratios have been used to reconstruct records of upwelling, river and groundwater discharge, and sediment and dust input to the coastal ocean. However, this proxy has not yet been explicitly tested to determine if Ba inclusion in the coral skeleton is directly proportional to seawater Ba concentration and to further determine how additional factors such as temperature and calcification rate control coral Ba/Ca ratios. We measured the inclusion of Ba within aquaria reared juvenile corals (Favia fragum) at three temperatures (∼27.7, 24.6 and 22.5 °C) and three seawater Ba concentrations (73, 230 and 450 nmol kg−1). Coral polyps were settled on tiles conditioned with encrusting coralline algae, which complicated chemical analysis of the coral skeletal material grown during the aquaria experiments. We utilized Sr/Ca ratios of encrusting coralline algae (as low as 3.4 mmol mol−1) to correct coral Ba/Ca for this contamination, which was determined to be 26 ± 11% using a two end member mixing model. Notably, there was a large range in Ba/Ca across all treatments, however, we found that Ba inclusion was linear across the full concentration range. The temperature sensitivity of the distribution coefficient is within the range of previously reported values. Finally, calcification rate, which displayed large variability, was not correlated to the distribution coefficient. The observed temperature dependence predicts a change in coral Ba/Ca ratios of 1.1 μmol mol−1 from 20 to 28 °C for typical coastal ocean Ba concentrations of 50 nmol kg−1. Given the linear uptake of Ba by corals observed in this study, coral proxy records that demonstrate peaks of 10–25 μmol mol−1 would require coastal seawater Ba of between 60 and 145 nmol kg−1. Further validation of the coral Ba/Ca proxy requires evaluation of changes in seawater chemistry associated with the environmental perturbation recorded by the coral as well as verification of these results for Porites species, which are widely used in paleo reconstructions.M.E.G. was supported by a NDSEG graduate fellowship. Funding for this research came from the NSF Chemical Oceanography program (OCE-0751525) and the Coastal Ocean Institute, the Ocean and Climate Change Institute and the Ocean Ventures Fund at Woods Hole Oceanographic Institution

Water salinity and inundation control soil carbon decomposition during salt marsh restoration: An incubation experiment.

© The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Wang, F., Kroeger, K. D., Gonneea, M. E., Pohlman, J. W., & Tang, J. Water salinity and inundation control soil carbon decomposition during salt marsh restoration: An incubation experiment. Ecology and Evolution, 9(4), (2019):1911-1921, doi:10.1002/ece3.4884.Coastal wetlands are a significant carbon (C) sink since they store carbon in anoxic soils. This ecosystem service is impacted by hydrologic alteration and management of these coastal habitats. Efforts to restore tidal flow to former salt marshes have increased in recent decades and are generally associated with alteration of water inundation levels and salinity. This study examined the effect of water level and salinity changes on soil organic matter decomposition during a 60‐day incubation period. Intact soil cores from impounded fresh water marsh and salt marsh were incubated after addition of either sea water or fresh water under flooded and drained water levels. Elevating fresh water marsh salinity to 6 to 9 ppt enhanced CO2 emission by 50%−80% and most typically decreased CH4 emissions, whereas, decreasing the salinity from 26 ppt to 19 ppt in salt marsh soils had no effect on CO2 or CH4 fluxes. The effect from altering water levels was more pronounced with drained soil cores emitting ~10‐fold more CO2 than the flooded treatment in both marsh sediments. Draining soil cores also increased dissolved organic carbon (DOC) concentrations. Stable carbon isotope analysis of CO2 generated during the incubations of fresh water marsh cores in drained soils demonstrates that relict peat OC that accumulated when the marsh was saline was preferentially oxidized when sea water was introduced. This study suggests that restoration of tidal flow that raises the water level from drained conditions would decrease aerobic decomposition and enhance C sequestration. It is also possible that the restoration would increase soil C decomposition of deeper deposits by anaerobic oxidation, however this impact would be minimal compared to lower emissions expected due to the return of flooding conditions.We acknowledge collaboration and support from Tim Smith of the Cape Cod National Seashore, James Rassman and Tonna‐Marie Surgeon‐Rogers of the Waquoit Bay National Estuarine Research Reserve, Margot McKlveen of the Marine Biological Laboratory, Jennifer O'keefe Suttles, Wally Brooks and Michael Casso of the USGS, and Amanda Spivak of the Woods Hole Oceanographic Institution. This study was funded by the NOAA National Estuarine Research Reserve Science Collaborative (NA09NOS4190153 and NA14NOS4190145) awarded to JT and KK, MIT Sea Grant (2015‐R/RC‐141), and USGS‐Land Carbon and Coastal & Marine Geology projects. F.W. was also supported by funding from Natural Science Foundation of China (31300419, 31670621, 31870463). Any use of trade names is for descriptive purposes and does not imply endorsement by the U.S. government

