Molecular dissolved organic matter composition in lakes across Sweden as relative intensities of FT-ICR-MS peaks and PARAFAC components and optical indices

Whether intrinsic molecular properties or extrinsic factors such as environmental conditions control the decomposition of natural organic matter across soil, marine and freshwater systems has been subject to debate. Comprehensive evaluations of the controls that molecular structure exerts on organic matter's persistence in the environment have been precluded by organic matter's extreme complexity. Here we examine dissolved organic matter from 109 Swedish lakes using ultrahigh-resolution mass spectrometry and optical spectroscopy to investigate the constraints on its persistence in the environment. We find that degradation processes preferentially remove oxidized, aromatic compounds, whereas reduced, aliphatic and N-containing compounds are either resistant to degradation or tightly cycled and thus persist in aquatic systems. The patterns we observe for individual molecules are consistent with our measurements of emergent bulk characteristics of organic matter at wide geographic and temporal scales, as reflected by optical properties. We conclude that intrinsic molecular properties are an important control of overall organic matter reactivity.

Geochemistry of sediments from the Eastern Cape Basin

Sediment cores retrieved in the Benguela coastal upwelling system off Namibia show very distinct enrichments of solid phase barium at the sulfate/methane transition (SMT). These barium peaks represent diagenetic barite (BaSO4) fronts which form by the reaction of upwardly diffusing barium with interstitial sulfate. Calculated times needed to produce these barium enrichments indicate a formation time of about 14,000 yr. Barium spikes a few meters below the SMT were observed at one of the investigated sites (GeoB 8455). Although this sulfate-depleted zone is undersaturated with respect to barite, the dominant mineral phase of these buried barium enrichments was identified as barite by scanning electron microscopy (SEM). This is the first study which reports the occurrence/preservation of pronounced barite enrichments in sulfate-depleted sediments buried a few meters below the SMT. At site GeoB 8455 high concentrations of dissolved barium in pore water as well as barium in the solid phase were observed. Modeling the measured barium concentrations at site GeoB 8455 applying the numerical model CoTReM reveals that the dissolution rate of barite directly below the SMT is about one order of magnitude higher than at the barium enrichments deeper in the sediment core. This indicates that the dissolution of barite at these deeper buried fronts must be retarded. Thus, the occurrence of the enrichments in solid phase barium at site GeoB 8455 could be explained by decreased dissolution rates of barite due to the changes in the concentration of barite in the sediment, as well as changes in the saturation state of fluids. Furthermore, the alteration of barite into witherite (BaCO3) via the transient phase barium sulfide could lead to the preservation of a former barite front as BaCO3. The calculations and modeling indicate that a relocation of the barite front to a shallower depth occurred between the last glacial maxium (LGM) and the Pleistocene/Holocene transition. We suggest that an upward shift of the SMT occurred at that time, most likely as a result of an increase in the methanogenesis rates due to the burial of high amounts of organic matter below the SMT.

Terrestrial organic matter in marine sediments of the Central Equatorial Atlantic

Terrestrial organic matter (OM) in pelagic sediments is discussed with regard to depositional processes and land-sea interactions in the modern and past glacial/interglacial Equatorial Atlantic. Special emphasis is placed on a critical evaluation of different analytical approaches (C/N, Rock-Eval Pyrolysis, stable carbon isotopes, palynology, organic petrology, and selected biomarkers) which are currently used for the qualitative and quantitative assessment of terrigenous organic carbon. If binary mixing equations are used to calculate terrestrial and marine proportions of organic carbon, we consider the definition of endmember values to be most critical since these values may be biased by a great number of independent controls. A combination of geochemical methods including optical studies (organic petrology and palynology) is therefore suggested to evaluate each individual proxy. Organic geochemical analyses performed on sediments from the modern and Late Quaternary Equatorial Atlantic evidence fluctuations in eolian supply of terrigenous OM related to changes in intensity of the trade winds. Quantification of this organic fraction leads to differing proportions depending on the approach applied, i.e. the organic carbon isotopic composition or maceral analyses. Modern distribution of terrigenous OM reveals a decrease in supply towards the basin contributing less than a fifth of the total OM in pelagic areas. Organic geochemical data indicate that sedimentation in the modern northeastern Brasil Basin is affected by lateral advection of reworked OM probably from southern source areas. Glacial/interglacial deposits from the pelagic Equatorial Atlantic (ODP Site 663), covering isotopic stages 12 and 11, reveal that deposition of terrigenous OM was higher under past glacial conditions, in correspondence to generally enhanced dust fluxes. Proportions of terrigenous OM, however, never exceed 50% of the total OM according to maceral analyses. Other estimates, recently proposed by Verardo and Ruddiman (1996), are considered to be too high probably for analytical reasons. Palynological records in the Equatorial Atlantic parallel dust records. Increased portions of grass pollen suggest the admixture of C4-plant material under modern and past glacial conditions. It is therefore assumed, as one possible interpetation, that C4-plant debris has an effect on sedimentary d13Corg and might explain differences between isotopic and microscopic quantitative estimates. Using the difference between these two records, we calculate that maximum supply of C4-material remains below 20% of the total OM for the deep modern and past glacial/interglacial Equatorial Atlantic.

