Particle Flux in the deep Sargasso Sea : the 35-Year Oceanic Flux Program time series

Author Posting. © The Oceanography Society, 2014. This article is posted here by permission of The Oceanography Society for personal use, not for redistribution. The definitive version was published in Oceanography 27, no. 1 (2014): 142–147, doi:10.5670/oceanog.2014.17.The Oceanic Flux Program (OFP) sediment trap time series, the longest running time series of its kind, has continuously measured particle fluxes in the deep Sargasso Sea since 1978. OFP results provided the first direct observation of seasonality in the deep ocean, and they have documented the tight coupling between deep fluxes and upper ocean processes and the intensity of biological reprocessing of sinking flux in the ocean interior. The synergy among OFP and other research programs co-located at the Bermuda time-series site has provided unprecedented opportunities to study the linkages among ocean physics, biology, and chemistry; particle flux generation; and particle recycling in the ocean interior. The OFP time series is beginning to reveal how basin-scale climatic forcing, such as the North Atlantic Oscillation, affects the deep particle flux.We gratefully acknowledge the National Science Foundation’s continuous financial support of the Oceanic Flux Program time series for the past 35 years, most recently by NSF grants OCE 1234294 and OCE 0927098

Carbon Isotopic Studies of Assimilated and Ecosystem Respired CO2 in a Southeastern Pine Forest

Carbon dioxide is the major “greenhouse” gas responsible for global warming. Southeastern pine forests appear to be among the largest terrestrial sinks of carbon dioxide in the US. This collaborative study specifically addressed the isotopic signatures of the large fluxes of carbon taken up by photosynthesis and given off by respiration in this ecosystem. By measuring these isotopic signatures at the ecosystem level, we have provided data that will help to more accurately quantify the magnitude of carbon fluxes on the regional scale and how these fluxes vary in response to climatic parameters such as rainfall and air temperature. The focus of the MBL subcontract was to evaluate how processes operating at the physiological and ecosystem scales affects the resultant isotopic signature of plant waxes that are emitted as aerosols into the convective boundary layer. These wax aerosols provide a large-spatial scale integrative signal of isotopic discrimination of atmospheric carbon dioxide by terrestrial photosynthesis (Conte and Weber 2002). The ecosystem studies have greatly expanded of knowledge of wax biosynthetic controls on their isootpic signature The wax aerosol data products produced under this grant are directly applicable as input for global carbon modeling studies that use variations in the concentration and carbon isotopic composition of atmospheric carbon dioxide to quantify the magnitude and spatial and temporal patterns of carbon uptake on the global scale

The Aquatic Particle Number Quandry

Optical surveys of aquatic particles and their particle size spectra have become important tools in studies of light propagation in water, classification of water masses, and the dynamics of trophic interactions affecting particle aggregation and flux. Here, we demonstrate that typical settings used in image analysis vastly underestimate particle numbers due to the particle – gel continuum. Applying a wide range of threshold values to change the sensitivity of our detection system, we show that macrogels cannot be separated from more dense particles, and that a true particle number per volume cannot be ascertained; only relative numbers in relation to a defined threshold value can be reported. A quandary thus presents itself between choosing a detection threshold low enough to accurately record orders of magnitude more particles on one hand or selecting a higher threshold to yield better image quality of plankton on the other. By observing the dynamics of coagulation and dissolution steps unique to cation-bridged gels abundant in aquatic systems, we find naturally occurring gels, and microscopic particles attached to them, to cause the ill-defined particle numbers. In contrast, the slopes in particle number spectra remained largely unaffected by varying sensitivity settings of the image analysis. The inclusion of fainter particles that are not typically captured by imaging systems provides a window into the true microscale spatial heterogeneity at scales relevant to small plankton organisms and processes that are dependent on particle density such as surface-associated chemical reactions as well as particle coagulation and aggregation dynamics

Scavenging, cycling and removal fluxes of 210Po and 210Pb at the Bermuda time-series study site

