Dissolved organic matter molecular composition and concentrations from a large scale mesocosm study KOSMOS 2013 Kristineberg) on ocean acidification

Marine dissolved organic matter (DOM) represents one of the largest active carbon reservoirs on Earth. Changes in pool size or composition could have major impacts on the global carbon cycle. Ocean acidification is a potential driver for these changes because it influences marine primary production and heterotrophic respiration. Here we show that ocean acidification as expected for a 'business-as-usual' emission scenario in the year 2100 (900 µatm) does not affect the DOM pool with respect to its size and molecular composition. We applied ultrahigh-resolution mass spectrometry to monitor the production and turnover of 7,360 distinct molecular DOM features in an unprecedented long-term mesocosm study in a Swedish Fjord, covering a full cycle of marine production. DOM concentration and molecular composition did not differ significantly between present-day and year 2100 CO2 levels. Our findings are likely applicable to other coastal and productive marine ecosystems in general.

Molecular composition in surface and subsurface sediments of the Helgoland mud area, North Sea

The role of microorganisms in the cycling of sedimentary organic carbon is a crucial one. To better understand relationships between molecular composition of a potentially bioavailable fraction of organic matter and microbial populations, bacterial and archaeal communities were characterized using pyrosequencing-based 16S rRNA gene analysis in surface (top 30 cm) and subsurface/deeper sediments (30-530 cm) of the Helgoland mud area, North Sea. Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) was used to characterize a potentially bioavailable organic matter fraction (hot-water extractable organic matter, WE-OM). Algal polymer-associated microbial populations such as members of the Gammaproteobacteria, Bacteroidetes, and Verrucomicrobia were dominant in surface sediments while members of the Chloroflexi (Dehalococcoidales and candidate order GIF9) and Miscellaneous Crenarchaeota Groups (MCG), both of which are linked to degradation of more recalcitrant, aromatic compounds and detrital proteins, were dominant in subsurface sediments. Microbial populations dominant in subsurface sediments (Chloroflexi, members of MCG, and Thermoplasmata) showed strong correlations to total organic carbon (TOC) content. Changes of WE-OM with sediment depth reveal molecular transformations from oxygen-rich [high oxygen to carbon (O/C), low hydrogen to carbon (H/C) ratios] aromatic compounds and highly unsaturated compounds toward compounds with lower O/C and higher H/C ratios. The observed molecular changes were most pronounced in organic compounds containing only CHO atoms. Our data thus, highlights classes of sedimentary organic compounds that may serve as microbial energy sources in methanic marine subsurface environments.

Light absorption and phytoplankton biomass in the Black Sea in spring 1995

Spectra of light absorption by suspended matter, phytoplankton, and detritus in the central and coastal parts of the Black Sea over the spring period (March-April 1995) were determined. Vertical homogeneity of the upper 40 m layer with respect to parameters in study was noted. Value of light absorption by phytoplankton normalized with respect to chlorophyll a was virtually independent of chlorophyll a concentration. A linear relationship between light absorption by phytoplankton and chlorophyll a concentration was established at the red spectral maximum. It is described by the equation y = 0.0153x; R**2 = 0.61. The average ratio of absorption values in the peaks was 2.29. Contribution of detritus to total light absorption at wavelength 440 nm was 23-62% regardless of depth and chlorophyll a concentration.

Phytoplankton pigments and biomass in the northeastern Sea of Okhotsk from March 23 to April 14, 1998

