Particulate organic matter and ballast fluxes measured using time-series and settling velocity sediment traps in the northwestern Mediterranean Sea

Prompted by recent data analyses suggesting that the flux of particulate organic carbon sinking into deep waters is determined by fluxes of mineral ballasts, we undertook a study of the relationships among organic matter (OM), calcium carbonate, opal, lithogenic material, and excess aluminum fluxes as part of the MedFlux project. We measured fluxes of particulate components during Spring and Summer of 2003, and Spring of 2005, using a swimmer-excluding sediment trap design capable of measuring fluxes both in a time-series (TS) mode and in a configuration for obtaining particle settling velocity (SV) profiles. On the basis of these studies, we suggest that distinct OM–ballast associations observed in particles sinking at a depth of 200 m imply that the mechanistic basis of the organic matter–ballast association is set in the upper water column above the Twilight Zone, and that the importance of different ballast types follows the seasonal succession of phytoplankton. As in other studies, carbonate appears to enhance the flux of organic matter over opal. Particles must be at least half organic matter before their settling velocity is affected by ballast concentration. This lack of change in ballast composition with SV in particles with <40% OM content suggests that particle SV reaches a maximum because of the increasing importance of inertial drag. Relative amounts of OM and opal decrease with depth due to decomposition and dissolution; carbonates and lithogenic material contribute about the same amount to total mass, or increase slightly, throughout the water column. The high proportion of excess Al cannot be explained by its incorporation into diatom opal or reverse weathering, so Al is most likely adsorbed to particulate oxides. On shorter time scales, dust appears to increase particle flux through its role in aggregation rather than by nutrient inputs enhancing productivity. We suggest that the role of dust as a catalyst in particle formation may be a central mechanism in flux formation in this region, particularly when zooplankton fecal pellet production is low.     

Settling velocity spectra and the ballast ratio hypothesis

Recently it has been observed that a strong quantitative relationship exists between asymptotic fluxes of particulate organic carbon (POC) to the deep ocean and asymptotic fluxes of “ballast” minerals (opal; calcium carbonate; dust). It has further been suggested that this relationship might provide a mechanistic basis for improved representations of remineralization in ocean carbon models. Since the depth scale of remineralization z* is the ratio k/v of a remineralization rate k and a settling velocity (SV) v, a mechanistic understanding of settling velocities will be crucial in developing such models.Historically, there have been two approaches to estimating the speed with which POC is transported to the deep ocean. First, settling speeds of single particles have been observed directly in both field and laboratory settings; estimates of fecal pellet sinking velocities tend to be higher and more variable than those of aggregates. Second, estimates have been made of the velocity at which temporal patterns in flux propagate between pairs of sediment traps separated in depth (the “benchmark approach”); recent studies have shown these results to be variable and to depend on mineral ballasting. Here we present SV estimates using a relatively new technology: indented rotating sphere (IRS) sediment traps run in settling velocity (SV) mode. In this approach, particles are separated into SV classes during settling to collection cups. In MedFlux, SV data were collected concurrently with time-series (TS) data; the latter were used to construct benchmark estimates for comparison to the SV estimates. From the SV data, the range of modal settling velocities (sinking velocities having the largest time-averaged mass flux densities on a logarithmic scale of SV) in the fast-sinking fraction was estimated to be 287–503 m/d; the average of these modal values is 353 m/d, with standard deviation 76 m/d. In contrast, mean settling velocities of the fast-sinking fraction depend on the range of settling velocity classes included in the estimate. If only SV classes settling at >50 m/d are included, the range of SVs at MedFlux was 214–298 m/d, with average mean value 242 m/d and standard deviation 31 m/d. These mean-velocity results are in excellent agreement with benchmark estimates of signal propagation velocities at Medflux (220±65 m/d); they are also well within the range of other recent benchmark studies. The agreement between the benchmark estimates and mean settling velocity estimates at MedFlux, but not with modal velocities, argues that the benchmark method estimates mean settling velocities.     

The use of soft X-ray spectromicroscopy to investigate the distribution and composition of organic matter in a diatom frustule and a biomimetic analog

