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1. Data report: X-ray fluorescence studies of Site U1457 sediments, Laxmi Basin, Arabian Sea

   https://doi.org/10.14379/iodp.proc.355.203.2018  

   Lyle, M. ; Kulhanek, D.K. ; Bowen, M.G. ; Hahn, A. ( December 2018 , Proceedings of the International Ocean Discovery Program)

   Bulk sediment chemistry was measured at 2 cm resolution along cores from International Ocean Discovery Program (IODP) Site U1457 using the X-ray fluorescence (XRF) core scanner at the IODP Gulf Coast Repository. The Pleistocene splice section assembled from Holes U1457A and U1457B was scanned in its entirety, and nearly continuous sediment bulk chemistry profiles were constructed to a depth of 125 m core composite depth below seafloor (CCSF). Some sections of Hole U1457C were also scanned: (1) an upper Miocene hemipelagic section and (2) a 30 m lower Paleocene section directly overlying basalt. In the Pleistocene spliced sections, 2 cm spacing represents a sampling resolution of 150–300 y, whereas in the upper Miocene section this spacing represents about 500 y between samples. We report data and acquisition conditions for major and many minor elements. We find large variability in CaCO3 content in the Pleistocene section, from around 14 to 89 wt%. We used discrete shipboard CaCO3 measurements to calibrate the XRF Ca data. CaCO3 has cyclic variability and correlates with light sediment colors. Variation in aluminosilicate elements is largely caused by changes in dilution by CaCO3. The lower part of the spliced section, presumably representing distal Indus Fan deposits, hasmore »a distinctive but more uniform composition than the upper part.« less
2. Florida mangrove saltmarsh reference surface soils

   https://doi.org/10.6073/pasta/0e08cbe07c84488cb7b9dd16669946d0  

   Lewis, David Bruce ( January 2021 )