Author Posting. © The Author(s), 2012. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Deep Sea Research Part II: Topical Studies in Oceanography 93 (2013):108–118, doi:10.1016/j.dsr2.2013.01.005.Quantifying relative affinities of Po and Pb in different populations of marine particulate matter is of great importance in utilizing 210Po as a tracer for carbon cycling. We collected and analyzed water samples for the concentrations of dissolved and total 210Po and 30 210Pb from the upper 600 m of the water column at Bermuda Time-series Study site (September 1999 to September 2000) to investigate their seasonality of concentrations and their activity ratio (210Po/210Pb activity ratio, AR). Sinking particles collected in sediment traps at depths of 500 m, 1500 m, and 3200 m from the Oceanic Flux Program (OFP) time-series sediment traps were analyzed over a period of 12 months (May 1999 to May 2000). The objective was to compare the deficiencies of 210Po with respect to 210Pb in the water column to that measured in the sediment traps and to assess the relative affinities of Po and Pb with different particle pools. Inventories of 210Po in the upper 500 m water column varied by a factor of 2, indicating seasonal variations of particulate flux dominated the removal of 210Po. The 210Po/210Pb ARs in the dissolved phase were generally less than the secular equilibrium value (1.0) in the upper 600 m, while were generally greater than 1.0 in the particulate phase, indicating higher removal rates of 210Po relative to 210Pb by particulate matter. The measured fluxes of 210Po and 210Pb in the 500 m, 1500 m, and 3200 m traps increased with depth, while the 210Po/210Pb ARs decreased with depth except from May-August 1999. From the measured fluxes of 210Po and 210Pb at these three traps and the concentrations of 210Po and 210Pb in the water column, this region appears to be a sink for 210Pb which is likely brought-in by lateral advection.GHH’s sabbatical leave was supported by Korea Ocean Research and Development Institute (renamed as Korea Institute of Ocean Science and Technology) (PG47900 and PE98742). The Oceanic Flux Program has been supported since inception by the NSF Chemical Oceanography Program, most recently by grants OCE-0325627/0509602, OCE-0623505 and OCE-0927098. Partial support in writing this manuscript was supported by OCE-0961351 (MB)

Hurricanes enhance labile carbon export to the deep ocean

Author Posting. © American Geophysical Union, 2019. 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 46 (2019): 10484–10494, doi:10.1029/2019GL083719.Tropical cyclones (hurricanes) generate intense surface ocean cooling and vertical mixing resulting in nutrient upwelling into the photic zone and episodic phytoplankton blooms. However, their influence on the deep ocean remains unknown. Here we present evidence that hurricanes also impact the ocean's biological pump by enhancing export of labile organic material to the deep ocean. In October 2016, Category 3 Hurricane Nicole passed over the Bermuda Time Series site in the oligotrophic NW Atlantic Ocean. Following Nicole's passage, particulate fluxes of lipids diagnostic of fresh phytodetritus, zooplankton, and microbial biomass increased by 30–300% at 1,500 m depth and 30–800% at 3,200 m depth. Mesopelagic suspended particles following Nicole were also enriched in phytodetrital material and in zooplankton and bacteria lipids, indicating particle disaggregation and a deepwater ecosystem response. Predicted climate‐induced increases in hurricane frequency and/or intensity may significantly alter ocean biogeochemical cycles by increasing the strength of the biological pump.This work and the Oceanic Flux Program time series were supported by the National Science Foundation Chemical Oceanography Program Grant OCE 1536644. The Bermuda Atlantic Time Series and Hydrostation S time series were supported by NSF Grants OCE 1756105 and OCE 1633125, respectively. We acknowledge the contributions of BATS technicians with CTD and pigment analyses. We sincerely thank the officers and crew of R/V Atlantic Explorer (Bermuda Institute of Ocean Sciences) for their expert assistance on the cruises. The data used in this study are listed in the figures, tables, and references, and are also available in the NSF's Biological and Chemical Oceanography Data Management Office (BCO‐DMO, https://doi.org/10.1575/1912/bco‐dmo.775902.1).2020-02-1

Sugars as source indicators of biogenic organic carbon in aerosols collected above the Howland Experimental Forest, Maine