Studies were carried out in the northeastern Sea of Okhotsk, in the zone of interaction of the West Kamchatka and Compensating Currents at the beginning of spring seasonal succession from March 23 to April 14,1998. Samples for analysis of pigmentary and species compositions of phytoplankton were taken from the sea surface layer, depth 0.5 m. To reduce influence of micropatchiness on phytoplankon distribution at each station subsamples 0.7-1 l were collected every 50-100 m. These subsamples were used to make integral samples 4.5-8.0 l. Phytoplankton biomass and concentration of chlorophyll a varied from 18.7 to 490.9 mg/m**3 and from 0.129 to 2.422 mg/m**3, respectively. Total concentration of phytoplankton pigments varied from 0.622 to 6.679 mg/m**3. In samples studied 51 species of microalgae from 5 orders were found. In terms of the number of species, Bacillariophyta (31 species) and Dinophyta (15 species) prevailed. Diatomaceous algae make up more than 80% of the total phytoplankton biomass in waters of the Compensating Current, from 50 to 80% in intermediate waters, and less than 50% in waters of the West Kamchatka Current. Phytoplankton populations consisting primarily of diatoms were characterized by very low chlorophyll a to biomass ratio (0.1 %). It is three times lower than the ratio observed in phytoplankton populations that were close by species composition and size composition in this area in the late April-early May 1996.

Porphyrin geochemistry of DSDP Hole 71-511

Late Jurassic-early Cretaceous black shales and an overlying sequence of Albian-Campanian zeolitic claystones from the Falkland Plateau (DSDP/IPOD Leg 71, Site 511) were analyzed for tetrapyrrole pigment type and abundance. The "black shale" sequence was found to be rich in DPEP-series dominated free-base, nickel (Ni) and, to a lesser extent, vanadyl (V = 0) porphyrins. A low level of organic maturity (i.e. precatagenesis) is indicated for these strata as nickel chelation by free-base porphyrins is only 50-75% complete, proceeding down-hole to 627 meters sub-bottom. Electronic and mass spectral data reveal that the proposed benzo-DPEP (BD) and tetrahydrobenzo-DPEP (THBD) series are present in the free-base and Ni species, as well as the more usual occurrence in V = 0 porphyrin arrays. Highly reducing conditions are suggested by an abundance of the PAH perylene, substantial amounts of the THBD/BD series and a redox equilibrium between free-base DPEP and 7,8-dihydro-DPEP series, which exist in a 7:1 molar ratio. The Albian-Campanian claystone strata were found to be tetrapyrrolepoor, and those pigments present were typed as Cu/Ni highly dealkylated (C26 max.) etioporphyrins, thought to be derived via redeposition and oxidation of terrestrial organic matter (OM). Results from the present study are correlated to our past analyses of Jurassic-Cretaceous sediments from Atlantic margins in an effort to relate tetrapyrrole quality and quantity to basin evolution and OM sources in the proto-Atlantic.

Mineralogical, geochemical, and lipid biomarker study of cabonate precipitates at station GeoB9908-1

Carbonate precipitates recovered from 2,000 m water depth at the Dolgovskoy Mound (Shatsky Ridge, north eastern Black Sea) were studied using mineralogical, geochemical and lipid biomarker analyses. The carbonates differ in shape from simple pavements to cavernous structures with thick microbial mats attached to their lower side and within cavities. Low d13C values measured on carbonates (-41 to -32 per mill V-PDB) and extracted lipid biomarkers indicate that anaerobic oxidation of methane (AOM) played a crucial role in precipitating these carbonates. The internal structure of the carbonates is dominated by finely laminated coccolith ooze and homogeneous clay layers, both cemented by micritic high-magnesium calcite (HMC), and pure, botryoidal, yellowish low-magnesium calcite (LMC) grown in direct contact to microbial mats. d18O measurements suggest that the authigenic HMC precipitated in equilibrium with the Black Sea bottom water while the yellowish LMC rims have been growing in slightly 18O-depleted interstitial water. Although precipitated under significantly different environmental conditions, especially with respect to methane availability, all analysed carbonate samples show lipid patterns that are typical for ANME-1 dominated AOM consortia, in the case of the HMC samples with significant contributions of allochthonous components of marine and terrestrial origin, reflecting the hemipelagic nature of the primary sediment.

Global macrozoobenthos production and energy budget data base V150731, with link to database

I developed a new model for estimating annual production-to-biomass ratio P/B and production P of macrobenthic populations in marine and freshwater habitats. Self-learning artificial neural networks (ANN) were used to model the relationships between P/B and twenty easy-to-measure abiotic and biotic parameters in 1252 data sets of population production. Based on log-transformed data, the final predictive model estimates log(P/B) with reasonable accuracy and precision (r2 = 0.801; residual mean square RMS = 0.083). Body mass and water temperature contributed most to the explanatory power of the model. However, as with all least squares models using nonlinearly transformed data, back-transformation to natural scale introduces a bias in the model predictions, i.e., an underestimation of P/B (and P). When estimating production of assemblages of populations by adding up population estimates, accuracy decreases but precision increases with the number of populations in the assemblage.

