A 31,000-year high-resolution record from two sediment cores off northwest Africa

Benthic foraminiferal assemblage compositions and sedimentary geochemical parameters were analyzed in two radiocarbon dated sediment cores from the upwelling area off NW Africa at 12°N, to reconstruct productivity changes during the last 31 kyr. High-latitude cold events and variations in low-latitude summer insolation influenced humidity, wind systems, and the position of the tropical rain belt over this time period. This in turn caused changes in intensity and seasonality of primary productivity off the southern Northwest African continental margin. High accumulation rates of benthic foraminifera, carbonate, and organic carbon during times of north Atlantic melt water events Heinrich 2 (25.4 to 24.3 kyr BP) and 1 (16.8 to 15.8 kyr BP) indicate high productivity. Dominance of infaunal benthic foraminiferal species and high numbers of deep infaunal specimens during that time indicate a strong and sustained supply of refractory organic matter reworked from the upper slope and shelf. A more southerly position of the tropical rainbelt and the Northeast trade wind belt during Heinrich 2 and 1 may have enhanced wind intensity and almost permanent upwelling, driving this scenario. A phytodetritus-related benthic fauna indicates seasonally pulsed input of labile organic matter but generally low year-round productivity during the Last Glacial Maximum (23 to 18 kyr BP). The tropical rainbelt is more expanded to the North than during Heinrich Events, and relatively weak NE trade winds resulted in seasonal and weak upwelling, thus lower productivity. High productivity characterized by a seasonally high input of labile organic matter, is indicated for times of orbital forced warming, such as the African Humid Period (9.8 to 7 kyr BP). An intensified African monsoon during boreal summer and the northernmost position of the tropical rainbelt within the last 31 kyr resulted in enhanced river discharge from the northward-extended drainage area (or river basin) initiating intense phytoplankton blooms. In the late Holocene (4 to 0 kyr BP) strong carbonate dissolution may have been caused by even more enhanced organic matter fluxes to the sea floor. Increasing aridity on the continent and stronger NE trade winds induced intensive, seasonal coastal upwelling.

Speciations of Mn and Fe in Fe-Mn nodules from the western part of the Clarion-Clipperton ore province

Hydrogenic forms of iron and manganese occurrence were studied in samples of ferromanganese nodules sampled within two polygons during Cruise 28 of R/V Dmitry Mendeleeev (1982) in the western part of the Clarion-Clipperton ore province. Contents of labile exchangeable Fe and Mn, amorphous hydroxides and poorly soluble compounds of Fe and Mn were analyzed. In nodules from DM28-2474 Polygon labile exchangeable Fe and Mn and amorphous hydroxides dominated; in nodules from DM28-2483 Polygon poorly soluble compounds dominated. Analysis of contents of labile forms of Fe and Mn occurrence in different morphological types of nodules distinguished predominantly hydrogenous botryoidal nodules, spheroidal and ellipsoidal intergrowth nodules, and hydrogenic-diagenetic discoid nodules.

Seasonally aggregated values of dissolved inorganic phosphorus in soil solution of the Jena Experiment (Main Experiment, year 2003)

This data set contains measurements of inorganic phosphorus in samples of soil solution collected in 2003 from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below) that have been aggregated to seasonal values. In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Glass suction plates with a diameter of 12 cm, 1 cm thickness and a pore size of 1-1.6 µm (UMS GmbH, Munich, Germany) were installed in April 2002 in depths of 10, 20, 30 and 60 cm to collect soil solution. Manual soil matric potential measurements were used to regulate the vacuum system. Manual soil matric potential measurements were used to regulate the vacuum system. The sampling bottles were continuously evacuated to a negative pressure between 50 and 350 mbar, such that the suction pressure was about 50 mbar above the actual soil water tension. Thus, only the soil leachate was collected. Cumulative soil solution was sampled biweekly and analyzed for dissolved inorganic P (PO4P). Here volume-weighted mean values are provided as aggregated seasonal values (spring = March to May, summer = June to August, fall = September to November, winter = December to February) for 2003 in spring, fall, and winter. To calculate these values, the sampled volume of soil solution is used as weight for P concentrations of the respective sampling date. Inorganic phosphorus concentrations in the soil solution were measured photometrically with a continuous flow analyzer (CFA SAN++, Skalar [Breda, The Netherlands]). Ammonium molybdate catalyzed by antimony tartrate reacts in an acidic medium with phosphate and forms a phospho-molybdic acid complex. Ascorbic acid reduces this complex to an intensely blue-colored complex. As the molybdic complex forms under strongly acidic conditions, we could not exclude the hydrolysis of labile organic P compounds in our samples. Furthermore, the molybdate reaction is not sensitive for condensed phosphates. The detection limits of both TDP and PO4P were 0.02 mg P l-1 (CFA, Skalar).