   Abstract

   Site description. This data package consists of data obtained from sampling surface soil (the 0-7.6 cm depth profile) in black mangrove (Avicennia germinans) dominated forest and black needlerush (Juncus roemerianus) saltmarsh along the Gulf of Mexico coastline in peninsular west-central Florida, USA. This location has a subtropical climate with mean daily temperatures ranging from 15.4 °C in January to 27.8 °C in August, and annual precipitation of 1336 mm. Precipitation falls as rain primarily between June and September. Tides are semi-diurnal, with 0.57 m median amplitudes during the year preceding sampling (U.S. NOAA National Ocean Service, Clearwater Beach, Florida, station 8726724). Sea-level rise is 4.0 ± 0.6 mm per year (1973-2020 trend, mean ± 95 % confidence interval, NOAA NOS Clearwater Beach station). The A. germinans mangrove zone is either adjacent to water or fringed on the seaward side by a narrow band of red mangrove (Rhizophora mangle). A near-monoculture of J. roemerianus is often adjacent to and immediately landward of the A. germinans zone. The transition from the mangrove to the J. roemerianus zone is variable in our study area. An abrupt edge between closed-canopy mangrove and J. roemerianus monoculture may extend for up to several hundred meters in some locations, while other stretches of ecotone present a gradual transition where smaller, widely spaced trees are interspersed into the herbaceous marsh. Juncus roemerianus then extends landward to a high marsh patchwork of succulent halophytes (including Salicornia bigellovi, Sesuvium sp., and Batis maritima), scattered dwarf mangrove, and salt pans, followed in turn by upland vegetation that includes Pinus sp. and Serenoa repens. Field design and sample collection. We established three study sites spaced at approximately 5 km intervals along the western coastline of the central Florida peninsula. The sites consisted of the Salt Springs (28.3298°, -82.7274°), Energy Marine Center (28.2903°, -82.7278°), and Green Key (28.2530°, -82.7496°) sites on the Gulf of Mexico coastline in Pasco County, Florida, USA. At each site, we established three plot pairs, each consisting of one saltmarsh plot and one mangrove plot. Plots were 50 m^2 in size. Plots pairs within a site were separated by 230-1070 m, and the mangrove and saltmarsh plots composing a pair were 70-170 m apart. All plot pairs consisted of directly adjacent patches of mangrove forest and J. roemerianus saltmarsh, with the mangrove forests exhibiting a closed canopy and a tree architecture (height 4-6 m, crown width 1.5-3 m). Mangrove plots were located at approximately the midpoint between the seaward edge (water-mangrove interface) and landward edge (mangrove-marsh interface) of the mangrove zone. Saltmarsh plots were located 20-25 m away from any mangrove trees and into the J. roemerianus zone (i.e., landward from the mangrove-marsh interface). Plot pairs were coarsely similar in geomorphic setting, as all were located on the Gulf of Mexico coastline, rather than within major sheltering formations like Tampa Bay, and all plot pairs fit the tide-dominated domain of the Woodroffe classification (Woodroffe, 2002, "Coasts: Form, Process and Evolution", Cambridge University Press), given their conspicuous semi-diurnal tides. There was nevertheless some geomorphic variation, as some plot pairs were directly open to the Gulf of Mexico while others sat behind keys and spits or along small tidal creeks. Our use of a plot-pair approach is intended to control for this geomorphic variation. Plot center elevations (cm above mean sea level, NAVD 88) were estimated by overlaying the plot locations determined with a global positioning system (Garmin GPS 60, Olathe, KS, USA) on a LiDAR-derived bare-earth digital elevation model (Dewberry, Inc., 2019). The digital elevation model had a vertical accuracy of ± 10 cm (95 % CI) and a horizontal accuracy of ± 116 cm (95 % CI). Soil samples were collected via coring at low tide in June 2011. From each plot, we collected a composite soil sample consisting of three discrete 5.1 cm diameter soil cores taken at equidistant points to 7.6 cm depth. Cores were taken by tapping a sleeve into the soil until its top was flush with the soil surface, sliding a hand under the core, and lifting it up. Cores were then capped and transferred on ice to our laboratory at the University of South Florida (Tampa, Florida, USA), where they were combined in plastic zipper bags, and homogenized by hand into plot-level composite samples on the day they were collected. A damp soil subsample was immediately taken from each composite sample to initiate 1 y incubations for determination of active C and N (see below). The remainder of each composite sample was then placed in a drying oven (60 °C) for 1 week with frequent mixing of the soil to prevent aggregation and liberate water. Organic wetland soils are sometimes dried at 70 °C, however high drying temperatures can volatilize non-water liquids and oxidize and decompose organic matter, so 50 °C is also a common drying temperature for organic soils (Gardner 1986, "Methods of Soil Analysis: Part 1", Soil Science Society of America); we accordingly chose 60 °C as a compromise between sufficient water removal and avoidance of non-water mass loss. Bulk density was determined as soil dry mass per core volume (adding back the dry mass equivalent of the damp subsample removed prior to drying). Dried subsamples were obtained for determination of soil organic matter (SOM), mineral texture composition, and extractable and total carbon (C) and