Particle camera and settling chamber measurements at site PC (GeoB11834-3) and SC (GeoB12914-4) off Cape Blanc/Mauritania

Particles sinking out of the euphotic zone are important vehicles of carbon export from the surface ocean. Most of the particles produce heavier aggregates by coagulating with each other before they sink. We implemented an aggregation model into the biogeochemical model of Regional Oceanic Modelling System (ROMS) to simulate the distribution of particles in the water column and their downward transport in the Northwest African upwelling region. Accompanying settling chamber, sediment trap and particle camera measurements provide data for model validation. In situ aggregate settling velocities measured by the settling chamber were around 55 m d**-1. Aggregate sizes recorded by the particle camera hardly exceeded 1 mm. The model is based on a continuous size spectrum of aggregates, characterised by the prognostic aggregate mass and aggregate number concentration. Phytoplankton and detritus make up the aggregation pool, which has an averaged, prognostic and size dependent sinking. Model experiments were performed with dense and porous approximations of aggregates with varying maximum aggregate size and stickiness as well as with the inclusion of a disaggregation term. Similar surface productivity in all experiments has been generated in order to find the best combination of parameters that produce measured deep water fluxes. Although the experiments failed to represent surface particle number spectra, in the deep water some of them gave very similar slope and spectrum range as the particle camera observations. Particle fluxes at the mesotrophic sediment trap site off Cape Blanc (CB) have been successfully reproduced by the porous experiment with disaggregation term when particle remineralisation rate was 0.2 d**-1. The aggregation-disaggregation model improves the prediction capability of the original biogeochemical model significantly by giving much better estimates of fluxes for both upper and lower trap. The results also point to the need for more studies to enhance our knowledge on particle decay and its variation and to the role that stickiness play in the distribution of vertical fluxes.

Accumulation rates of dinoflagellate cysts at trap sites CB2, CB3, CB4, and CB9 off Cape Blanc

A 5-year sediment trap survey in the upwelling area off Cape Blanc (NW Africa) provides information on the seasonal and annual resting cyst production of dinoflagellates, their sinking characteristics and preservation potential. Strong annual variation in cyst production characterizes the region. Cyst production of generally all investigated species, including Alexandrium pseudogonyaulax (Biecheler) T. Horig. ex T. Kita et Fukuyo (cyst genus Impagidinium) and Gonyaulax spinifera (Clap. et J. Lachm.) Diesing (cyst genus Nematosphaeropsis) was enhanced with increasing upper water nutrient and trace-element concentrations. Cyst production of Lingulodinium polyedrum (F. Stein) J. D. Dodge was the highest at the transition between upwelling and upwelling-relaxation. Cyst production of Protoperidinium americanum (Gran et Braarud) Balech, Protoperidinium monospinum (Paulsen) K. A. F. Zonn. et B. Dale, and Protoperidinium stellatum (D. Wall) Balech, and heterotrophic dinoflagellates forming Brigantedinium spp. and Echinidinium aculeatum Zonn., increased most pronouncedly during upwelling episodes. Production of Protoperidinium conicum (Gran) Balech and Protoperidinium pentagonum (Gran) Balech cysts and total diatom valves were related, providing evidence of a predator-prey relationship. The export cyst-flux of E. aculeatum, P. americanum, P. monospinum, and P. stellatum was strongly linked to the flux of total diatom valves and CaCO3, whereas the export production of Echinidinium granulatum Zonn. and Protoperidinium subinerme (Paulsen) A. R. Loebl. correlated with total organic carbon, suggesting potential consumption of diatoms, prymnesiophytes, and organic matter, respectively. Sinking velocities were at least 274 m · d**-1, which is in range of the diatom- and coccolith-based phytoplankton aggregates and "slower" fecal pellets. Species-selective degradation did not occur in the water column, but on the ocean floor.