Diatoms play a significant role in the global carbon cycle through their role in biogenic silica production and the transport of organic matter to the seafloor. Recent work has shown that silicified diatom frustules contain a significant amount of organic matter, and that the proportion of diatom-bound organic matter increases with depth in the water column and sediments. Here, we investigate the association between organic matter and the mineral phase. We used a combination of scanning transmission X-ray microscopy (STXM) and carbon X-ray absorption near-edge structure (XANES) spectroscopy to characterize the distribution and composition of organic matter in frustules of the diatom Cylindrotheca closterium and a biomimetic silica gel. To our knowledge, this study represents the first successful attempt to simultaneously image and obtain chemical information about the organic matter within a diatom frustule using X-ray spectromicroscopy near the carbon edge. Organic carbon, most likely protein, was distributed throughout the frustules and was not removed by harsh chemical treatment. The physical structure of the frustules appeared to be related to the chemical composition of this organic matter, with aromatic or unsaturated carbon being concentrated in the most intricately patterned regions of the frustule. A similar physical and chemical structure was observed in a biomimetic silica gel precipitated spontaneously with polylysine. These results are consistent with the theory that organic constituents of diatom frustules direct silica precipitation and become incorporated within the silica matrix as it forms. The relationship between organic matter composition and silica morphology, the failure of harsh chemical treatments to remove this organic matter, and the spontaneous nature of the co-precipitation of silica and organic matter indicate some chemical interaction between the siliceous and organic components of diatom frustules. Frustule-bound organic matter should therefore be protected from decomposition in the water column or diagenetic alteration in sediments unless the frustule dissolves.     

The development of the Space Environment Viability of Organics (SEVO) experiment aboard the Organism/Organic Exposure to Orbital Stresses (O/OREOS) satellite

The Space Environment Viability of Organics (SEVO) experiment is one of two scientific payloads aboard the triple-cube satellite Organism/ORganic Exposure to Orbital Stresses (O/OREOS). O/OREOS is the first technology demonstration mission of the NASA Astrobiology Small Payloads Program. The 1-kg, 1000-cm³ SEVO cube is investigating the chemical evolution of organic materials in interstellar space and planetary environments by exposing organic molecules under controlled conditions directly to the low-Earth orbit (LEO) particle and electromagnetic radiation environment. O/OREOS was launched on November 19, 2010 into a 650-km, 72°-inclination orbit and has a nominal operational lifetime of six months. Four classes of organic compounds, namely an amino acid, a quinone, a polycyclic aromatic hydrocarbon (PAH), and a metallo-porphyrin are being studied. Initial reaction conditions were established by hermetically sealing the thin-film organic samples in self-contained micro-environments. Chemical changes in the samples caused by direct exposure to LEO radiation and by interactions with the irradiated microenvironments are monitored in situ by ultraviolet/visible/near-infrared (UV/VIS/NIR) absorption spectroscopy using a novel compact fixed-grating CCD spectrometer with the Sun as its light source. The goals of the O/OREOS mission include: (1) demonstrating key small satellite technologies that can enable future low-cost astrobiology experiments, (2) deploying a miniature UV/VIS/NIR spectrometer suitable for in-situ astrobiology and other scientific investigations, (3) testing the capability to establish a variety of experimental reaction conditions to enable the study of astrobiological processes on small satellites, and (4) measuring the chemical evolution of organic molecules in LEO under conditions that can be extrapolated to interstellar and planetary environments. In this paper, the science and technology development of the SEVO instrument payload and its measurements are described.     

Vertex-centred discretization of multiphase compositional Darcy flows on general meshes

This paper concerns the discretisation on general 3D meshes of multiphase compositional Darcy flows in heterogeneous anisotropic porous media. Extending Coats’ formulation [15] to an arbitrary number of phases, the model accounts for the coupling of the mass balance of each component with the pore volume conservation and the thermodynamical equilibrium and dynamically manages phase appearance and disappearance. The spatial discretisation of the multiphase compositional Darcy flows is based on a generalisation of the Vertex Approximate Gradient scheme, already introduced for single-phase diffusive problems in [24]. It leads to an unconditionally coercive scheme for arbitrary meshes and permeability tensors. The stencil of this vertex-centred scheme typically comprises 27 points on topologically Cartesian meshes, and the number of unknowns on tetrahedral meshes is considerably reduced, compared with the usual cell-centred approaches. The efficiency of our approach is exhibited on several examples, including the nearwell injection of miscible CO₂ in a saline aquifer taking into account the vaporisation of H₂O in the gas phase as well as the precipitation of salt.     

Influence of Shoreline Stabilization Structures on the Nearshore Sedimentary Environment in Mesohaline Chesapeake Bay