nitrogen (N) within the following week. Sample analyses. A dried subsample was apportioned from each composite sample to determine SOM as mass loss on ignition at 550 °C for 4 h. After organic matter was removed from soil via ignition, mineral particle size composition was determined using a combination of wet sieving and density separation in 49 mM (3 %) sodium hexametaphosphate ((NaPO_3)_6) following procedures in Kettler et al. (2001, Soil Science Society of America Journal 65, 849-852). The percentage of dry soil mass composed of silt and clay particles (hereafter, fines) was calculated as the mass lost from dispersed mineral soil after sieving (0.053 mm mesh sieve). Fines could have been slightly underestimated if any clay particles were burned off during the preceding ignition of soil. An additional subsample was taken from each composite sample to determine extractable N and organic C concentrations via 0.5 M potassium sulfate (K_2SO_4) extractions. We combined soil and extractant (ratio of 1 g dry soil:5 mL extractant) in plastic bottles, reciprocally shook the slurry for 1 h at 120 rpm, and then gravity filtered it through Fisher G6 (1.6 μm pore size) glass fiber filters, followed by colorimetric detection of nitrite (NO_2^-) + nitrate (NO_3^-) and ammonium (NH_4^+) in the filtrate (Hood Nowotny et al., 2010,Soil Science Society of America Journal 74, 1018-1027) using a microplate spectrophotometer (Biotek Epoch, Winooski, VT, USA). Filtrate was also analyzed for dissolved organic C (referred to hereafter as extractable organic C) and total dissolved N via combustion and oxidation followed by detection of the evolved CO_2 and N oxide gases on a Formacs HT TOC/TN analyzer (Skalar, Breda, The Netherlands). Extractable organic N was then computed as total dissolved N in filtrate minus extractable mineral N (itself the sum of extractable NH_4-N and NO_2-N + NO_3-N). We determined soil total C and N from dried, milled subsamples subjected to elemental analysis (ECS 4010, Costech, Inc., Valencia, CA, USA) at the University of South Florida Stable Isotope Laboratory. Median concentration of inorganic C in unvegetated surface soil at our sites is 0.5 % of soil mass (Anderson, 2019, Univ. of South Florida M.S. thesis via methods in Wang et al., 2011, Environmental Monitoring and Assessment 174, 241-257). Inorganic C concentrations are likely even lower in our samples from under vegetation, where organic matter would dilute the contribution of inorganic C to soil mass. Nevertheless, the presence of a small inorganic C pool in our soils may be counted in the total C values we report. Extractable organic C is necessarily of organic C origin given the method (sparging with HCl) used in detection. Active C and N represent the fractions of organic C and N that are mineralizable by soil microorganisms under aerobic conditions in long-term soil incubations. To quantify active C and N, 60 g of field-moist soil were apportioned from each composite sample, placed in a filtration apparatus, and incubated in the dark at 25 °C and field capacity moisture for 365 d (as in Lewis et al., 2014, Ecosphere 5, art59). Moisture levels were maintained by frequently weighing incubated soil and wetting them up to target mass. Daily CO_2 flux was quantified on 29 occasions at 0.5-3 week intervals during the incubation period (with shorter intervals earlier in the incubation), and these per day flux rates were integrated over the 365 d period to compute an estimate of active C. Observations of per day flux were made by sealing samples overnight in airtight chambers fitted with septa and quantifying headspace CO_2 accumulation by injecting headspace samples (obtained through the septa via needle and syringe) into an infrared gas analyzer (PP Systems EGM 4, Amesbury, MA, USA). To estimate active N, each incubated sample was leached with a C and N free, 35 psu solution containing micronutrients (Nadelhoffer, 1990, Soil Science Society of America Journal 54, 411-415) on 19 occasions at increasing 1-6 week intervals during the 365 d incubation, and then extracted in 0.5 M K_2SO_4 at the end of the incubation in order to remove any residual mineral N. Active N was then quantified as the total mass of mineral N leached and extracted. Mineral N in leached and extracted solutions was detected as NH_4-N and NO_2-N + NO_3-N via colorimetry as above. This incubation technique precludes new C and N inputs and persistently leaches mineral N, forcing microorganisms to meet demand by mineralizing existing pools, and thereby directly assays the potential activity of soil organic C and N pools present at the time of soil sampling. Because this analysis commences with disrupting soil physical structure, it is biased toward higher estimates of active fractions. Calculations. Non-mobile C and N fractions were computed as total C and N concentrations minus the extractable and active fractions of each element. This data package reports surface-soil constituents (moisture, fines, SOM, and C and N pools and fractions) in both gravimetric units (mass constituent / mass soil) and areal units (mass constituent / soil surface area integrated through 7.6 cm soil depth, the depth of sampling). Areal concentrations were computed as X × D × 7.6, where X is the gravimetric concentration of a soil constituent, D is soil bulk density (g dry soil / cm^3), and 7.6 is the sampling depth in cm.
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3. Late Miocene to Holocene high-resolution eastern equatorial Pacific carbonate records: stratigraphy linked by dissolution and paleoproductivity