Microbiological investigations of the Canadian tundra

Microbial communities were analyzed at 17 sites visited during the expedition Tundra Northwest 1999 (TNW-99) by microscopic analyses (epifluorescence microscopy and image analyses). The data were used to describe the communities of bacteria, fungi and algae in detail by number, biovolume and biomass. Great variability was found, which could be related to organic matter content of soils and features of vegetation patterns. The amounts (numbers and abundance) of organisms and data on microbial biomass are discussed in relation to other polar environments of the Northern and Southern Hemispheres.

Dissolved organic matter in the Lena Delta in 2009

Large Arctic rivers discharge significant amounts of dissolved organic matter (DOM) into the Arctic Ocean. We sampled natural waters of the Lena River, the Buor-Khaya Bay (Laptev Sea), permafrost melt water creeks, ice complex melt water creeks and a lake. The goal of this study was to characterize the molecular DOM composition with respect to different water bodies within the Lena Delta. We aimed at an identification of source-specific DOM molecular markers and their relative contribution to DOM of different origin. The molecular characterization was performed for solid-phase extracted DOM by Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). Average dissolved organic carbon concentrations in the original samples were 490±75 µmol C/L for riverine and bay samples and 399±115 µmol C/L for permafrost melt water creeks. Average TDN concentrations were elevated in the permafrost melt waters (19.7±7.1 µmol N/L) in comparison to the river and the bay (both 13.2±2.6 µmol N/L). FT-ICR MS and statistical tools demonstrated that the origin of DOM in the Lena Delta was systematically reflected in its molecular composition. Magnitude weighted parameters calculated from MS data (O/Cwa, H/Cwa, C/Nwa) highlighted preliminary sample discrimination. The highest H/Cwa of 1.315 was found for DOM in melt water creeks in comparison to 1.281 for river and 1.230 for the bay samples. In the bay samples we observed a higher fraction of oxygen-rich components which was reflected in an O/Cwa ratio of 0.445 in comparison to 0.425 and 0.427 in the river and creeks, respectively. From the southernmost location to the bay a relative depletion of nitrogenous molecular markers and an enrichment of oxidized DOM components occurred. The highest contribution of nitrogenous components was indicative for creeks reflected in a C/Nwa of 104 in comparison to 143 and 176 in the river and bay, respectively. These observations were studied on a molecular formula level using principal component and indicator value analyses. The results showed systematic differences with respect to water origin and constitute an important basis for a better mechanistic understanding of DOM transformations in the changing Arctic rivers.

Mesocosm experiment Cape Verde 2012: Data

Two 7-day mesocosm experiments were conducted in October 2012 at the Instituto Nacional de Desenvolvimento das Pescas (INDP), Mindelo, Cape Verde. Surface water was collected at night before the start of the respective experiment with RV Islândia south of São Vicente (16°44.4'N, 25°09.4'W) and transported to shore using four 600L food safe intermediate bulk containers. Sixteen mesocosm bags were distributed in four flow-through water baths and shaded with blue, transparent lids to approximately 20% of surface irradiation. Mesocosm bags were filled from the containers by gravity, using a submerged hose to minimize bubbles. The accurate volume inside the individual bags was calculated after addition of 1.5 mmol silicate and measuring the resulting silicate concentration. The volume ranged from 105.5 to 145 L. The experimental manipulation comprised addition of different amounts of inorganic N and P. In the first experiment, the P supply was changed at constant N supply in thirteen of the sixteen units, while in the second experiment the N supply was changed at constant P supply in twelve of the sixteen units. In addition to this, "cornerpoints" were chosen that were repeated during both experiments. Four cornerpoints should have been repeated, but setting the nutrient levels in one mesocosm was not succesfull and therefore this mesocosm also was set at the center point conditions. Experimental treatments were evenly distributed between the four water baths. Initial sampling of the mesocosms on day 1 of each run was conducted between 9:45 and 11:30. After nutrient manipulation, sampling was conducted on a daily basis between 09:00 and 10:30 for days 2 to 8.