A Late Pleistocene sea level stack

Late Pleistocene sea level has been reconstructed from ocean sediment core data using a wide variety of proxies and models. However, the accuracy of individual reconstructions is limited by measurement error, local variations in salinity and temperature, and assumptions particular to each technique. Here we present a sea level stack (average) which increases the signal-to-noise ratio of individual reconstructions. Specifically, we perform principal component analysis (PCA) on seven records from 0-430 ka and five records from 0-798 ka. The first principal component, which we use as the stack, describes ~80 % of the variance in the data and is similar using either five or seven records. After scaling the stack based on Holocene and Last Glacial Maximum (LGM) sea level estimates, the stack agrees to within 5 m with isostatically adjusted coral sea level estimates for Marine Isotope Stages 5e and 11 (125 and 400 ka, respectively). When we compare the sea level stack with the d18O of benthic foraminifera, we find that sea level change accounts for about ~40 % of the total orbital-band variance in benthic d18O, compared to a 65 % contribution during the LGM-to-Holocene transition. Additionally, the second and third principal components of our analyses reflect differences between proxy records associated with spatial variations in the d18O of seawater.

Sedimentology and geochemistry of ODP Leg 129 siliceous deposits

Siliceous deposits drilled on Ocean Drilling Program Leg 129 accumulated within a few degrees of the equator during the Jurassic through early Tertiary, as constrained by paleomagnetic data. During the Jurassic and Early Cretaceous, radiolarian ooze, mixed with a minor amount of pelagic clay, was deposited near the equator, and overall accumulation rates were moderate to low. At a smaller scale, in more detail, periods of relatively higher accumulation rates alternated with periods of very low accumulation rates. Higher rates are represented by radiolarite and limestone; lower rates are represented by radiolarian claystone. Our limited data from Leg 129 suggests that accumulation of biogenic deposits was not symmetrical about the equator or consistent over time. In the Jurassic, sedimentation was siliceous; in the Cretaceous there was significant calcareous deposition; in the Tertiary claystone indicates significantly lower accumulation rates at least the northern part of the equatorial zone. Accumulation rates for Leg 129 deposits in the Cretaceous were higher in the southern part of the equatorial zone than in the northern part, and the southern side of this high productivity zone extended to approximately 15°S, while the northern side extended only to about 5°N. Accumulation rates are influenced by relative contributions from various sediment sources. Several elements and element ratios are useful for discriminating sedimentary sources for the equatorial depositional environments. Silica partitioning calculations indicate that silica is dominantly of biogenic origin, with a detrital component in the volcaniclastic turbidite units, and a small hydrothermal component in the basal sediments on spreading ridge basement of Jurassic age at Site 801. Iron in Leg 129 sediments is dominantly of detrital origin, highest in the volcaniclastic units, with a minor hydrothermal component in the basal sediments at Site 801. Manganese concentrations are highest in the units with the lowest accumulation rates. Fe/Mn ratios are >3 in all units, indicating negligible hydrothermal influence. Magnesium and aluminum concentrations are highest in the volcaniclastic units and in the basal sediments at Site 801. Phosphorous is very low in abundance and may be detrital, derived from fish parts. Boron is virtually absent, as is typical of deep-water deposits. Rare earth element concentrations are slightly higher in the volcaniclastic deposits, suggesting a detrital source, and lower in the rest of the lithologic units. Rare earth element abundances are also low relative to "average shale." Rare earth element patterns indicate all samples are light rare earth element enriched. Siliceous deposits in the volcaniclastic units have patterns which lack a cerium anomaly, suggesting some input of rare earth elements from a detrital source; most other units have a distinct negative Ce anomaly similar to seawater, suggesting a seawater source, through adsorption either onto biogenic tests or incorporation into authigenic minerals for Ce in these units. The Al/(Al + Fe + Mn) ratio indicates that there is some detrital component in all the units sampled. This ratio plotted against Fe/Ti shows that all samples plot near the detrital and basalt end-members, except for the basal samples from Site 801, which show a clear trend toward the hydrothermal end-member. The results of these plots and the association of high Fe with high Mg and Al indicate the detrital component is dominantly volcaniclastic, but the presence of potassium in some samples suggests some terrigenous material may also be present, most likely in the form of eolian clay. On Al-Fe-Mn ternary plots, samples from all three sites show a trend from biogenic ooze at the top of the section downhole to oceanic basalt. On Si-Fe-Mn ternary plots, the samples from all three sites fall on a trend between equatorial mid-ocean spreading ridges and north Pacific red clay. Copper-barium ratios show units that have low accumulation rates plot in the authigenic field, and radiolarite and limestone samples that have high accumulation rates fall in the biogenic field.