Shorelines around many estuaries and coastal embayments are rapidly eroding (approximately several meters/year), with more rapid erosion rates expected in the future due to natural and anthropogenic stressors. In response, a variety of techniques have been used to stabilize shorelines, but there are limited quantitative, long-term data available about their effects on the sedimentary environment immediately adjacent to them (i.e., the nearshore). This study evaluated changes in sediment characteristics (mud and organic content) and accumulation rates associated with installation of breakwaters, riprap, and living shorelines with (“hybrid”) and without (“soft”) a structural component. ²¹⁰Pb (half-life 22.3 years) geochronologies were used to identify horizons in core profiles that corresponded to years when structures were built. Sites with naturally eroding shorelines (i.e., no structures) were used as a control group at which any sedimentary changes represent broad environmental trends, in contrast to changes at the protected sites that also include the influence of structures. Observations were placed within the context of modeled wave climate, shoreline-erosion rates, land use, dominant sediment source, and the apparent effect on submersed aquatic vegetation (SAV) inhabiting the nearshore sedimentary environment. The main conclusion of this study is that there was no “one size fits all” answer to anticipated impacts of structures on nearshore sedimentary environments. Instead, specific changes associated with structures depended on individual site characteristics, but could be predicted with multiple linear regression models that included structure type, shoreline-erosion rate, dominant sediment source, and land use. Riprap or breakwater installation had either positive or no obvious impact on SAV at six of seven sites but negatively impacted SAV at one riprapped site. No obvious impacts on SAV were observed at living shoreline sites.     

Characterization of sinking particles from the northwest Mediterranean Sea using advanced solid-state NMR

Sinking particles are the major transporter of organic carbon from surface to the deep ocean, and their chemical composition changes dramatically with depth. However, the exact mechanism controlling the chemical transformation as particles sink is not well understood, and little detail is known about the structural changes. This is mainly due to the paucity of techniques available to analyze the major macromolecular components of sinking particles. Here we applied advanced solid-state NMR techniques, including cross polarization/magic angle spinning (CPMAS), direct polarization/magic angle spinning (DPMAS), two-dimensional ¹H-¹³C heteronuclear correlation (2D HETCOR) and ¹H T₁ inversion recovery, on sinking particles collected in the northwest Mediterranean Sea. The CPMAS ¹³C NMR spectrum of the 200-m particles is significantly different from that of the DPMAS ¹³C NMR spectrum: CPMAS overestimates the NCH and CHO groups, but underestimates the aliphatic components, which is attributed to the high mobility of polymethylene units. Thus DPMAS is more suitable for quantifying organic composition of sinking particles. Using 2D HETCOR with ¹H spin diffusion, we estimated that the size of domains (similar structural entities either physically or chemically grouped together) in the 200-m sinking particles can be as large as tens of nanometers. The results of CPMAS ¹³C NMR and ¹H inversion recovery on sinking particles from 200, 520 and 920 m indicate that the macromolecular heterogeneity observed in surface particles virtually disappears as particles sink into the deep ocean. This suggests that the macromolecular components at depth are different in structural composition than those in surface waters, and may be compositionally homogenized as particles sink.     

Sterol diagenesis in Recent sediments from Buzzards Bay,Massachusetts

Sections of a 42 cm core from one area and surface sediments from two other areas of Buzzards Bay, Massachusetts were analyzed for sterols. The distribution of sterols in surface sediments appears to be influenced by benthic faunal composition or factors controlling this composition. A comparison of sterols extracted by Soxhlet-extraction with sterols extracted after subsequent saponification of the sediment showed that the former sterols decrease in concentration while the latter saponified sterols increase in concentration with depth. In both fractions, the individual sterol compositions are similar. A transformation between Soxhlet-extractable and non-Soxhlet-extractable saponified sterols appears to be occurring over the 130 yrs sampled by the core. This transformation is probably due to chemical/physical processes rather than biological processes. Comparison with fatty acid data shows that early diagenesis of sterols is slower than early diagenesis of fatty acids.     

Loss and recycling of amino acids and protein from smooth cordgrass (Spartina alterniflora) litter

We investigated the source and composition of free and protein-bound amino acids during the decomposition ofSpartina alterniflora Loisel in laboratory percolators and in a field experiment in the Great Sippewissett Marsh (Falmouth, Massachusetts). In the percolator experiment, 50% of the nitrogen (N) could be extracted fromS. alterniflora litter in 16 d. This extract consisted of dissolved free amino acid N (28%), suspended protein amino acid N (16%), inorganic N (12%), and nitrogen from unidentified compounds (44%). Much of the free amino acid nitrogen was utilized by detrital microorganisms, resulting in a greater loss of suspended protein amino acid (SPAA) nitrogen from the biologically active percolator due to microbials biomass. Suspended microbial mass accounted for at least 50% of the SPAA washed out of the biologically active percolator. In the field study, 38% of the original litter nitrogen was leached fromS. alterniflora litter in litterbags during the first 13 d. After this initial leaching period, the concentration (41% to 69% of total nitrogen) and composition of most amino acids bound in the litter did not change over the 23-month period of the experiment. Increases in microbial protein did not account for increases in total nitrogen which occurred during the decomposition of the litter. Similarly, adsorbed ammonium did not appear to be responsible for this increase.