Mesocosm experiment Cape Verde 2012: Setup

Two 7-day mesocosm experiments were conducted in October 2012 at the Instituto Nacional de Desenvolvimento das Pescas (INDP), Mindelo, Cape Verde. Surface water was collected at night before the start of the respective experiment with RV Islândia south of São Vicente (16°44.4'N, 25°09.4'W) and transported to shore using four 600L food safe intermediate bulk containers. Sixteen mesocosm bags were distributed in four flow-through water baths and shaded with blue, transparent lids to approximately 20% of surface irradiation. Mesocosm bags were filled from the containers by gravity, using a submerged hose to minimize bubbles. The accurate volume inside the individual bags was calculated after addition of 1.5 mmol silicate and measuring the resulting silicate concentration. The volume ranged from 105.5 to 145 L. The experimental manipulation comprised addition of different amounts of inorganic N and P. In the first experiment, the P supply was changed at constant N supply in thirteen of the sixteen units, while in the second experiment the N supply was changed at constant P supply in twelve of the sixteen units. In addition to this, "cornerpoints" were chosen that were repeated during both experiments. Four cornerpoints should have been repeated, but setting the nutrient levels in one mesocosm was not succesfull and therefore this mesocosm also was set at the center point conditions. Experimental treatments were evenly distributed between the four water baths. Initial sampling of the mesocosms on day 1 of each run was conducted between 9:45 and 11:30. After nutrient manipulation, sampling was conducted on a daily basis between 09:00 and 10:30 for days 2 to 8.

Mesocosm experiment Cape Verde 2012: Environmental conditions (PAR, cloud cover, pump)

Two 7-day mesocosm experiments were conducted in October 2012 at the Instituto Nacional de Desenvolvimento das Pescas (INDP), Mindelo, Cape Verde. Surface water was collected at night before the start of the respective experiment with RV Islândia south of São Vicente (16°44.4'N, 25°09.4'W) and transported to shore using four 600L food safe intermediate bulk containers. Sixteen mesocosm bags were distributed in four flow-through water baths and shaded with blue, transparent lids to approximately 20% of surface irradiation. Mesocosm bags were filled from the containers by gravity, using a submerged hose to minimize bubbles. The accurate volume inside the individual bags was calculated after addition of 1.5 mmol silicate and measuring the resulting silicate concentration. The volume ranged from 105.5 to 145 L. The experimental manipulation comprised addition of different amounts of inorganic N and P. In the first experiment, the P supply was changed at constant N supply in thirteen of the sixteen units, while in the second experiment the N supply was changed at constant P supply in twelve of the sixteen units. In addition to this, "cornerpoints" were chosen that were repeated during both experiments. Four cornerpoints should have been repeated, but setting the nutrient levels in one mesocosm was not succesfull and therefore this mesocosm also was set at the center point conditions. Experimental treatments were evenly distributed between the four water baths. Initial sampling of the mesocosms on day 1 of each run was conducted between 9:45 and 11:30. After nutrient manipulation, sampling was conducted on a daily basis between 09:00 and 10:30 for days 2 to 8.

Phytomass and soil carbon storage of different land cover classes in the Usa river basin