Author Posting. © The Authors, 2005. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Atmospheric Environment 40 (2006): 1694-1705, doi:10.1016/j.atmosenv.2005.11.001.Bulk aerosols (> 1 μm) were collected continuously above the canopy at the Howland Experimental Forest, Maine, USA from May to October 2002. Each sample integrated over an approximately two-week period. Mono- and disaccharide sugars were extracted using a microscale technique and were analyzed as their TMS derivatives by GC-MS. Concentrations of total aerosol sugars ranged from 10 to 180 ng m-3. Glucose was the most abundant sugar (40-75% of the total sugars). The monosaccharides arabinose, fructose, galactose, mannose, arabitol and mannitol, and the disaccharides sucrose, maltose and mycose (aka trehalose) were also present in lower concentrations. The sugar composition in the aerosols varied seasonally. Fructose and sucrose were prevalent in early spring and decreased in relative abundance as the growing season progressed. Sugar polyols (arabitol and mannitol) and the disaccharide mycose (a fungal metabolite) were more prevalent in autumn during the period of leaf senescence. The changes in the sugar composition in the aerosol samples appear to reflect the seasonality of sugar production and utilization by the ecosystem. Plant waxes were present as significant components also indicating an input from biogenic background. Smoke plumes from Quebec forest fires passed over the Howland site in early July 2002. Levoglucosan, a biomarker of biomass burning, increased by an order of magnitude in the aerosol samples collected during this time. Glucose, mannose, arabinose, galactose, and also, plant waxes increased in concentration by factors of 2-5 in the smoke-impacted samples, indicating that wildfires enhance atmospheric emissions of uncombusted organic compounds. In contrast, concentrations of fructose, sugar polyols and disaccharides were not significantly higher in the smoke-impacted samples and indicated that biomass burning was not a significant source of these compounds in the aerosols.This work was funded by a grant to MHC (DOE-NIGEC Grant 15460100) from the U.S. Department of Energy’s (DOE) National Institute for Global Environmental Change (NIGEC), through the NIGEC Northeast Regional Center at Harvard University

Molecular Nature of Marine Particulate Organic Iron-Carrying Moieties Revealed by Electrospray Ionization Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (ESI-FTICRMS)

Marine sinking particulate organic matter (POM), acting as a link between surface primary production and burial of organic matter in marine sediments, undergoes a variety of physical and biochemical alterations on its way to the deep ocean, resulting in an increase in its un-characterizable proportion with diagenesis. Further, the binding ligands in POM for iron, an essential nutrient to marine life and tightly coupled with organic matter, has rarely been studied. In the current study, we employed an approach combining sequential extraction with ultrahigh resolution mass spectrometry (ESI-FTICRMS), in order to explore and unravel the chemical characteristics of organic matter compounds relevant to marine particle flux within the mesopelagic and deep ocean, with a focus on the potential iron-carrying molecules. With increasing depth, POM increases in aliphaticity, and decreases in intensity-normalized O/C ratios, aromatics, and carboxylic-rich alicyclic molecules (CRAM)-like compounds. The potential iron-carrying molecules account for ∼14% of total identified molecules, and appear to have been incorporated into the marine particles via ion complexation, hydrophobic interaction, and/or interlayered “occlusion.” The relative abundance of iron-binding organic molecules in these three operationally-defined categories changes with depth: “surficially-complexed” fraction decreases with depth, the “interlayered-occluded” fraction increases to a comparable extent and “hydrophobic interaction” fraction occurs at all depths. Collectively, the potential iron-carrying organic molecules exhibit a set of unique molecular characteristics: a relatively lower average H/C ratio and a higher O/C ratio compared to bulk POM, a dominance of aromatics, black carbon-like compounds and CRAM-like compounds, and minor amounts of aliphatics. These molecules exhibit partial similar molecular features as precursors formed from photochemical reactions in the surface ocean, but they have been greatly modified by flux processes. Noticeably, a minor fraction of these iron-carrying molecules

Calibration of Mg/Ca thermometry in planktonic foraminifera from a sediment trap time series

Paired Mg/Ca and δ18O measurements on planktonic foraminiferal species (G. ruber white, G. ruber pink, G. sacculifer, G. conglobatus, G. aequilateralis, O. universa, N. dutertrei, P. obliquiloculata, G. inflata, G. truncatulinoides, G. hirsuta, and G. crassaformis) from a 6-year sediment trap time series in the Sargasso Sea were used to define the sensitivity of foraminiferal Mg/Ca to calcification temperature. Habitat depths and calcification temperatures were estimated from comparison of δ18O of foraminifera with equilibrium calcite, based on historical temperature and salinity data. When considered together, Mg/Ca (mmol/mol) of all species, except two, show a significant (r = 0.93) relationship with temperature (T °C) of the form Mg/Ca = 0.38 (±0.02) exp 0.090 (±0.003)T, equivalent to a 9.0 ± 0.3% change in Mg/Ca for a 1°C change in temperature. Small differences exist in calibrations between species and between different size fractions of the same species. O. universa and G. aequilateralis have higher Mg/Ca than other species, and in general, data can be best described with the same temperature sensitivity for all species and pre-exponential constants in the sequence O. universa > G. aequilateralis ≈ G. bulloides > G. ruber ≈ G. sacculifer ≈ other species. This approach gives an accuracy of ±1.2°C in the estimation of calcification temperature. The ∼9% sensitivity to temperature is similar to published studies from culture and core top calibrations, but differences exist from some literature values of pre-exponential constants. Different cleaning methodologies and artefacts of core top dissolution are probably implicated, and perhaps environmental factors yet understood. Planktonic foraminiferal Mg/Ca temperature estimates can be used for reconstructing surface temperatures and mixed and thermocline temperatures (using G. ruber pink, G. ruber white, G. sacculifer, N. dutertrei, P. obliquiloculata, etc.). The existence of a single Mg thermometry equation is valuable for extinct species, although use of species-specific equations will, where statistically significant, provide more accurate evaluation of Mg/Ca paleotemperature