Intertidal salt marshes as an important source of inorganic carbon to the coastal ocean

© The Author(s), 2016. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Limnology and Oceanography 61 (2016): 1916–1931, doi:10.1002/lno.10347.Dynamic tidal export of dissolved inorganic carbon (DIC) to the coastal ocean from highly productive intertidal marshes and its effects on seawater carbonate chemistry are thoroughly evaluated. The study uses a comprehensive approach by combining tidal water sampling of CO2 parameters across seasons, continuous in situ measurements of biogeochemically-relevant parameters and water fluxes, with high-resolution modeling in an intertidal salt marsh of the U.S. northeast region. Salt marshes can acidify and alkalize tidal water by injecting CO2 (DIC) and total alkalinity (TA). DIC and TA generation may also be decoupled due to differential effects of marsh aerobic and anaerobic respiration on DIC and TA. As marsh DIC is added to tidal water, the buffering capacity first decreases to a minimum and then increases quickly. Large additions of marsh DIC can result in higher buffering capacity in ebbing tide than incoming tide. Alkalization of tidal water, which mostly occurs in the summer due to anaerobic respiration, can further modify buffering capacity. Marsh exports of DIC and alkalinity may have complex implications for the future, more acidified ocean. Marsh DIC export exhibits high variability over tidal and seasonal cycles, which is modulated by both marsh DIC generation and by water fluxes. The marsh DIC export of 414 g C m−2 yr−1, based on high-resolution measurements and modeling, is more than twice the previous estimates. It is a major term in the marsh carbon budget and translates to one of the largest carbon fluxes along the U.S. East Coast.USGS Coastal & Marine Geology Program; U.S. National Science Foundation Grant Number: OCE-1459521; NOAA Science Collaborative Grant Number: NA09NOS4190153; USGS LandCarbon Progra

Deciphering the dynamics of inorganic carbon export from intertidal salt marshes using high-frequency measurements