This study describes detailed partitioning of phytomass carbon (C) and soil organic carbon (SOC) for four study areas in discontinuous permafrost terrain, Northeast European Russia. The mean aboveground phytomass C storage is 0.7 kg C/m**2. Estimated landscape SOC storage in the four areas varies between 34.5 and 47.0 kg C/m**2 with LCC (land cover classification) upscaling and 32.5-49.0 kg C/m**2 with soil map upscaling. A nested upscaling approach using a Landsat thematic mapper land cover classification for the surrounding region provides estimates within 5 ± 5% of the local high-resolution estimates. Permafrost peat plateaus hold the majority of total and frozen SOC, especially in the more southern study areas. Burying of SOC through cryoturbation of O- or A-horizons contributes between 1% and 16% (mean 5%) of total landscape SOC. The effect of active layer deepening and thermokarst expansion on SOC remobilization is modeled for one of the four areas. The active layer thickness dynamics from 1980 to 2099 is modeled using a transient spatially distributed permafrost model and lateral expansion of peat plateau thermokarst lakes is simulated using geographic information system analyses. Active layer deepening is expected to increase the proportion of SOC affected by seasonal thawing from 29% to 58%. A lateral expansion of 30 m would increase the amount of SOC stored in thermokarst lakes/fens from 2% to 22% of all SOC. By the end of this century, active layer deepening will likely affect more SOC than thermokarst expansion, but the SOC stores vulnerable to thermokarst are less decomposed.

Neogene palaeoceanographic and palaeoclimatic events inferred from palynological data: Cape Basin off South Africa, ODP Leg 175

Sites 1085, 1086 and 1087 were drilled off South Africa during Ocean Drilling Program (ODP) Leg 175 to investigate the Benguela Current System. While previous studies have focused on reconstructing the Neogene palaeoceanographic and palaeoclimatic history of these sites, palynology has been largely ignored, except for the Late Pliocene and Quaternary. This study presents palynological data from the upper Middle Miocene to lower Upper Pliocene sediments in Holes 1085A, 1086A and 1087C that provide complementary information about the history of the area. Abundant and diverse marine palynomorphs (mainly dinoflagellate cysts), rare spores and pollen, and dispersed organic matter have been recovered. Multivariate statistical analysis of dispersed organic matter identified three palynofacies assemblages (A, B, C) in the most continuous hole (1085A), and they were defined primarily by amorphous organic matter (AOM), and to a lesser extent black debris, structured phytoclasts, degraded phytoclasts, and marine palynomorphs. Ecostratigraphic interpretation based on dinoflagellate cyst, spore-pollen and palynofacies data allowed us to identify several palaeoceanographic and palaeoclimatic signals. First, the late Middle Miocene was subtropical, and sediments contained the highest percentages of land-derived organic matter, even though they are rich in AOM (palynofacies assemblage A). Second, the Late Miocene was cool-temperate and characterized by periods of intensified upwelling, increase in productivity, abundant and diverse oceanic dinoflagellate cysts, and the highest percentages of AOM (palynofacies assemblage C). Third, the Early to early Late Pliocene was warm-temperate with some dry intervals (increase in grass pollen) and intensified upwelling. Fourth, the Neogene "carbonate crash" identified in other southern oceans was recognized in two palynofacies A samples in Hole 1085A that are nearly barren of dinoflagellate cysts: one Middle Miocene sample (590 mbsf, 13.62 Ma) and one Upper Miocene sample (355 mbsf, 6.5 Ma). Finally, the extremely low percentages of pollen suggest sparse vegetation on the adjacent landmass, and Namib desert conditions were already in existence during the late Middle Miocene.

Plant communities and soil chemistry of shrub-steppe and pine savannah grasslands in southern British Columbia, Canada

Habitat fragmentation alters the edges of remnant habitat patches. We examined changes in the plant community and soil in relation to distance from edge and edge type for shrub-steppe and pine savannah grasslands in southern British Columbia, Canada. Community composition showed significant nonlinear relationships with distance-to-edge more frequently at paved roads and fruit crops than at dirt roads or control sites (i.e., in the interior of grassland patches), with changes typically extending 25-30 m. More exotic species and fewer native species were found near edges, and edges showed decreased cryptogam cover and increased bare ground, especially near paved roads. The soil factors that best predicted compositional changes were soil pH and Cu/Mn at paved roads, soil pH and nitrogen at fruit crops, and soil resistance at dirt roads. Variation partitioning suggested that both direct (e.g., propagule pressure) and indirect (environmental change) factors mediated edge-related community changes, and provided evidence that nonlinear responses at developed edges were not due to natural gradients. Given the range of grassland patch sizes in this region (many patches 1-100 ha), the edge effects we observed represent a considerable loss of "core" habitat, which must be accounted for in conservation planning and site restoration.