   https://doi.org/10.5194/cp-15-1715-2019  

   Lyle, Mitchell ; Drury, Anna Joy ; Tian, Jun ; Wilkens, Roy ; Westerhold, Thomas ( January 2019 , Climate of the Past)

   Abstract. Coherent variation in CaCO₃ burial is a feature ofthe Cenozoic eastern equatorial Pacific. Nevertheless, there has been along-standing ambiguity in whether changes in CaCO₃ dissolution or changesin equatorial primary production might cause the variability. Sinceproductivity and dissolution leave distinctive regional signals, a regionalsynthesis of data using updated age models and high-resolution stratigraphiccorrelation is an important constraint to distinguish between dissolutionand production as factors that cause low CaCO₃. Furthermore, the newchronostratigraphy is an important foundation for future paleoceanographicstudies. The ability to distinguish between primary production anddissolution is also important to establish a regional carbonate compensationdepth (CCD). We report late Miocene to Holocene time series of XRF-derived (X-rayfluorescence) bulk sediment composition and mass accumulation rates (MARs) from easternequatorial Pacific Integrated Ocean Drilling Program (IODP) sites U1335,U1337, and U1338 and Ocean Drilling Program (ODP) site 849, and we also report bulk-density-derived CaCO₃ MARs at ODP sites 848, 850, and 851. We usephysical properties, XRF bulk chemical scans, and images along withavailable chronostratigraphy to intercorrelate records in depth space. Wethen apply a new equatorial Pacific age model to create correlated agerecords for the last 8 Myr with resolutions of 1–2 kyr. Large magnitudechanges in CaCO₃ and bio-SiO₂ (biogenic opal)more »MARs occurred withinthat time period but clay deposition has remained relatively constant,indicating that changes in Fe deposition from dust is only a secondaryfeedback to equatorial productivity. Because clay deposition is relativelyconstant, ratios of CaCO₃ % or biogenic SiO₂ % to clayemulate changes in biogenic MAR. We define five major Pliocene–Pleistocene low CaCO₃ % (PPLC) intervalssince 5.3 Ma. Two were caused primarily by high bio-SiO₂ burial thatdiluted CaCO₃ (PPLC-2, 1685–2135 ka, and PPLC-5, 4465–4737 ka),while three were caused by enhanced dissolution of CaCO₃ (PPLC-1, 51–402 ka, PPLC-3, 2248–2684 ka, and PPLC-4, 2915–4093 ka). Regional patterns ofCaCO₃ % minima can distinguish between low CaCO₃ caused by highdiatom bio-SiO₂ dilution versus lows caused by high CaCO₃dissolution. CaCO₃ dissolution can be confirmed through scanning XRFmeasurements of Ba. High diatom production causes lowest CaCO₃ %within the equatorial high productivity zone, while higher dissolutioncauses lowest CaCO₃ percent at higher latitudes where CaCO₃ production islower. The two diatom production intervals, PPLC-2 and PPLC-5, havedifferent geographic footprints from each other because of regional changesin eastern Pacific nutrient storage after the closure of the Central American Seaway.Because of the regional variability in carbonate production andsedimentation, the carbonate compensation depth (CCD) approach is onlyuseful to examine large changes in CaCO₃ dissolution.

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4. Trace elements in mollusc shells and benthic foraminifera

   Brooks, HL ; Cruz-Uribe, AM ; Stone, JS ( May 2019 , North American Workshop on Laser Ablation 2019 Abstracts)

   Throughout the course of an organism’s life, the chemical signatures of environment, food consumption, and weather are recorded into their carbonate structures; these signatures can be directly linked to a time-resolved lifespan. Here we present trace element data from benthic foraminifera and tropical molluscs determined using an ESI NWR193UC excimer laser coupled with an Agilent 8900 triple quadrupole mass spectrometer in the MicroAnalytical Geochemistry and Isotope Characterization (MAGIC) Laboratory at the University of Maine. Benthic foraminifera are protists that live on the sea floor and produce calcite shells, progressively adding chambers. Changes in Mg/Ca in foraminifera are used as a proxy for ocean temperature. Laser ablation ICP-MS data for 18 trace elements were collected in individual growth chambers in foraminifera of the genus Uvigerina from the Bay of Plenty. Line scans were performed within thin (~10 µm) chamber walls using a spot size of 8 µm, beam energy density of 3 J/cm2, repetition rate of 12 Hz, and scan speeds of 2-3 µm/s. Concentrations were determined relative to the NIST610 glass. Ratios of Mg/Ca and other trace elements record the same range of values as those determined via bulk wet chemistry analysis of ~10 foraminifera for a given population, whichmore »suggests that LA-ICP-MS may be a viable alternative to wet chemistry. Trace element data were collected across shells of the warm-tropical mollusc species Chione subrugosa from the Ostra Base Camp area, Peru (78°37’22”W, 8°54’46”S). Previous studies of the area have suggested that a large climate transition occurred, transforming a warm water tropical bay into a desert surrounded by a coastal stand with cool waters. This area was occupied by humans at 6250-5450 radiocarbon years BP. This study examines Chione subrugosa, which were found in the living position at the fossilized Ostra Beach and are thought to have been the final living warm-tropical molluscs in the bay. Studies of modern molluscs have revealed that molluscs record massive climatic changes, such as El Niño, in their chemistry. Laser ablation provides a unique opportunity to examine chemical changes directly related to the changing coastal environment. Line scans transverse growth bands along the length of the shell, providing a high resolution record of daily variation in trace element chemistry over the lifespan of the mollusc. Eleven elements were analysed with a beam energy density of 2.4 J/cm2, repetition rate of 15 Hz, spot size of 5 x 25 µm, and a scan speed of 5 µm/s. Preliminary data suggest the preservation of yearly oscillations in trace elements, with high concentrations of La, Ce, U, and Pb during early shell growth. Continued study will examine catastrophic mollusc life events in an effort to link these with environmental climate changes over daily timescales.« less
5. An updated version of the global interior ocean biogeochemical data product, GLODAPv2.2020