© The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Marine Chemistry 206 (2018): 7-18, doi:10.1016/j.marchem.2018.08.005.The lateral export of carbon from coastal marshes via tidal exchange is a key component of the marsh carbon budget and coastal carbon cycles. However, the magnitude of this export has been difficult to accurately quantify due to complex tidal dynamics and seasonal cycling of carbon. In this study, we use in situ, high-frequency measurements of dissolved inorganic carbon (DIC) and water fluxes to estimate lateral DIC fluxes from a U.S. northeastern salt marsh. DIC was measured by a CHANnelized Optical Sensor (CHANOS) that provided an in situ concentration measurement at 15-min intervals, during periods in summer (July – August) and late fall (December). Seasonal changes in the marsh had strong effects on DIC concentrations, while tidally-driven water fluxes were the fundamental vehicle of marsh carbon export. Episodic events, such as groundwater discharge and mean sea water level changes, can impact DIC flux through altered DIC concentrations and water flow. Variability between individual tides within each season was comparable to mean variability between the two seasons. Estimated mean DIC fluxes based on a multiple linear regression (MLR) model of DIC concentrations and high-frequency water fluxes agreed reasonably well with those derived from CHANOS DIC measurements for both study periods, indicating that high-frequency, modeled DIC concentrations, coupled with continuous water flux measurements and a hydrodynamic model, provide a robust estimate of DIC flux. Additionally, an analysis of sampling strategies revealed that DIC fluxes calculated using conventional sampling frequencies (hourly to two-hourly) of a single tidal cycle are unlikely to capture a representative mean DIC flux compared to longer-term measurements across multiple tidal cycles with sampling frequency on the order of tens of minutes. This results from a disproportionately large amount of the net DIC flux occurring over a small number of tidal cycles, while most tides have a near-zero DIC export. Thus, high-frequency measurements (on the order of tens of minutes or better) over the time period of interest are necessary to accurately quantify tidal exports of carbon species from salt marshes.This work was funded by NSF Graduate Research Fellowship Program, NSF Ocean Sciences Postdoctoral Fellowship (OCE-1323728), Link FoundationOcean Engineering and Instrumentation Fellowship, National Institute of Science and Technology (NIST no. 60NANB10D024), the USGS LandCarbon and Coastal & Marine Geology Programs, NSF Chemical Oceanography Program (OCE-1459521), NSF Ocean Technology and Interdisciplinary Coordination program (OCE-1233654) and NOAA Science Collaborative (NA09NOS4190153)

Erratum : GEOTRACES radium isotopes interlaboratory comparison experiment

Author Posting. © Association for the Sciences of Limnology and Oceanography, 2012. This article is posted here by permission of Association for the Sciences of Limnology and Oceanography for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography: Methods 10 (2012): 617, doi:10.4319/lom.2012.10.617.In our original paper, Charette, M. A., H. Dulaiova, M. E. Gonneea, P. B. Henderson, W. S. Moore, J. C. Scholten, and M. K. Pham. 2012. GEOTRACES radium isotopes interlaboratory comparison experiment. Limonol. Oceanogr.: Methods 10:451, the incorrect headers were used for Table 9

GEOTRACES radium isotopes interlaboratory comparison experiment

Author Posting. © Association for the Sciences of Limnology and Oceanography, 2012. This article is posted here by permission of Association for the Sciences of Limnology and Oceanography for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography: Methods 10 (2012): 451-463, doi:10.4319/lom.2012.10.451.In anticipation of the international GEOTRACES program, which will study the global marine biogeochemistry of trace elements and isotopes, we conducted a multi-lab intercomparison for radium isotopes. The intercomparison was in two parts involving the distribution of: (1) samples collected from four marine environments (open ocean, continental slope, shelf, and estuary) and (2) a suite of four reference materials prepared with isotopic standards (circulated to participants as 'unknowns'). Most labs performed well with 228Ra and 224Ra determination, however, there were a number of participants that reported 226Ra, 223Ra, and 228Th (supported 224Ra) well outside the 95% confidence interval. Many outliers were suspected to be a result of poorly calibrated detectors, though other method specific factors likely played a role (e.g., detector leakage, insufficient equilibration). Most methods for radium analysis in seawater involve a MnO2 fiber column preconcentration step; as such, we evaluated the extraction efficiency of this procedure and found that it ranged from an average of 87% to 94% for the four stations. Hence, nonquantitative radium recovery from seawater samples may also have played a role in lab-to-lab variability.This work was funded by grants from the National Science Foundation (OCE- 0751461to M.A.C and H.D. and OCE- 0751867 to W.S.M.)