Global temperature calibration of the alkenone unsaturation index (UK′37) in surface waters and comparison with surface sediments

Author Posting. © American Geophysical Union, 2006. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 7 (2006): Q02005, doi:10.1029/2005GC001054.In this paper, we compile the current surface seawater C37 alkenone unsaturation (UK′37) measurements (n=629, −1 to 30°C temperature range) to derive a global, field-based calibration of UK′37 with alkenone production temperature. A single nonlinear “global” surface water calibration of UK′37 accurately predicts alkenone production temperatures over the diversity of modern-day oceanic environments and alkenone-synthesizing populations (T=−0.957 + 54.293(UK′37) − 52.894(UK′37)2 + 28.321(UK′37)3, r2=0.97, n=567). The mean standard error of estimation is 1.2°C with insignificant bias in estimated production temperature among the different ocean regions sampled. An exception to these trends is regions characterized by strong lateral advection and extreme productivity and temperature gradients (e.g., the Brazil-Malvinas Confluence). In contrast to the surface water data, the calibration of UK′37 in surface sediments with overlying annual mean sea surface temperature (AnnO) is best fit by a linear model (AnnO=29.876(UK′37) − 1.334, r2=0.97, n=592). The standard error of estimation (1.1°C) is similar to that of the surface water production calibration, but a higher degree of bias is observed among the regional data sets. The sediment calibration differs significantly from the surface water calibration. UK′37 in surface sediments is consistently higher than that predicted from AnnO and the surface water production temperature calibration, and the magnitude of the offset increases as the surface water AnnO decreases. We apply the global production temperature calibration to the coretop UK′37 data to estimate the coretop alkenone integrated production temperature (coretop IPT) and compare this with the overlying annual mean sea surface temperature (AnnO). We use simple models to explore the possible causes of the deviation observed between the coretop temperature signal, as estimated by UK′37, and AnnO. Our results indicate that the deviation can best be explained if seasonality in production and/or thermocline production as well as differential degradation of 37:3 and 37:2 alkenones both affect the sedimentary alkenone signal.C.R. acknowledges funding from the Deutsche Forschungsgemeinschaft (DFG)

Calcification and growth processes in planktonic foraminifera complicate the use of B/Ca and U/Ca as carbonate chemistry proxies

Although boron and uranium to calcium ratios (B/Ca, U/Ca) in planktonic foraminifera have recently received much attention as potential proxies for ocean carbonate chemistry, the extent of a carbonate chemistry control on these ratios remains contentious. Here, we use bi-weekly sediment trap samples collected from the subtropical North Atlantic in combination with measured oceanographic data from the same location to evaluate the dominant oceanographic controls on B/Ca and U/Ca in three depth-stratified species of planktonic foraminifera. We also test the control of biological, growth-related, processes on planktonic foraminiferal B and U incorporation by using foraminifer test area density (μg/μm2) (a monitor of test thickness) and test size from the same samples. B/Ca and U/Ca show little or no significant correlation with carbonate system parameters both within this study and in comparison with other published works. We provide the first evidence for a strong positive relationship between area density (test thickness) and B/Ca, and reveal that this is consistent in all species studied, suggesting a likely role for calcification in controlling boron partitioning into foraminiferal calcite. This finding is consistent with previous observations of less efficient discrimination against trace element ‘impurities’ (such as B), at higher calcification rates. We observe little or no dependency of B/Ca on test size. In marked contrast, we find that U/Ca displays a strong species-specific dependency on test size in all species, but no relationship with test thickness, implicating some other biological control (possibly related to growth), rather than a calcification control, on U incorporation into foraminiferal calcite. Our results caution against the use of B/Ca and U/Ca in planktonic foraminifera as reliable proxies for the ocean carbonate system and recommend that future work should concentrate on improving the mechanistic understanding of how planktonic foraminifer calcification and growth rates regulate boron and uranium incorporation into the test