   https://doi.org/10.5194/essd-12-3653-2020  

   Olsen, Are ; Lange, Nico ; Key, Robert M. ; Tanhua, Toste ; Bittig, Henry C. ; Kozyr, Alex ; Álvarez, Marta ; Azetsu-Scott, Kumiko ; Becker, Susan ; Brown, Peter J. ; et al ( January 2020 , Earth System Science Data)

   Abstract. The Global Ocean Data Analysis Project (GLODAP) is asynthesis effort providing regular compilations of surface-to-bottom oceanbiogeochemical data, with an emphasis on seawater inorganic carbon chemistryand related variables determined through chemical analysis of seawatersamples. GLODAPv2.2020 is an update of the previous version, GLODAPv2.2019.The major changes are data from 106 new cruises added, extension of timecoverage to 2019, and the inclusion of available (also for historicalcruises) discrete fugacity of CO2 (fCO2) values in the mergedproduct files. GLODAPv2.2020 now includes measurements from more than 1.2 million water samples from the global oceans collected on 946 cruises. Thedata for the 12 GLODAP core variables (salinity, oxygen, nitrate, silicate,phosphate, dissolved inorganic carbon, total alkalinity, pH, CFC-11, CFC-12,CFC-113, and CCl4) have undergone extensive quality control with afocus on systematic evaluation of bias. The data are available in twoformats: (i) as submitted by the data originator but updated to WOCEexchange format and (ii) as a merged data product with adjustments appliedto minimize bias. These adjustments were derived by comparing the data fromthe 106 new cruises with the data from the 840 quality-controlled cruises ofthe GLODAPv2.2019 data product using crossover analysis. Comparisons toempirical algorithm estimates provided additional context for adjustmentdecisions; this is new to this version. The adjustments are intendedmore »toremove potential biases from errors related to measurement, calibration, anddata-handling practices without removing known or likely time trends orvariations in the variables evaluated. The compiled and adjusted dataproduct is believed to be consistent to better than 0.005 in salinity, 1 % in oxygen, 2 % in nitrate, 2 % in silicate, 2 % in phosphate,4 µmol kg−1 in dissolved inorganic carbon, 4 µmol kg−1in total alkalinity, 0.01–0.02 in pH (depending on region), and 5 % inthe halogenated transient tracers. The other variables included in thecompilation, such as isotopic tracers and discrete fCO2, were notsubjected to bias comparison or adjustments. The original data and their documentation and DOI codes are available at theOcean Carbon Data System of NOAA NCEI(https://www.nodc.noaa.gov/ocads/oceans/GLODAPv2_2020/, lastaccess: 20 June 2020). This site also provides access to the merged dataproduct, which is provided as a single global file and as four regional ones– the Arctic, Atlantic, Indian, and Pacific oceans –under https://doi.org/10.25921/2c8h-sa89 (Olsen et al., 2020). Thesebias-adjusted product files also include significant ancillary andapproximated data. These were obtained by interpolation of, or calculationfrom, measured data. This living data update documents the GLODAPv2.2020methods and provides a broad overview of the secondary quality controlprocedures and results.« less