Twentieth century warming of the tropical Atlantic captured by Sr-U paleothermometry

Author Posting. © American Geophysical Union, 2017. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 32 (2017): 146–160, doi:10.1002/2016PA002976.Coral skeletons are valuable archives of past ocean conditions. However, interpretation of coral paleotemperature records is confounded by uncertainties associated with single-element ratio thermometers, including Sr/Ca. A new approach, Sr-U, uses U/Ca to constrain the influence of Rayleigh fractionation on Sr/Ca. Here we build on the initial Pacific Porites Sr-U calibration to include multiple Atlantic and Pacific coral genera from multiple coral reef locations spanning a temperature range of 23.15–30.12°C. Accounting for the wintertime growth cessation of one Bermuda coral, we show that Sr-U is strongly correlated with the average water temperature at each location (r2 = 0.91, P < 0.001, n = 19). We applied the multispecies spatial calibration between Sr-U and temperature to reconstruct a 96 year long temperature record at Mona Island, Puerto Rico, using a coral not included in the calibration. Average Sr-U derived temperature for the period 1900–1996 is within 0.12°C of the average instrumental temperature at this site and captures the twentieth century warming trend of 0.06°C per decade. Sr-U also captures the timing of multiyear variability but with higher amplitude than implied by the instrumental data. Mean Sr-U temperatures and patterns of multiyear variability were replicated in a second coral in the same grid box. Conversely, Sr/Ca records from the same two corals were inconsistent with each other and failed to capture absolute sea temperatures, timing of multiyear variability, or the twentieth century warming trend. Our results suggest that coral Sr-U paleothermometry is a promising new tool for reconstruction of past ocean temperatures.NSF Graduate Research Fellowships Grant Numbers: NSF-OCE-1338320, NSF-OCE-1031971, NSF-OCE-0926986; WHOI Access to the Sea Grant Numbers: 27500056, 0734826; NSF HRD; UPR Central Administration to EAHD through the Center for Applied Tropical Ecology and Conservation of UPR2017-08-1

Environmental controls, emergent scaling, and predictions of greenhouse gas (GHG) fluxes in coastal salt marshes

Author Posting. © American Geophysical Union, 2018. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Biogeosciences 123 (2018): 2234-2256, doi:10.1029/2018JG004556.Coastal salt marshes play an important role in mitigating global warming by removing atmospheric carbon at a high rate. We investigated the environmental controls and emergent scaling of major greenhouse gas (GHG) fluxes such as carbon dioxide (CO2) and methane (CH4) in coastal salt marshes by conducting data analytics and empirical modeling. The underlying hypothesis is that the salt marsh GHG fluxes follow emergent scaling relationships with their environmental drivers, leading to parsimonious predictive models. CO2 and CH4 fluxes, photosynthetically active radiation (PAR), air and soil temperatures, well water level, soil moisture, and porewater pH and salinity were measured during May–October 2013 from four marshes in Waquoit Bay and adjacent estuaries, MA, USA. The salt marshes exhibited high CO2 uptake and low CH4 emission, which did not significantly vary with the nitrogen loading gradient (5–126 kg · ha−1 · year−1) among the salt marshes. Soil temperature was the strongest driver of both fluxes, representing 2 and 4–5 times higher influence than PAR and salinity, respectively. Well water level, soil moisture, and pH did not have a predictive control on the GHG fluxes, although both fluxes were significantly higher during high tides than low tides. The results were leveraged to develop emergent power law‐based parsimonious scaling models to accurately predict the salt marsh GHG fluxes from PAR, soil temperature, and salinity (Nash‐Sutcliffe Efficiency = 0.80–0.91). The scaling models are available as a user‐friendly Excel spreadsheet named Coastal Wetland GHG Model to explore scenarios of GHG fluxes in tidal marshes under a changing climate and environment.National Oceanic and Atmospheric Administration Grant Numbers: NA09NOS4190153, NA14NOS4190145; National Science Foundation (NSF) Grant Numbers: 1705941, 1561941/1336911; USGS LandCarbon Program; NOAA National Estuarine Research Reserve Science Collaborative Grant Number: NA09NOS4190153 and NA14NOS41901452019-01-2

Groundwater discharge impacts marine isotope budgets of Li, Mg, Ca, Sr, and Ba

© 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.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.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