Biogeochemistry and microbiology of groundwater during acetate and bicarbonate amendment to an alluvial aquifer

These data are from a field experiment conducted in a shallow alluvial aquifer along the Colorado River in Rifle, Colorado, USA. In this experiment, bicarbonate-promoted uranium desorption and acetate amendment were combined and compared to an acetate amendment-only experiment in the same experimental plot. Data include names and location data for boreholes, geochemical data for all the boreholes between June 1, 2010 and January 1, 2011, microarray data provided as signal to noise ratio (SNR) for individual microarray probes, microarray data provided as signal to noise ratio (SNR) by Genus.

(Table 1) Elemental composition of benthic foraminifera from South Atlantic core top samples

The ocean plays a major role in the global carbon cycle, and attempts to reconstruct past changes in the marine carbonate system are increasing. The speciation of dissolved uranium is sensitive to variations in carbonate system parameters, and previous studies have shown that this is recorded in the uranium-to-calcium ratio (U/Ca) of the calcite shells of planktonic foraminifera. Here we test whether U/Ca ratios of deep-sea benthic foraminifera are equally suited as an indicator of the carbonate system. We compare U/Ca in two common benthic foraminifer species (Planulina wuellerstorfi and Cibicidoides mundulus) from South Atlantic core top samples with the calcite saturation state (Delta [CO3**2-] = [CO3**2-]in situ - [CO3**2-]sat) of the ambient seawater and find significant negative correlations for both species. Compared with planktonic foraminifera, the sensitivity of U/Ca in benthic foraminifera to changes in Delta [CO3**2-] is about 1 order of magnitude higher. Although Delta [CO3**2-] exerts the dominant control on the average foraminiferal U/Ca, the intertest and intratest variability indicates the presence of additional factors forcing U/Ca.

Dissolved organic matter composition derived from FT-ICR-MS analyses during HEINCKE cruise HE361

Dissolved organic matter (DOM) is the main substrate and energy source for heterotrophic bacterioplankton. To understand the interactions between DOM and the bacterial community (BC), it is important to identify the key factors on both sides in detail, chemically distinct moieties in DOM and the various bacterial taxa. Next-generation sequencing facilitates the classification of millions of reads of environmental DNA and RNA amplicons and ultrahigh-resolution mass spectrometry yields up to 10,000 DOM molecular formulae in a marine water sample. Linking this detailed biological and chemical information is a crucial first step toward a mechanistic understanding of the role of microorganisms in the marine carbon cycle. In this study, we interpreted the complex microbiological and molecular information via a novel combination of multivariate statistics. We were able to reveal distinct relationships between the key factors of organic matter cycling along a latitudinal transect across the North Sea. Total BC and DOM composition were mainly driven by mixing of distinct water masses and presumably retain their respective terrigenous imprint on similar timescales on their way through the North Sea. The active microbial community, however, was rather influenced by local events and correlated with specific DOM molecular formulae indicative of compounds that are easily degradable. These trends were most pronounced on the highest resolved level, that is, operationally defined 'species', reflecting the functional diversity of microorganisms at high taxonomic resolution.