Seasonally aggregated values of dissolved inorganic phosphorus in soil solution of the Jena Experiment (Main Experiment, year 2005)

This data set contains measurements of inorganic phosphorus in samples of soil solution collected in 2005 from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below) that have been aggregated to seasonal values. In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Glass suction plates with a diameter of 12 cm, 1 cm thickness and a pore size of 1-1.6 µm (UMS GmbH, Munich, Germany) were installed in April 2002 in depths of 10, 20, 30 and 60 cm to collect soil solution. Manual soil matric potential measurements were used to regulate the vacuum system. Manual soil matric potential measurements were used to regulate the vacuum system. The sampling bottles were continuously evacuated to a negative pressure between 50 and 350 mbar, such that the suction pressure was about 50 mbar above the actual soil water tension. Thus, only the soil leachate was collected. Cumulative soil solution was sampled biweekly and analyzed for dissolved inorganic P (PO4P). Here volume-weighted mean values are provided as aggregated seasonal values (spring = March to May, summer = June to August, fall = September to November, winter = December to February) for 2005 in spring, and winter. To calculate these values, the sampled volume of soil solution is used as weight for P concentrations of the respective sampling date. Inorganic phosphorus concentrations in the soil solution were measured photometrically with a continuous flow analyzer (CFA Autoanalyzer [Bran&Luebbe, Norderstedt, Germany]). Ammonium molybdate catalyzed by antimony tartrate reacts in an acidic medium with phosphate and forms a phospho-molybdic acid complex. Ascorbic acid reduces this complex to an intensely blue-colored complex. As the molybdic complex forms under strongly acidic conditions, we could not exclude the hydrolysis of labile organic P compounds in our samples. Furthermore, the molybdate reaction is not sensitive for condensed phosphates. The detection limits of both TDP and PO4P were 0.04 mg P l-1 (Autoanalyzer, Bran&Luebbe).

Dissolved phosphorus in soil solution of the Jena Experiment (Main Experiment, year 2002)

This data set contains measurements of dissolved phosphorus (total dissolved nitrogen: TDP, dissolved inorganic phosphorus: PO4P and dissolved organic phosphorus: DOP) in samples of soil water collected in 2002 from the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Glass suction plates with a diameter of 12 cm, 1 cm thickness and a pore size of 1-1.6 µm (UMS GmbH, Munich, Germany) were installed in April 2002 in depths of 10, 20, 30 and 60 cm to collect soil solution. Manual soil matric potential measurements were used to regulate the vacuum system. The sampling bottles were continuously evacuated to a negative pressure between 50 and 350 mbar, such that the suction pressure was about 50 mbar above the actual soil water tension. Thus, only the soil leachate was collected. Cumulative soil solution was sampled bi-weekly, in 2002 at the 23.10.2002; 05.11.2002; 20.11.2002; 05.12.2002; and 28.12.2002, and analyzed for dissolved inorganic P (PO4P) and total dissolved phosphorus (TDP). Inorganic phosphorus concentrations in the soil solution were measured photometrically with a continuous flow analyzer (CFA SAN++, Skalar [Breda, The Netherlands]). Ammonium molybdate catalyzed by antimony tartrate reacts in an acidic medium with phosphate and forms a phospho-molybdic acid complex. Ascorbic acid reduces this complex to an intensely blue-colored complex. Total dissolved P in soil solution was analyzed by irradiation with UV and oxidation with K2S2O8 followed by reaction with ammonium molybdate (Skalar catnr. 503-553w/r). As the molybdic complex forms under strongly acidic conditions, we could not exclude the hydrolysis of labile organic P compounds in our samples. Furthermore, the molybdate reaction is not sensitive for condensed phosphates. The detection limits of both TDP and PO4P were 0.02 mg P l-1 (CFA, Skalar). Dissolved organic P (DOP) in soil solution was calculated as the difference between TDP and PO4P. In a low number of samples, TDP was equal to or smaller than PO4P; in these cases, DOP was assumed to be zero.

Fluorescence of dissolved organic matter un marine sediments

The fluorescence of porewaters from marine sediment cores from six different areas was measured. In most cases, fluorescence was affected primarily by the diagenesis of organic carbon first through sulfate reduction and subsequently by methane generation. Typically, fluorescence, dissolved organic carbon (DOC), absorbance, alkalinity, and ammonium ion concentrations correlate quite well, increasing in the upper sections of anoxic sediments and co-varying in deeper sections of these cores. The good correlation of DOC with fluorescence in the three cores in which DOC was measured indicates that fluorescence can be used to make a first order estimate of DOC concentration in anoxic porewaters. Data are consistent with a model in which labile organic matter in the sediments is broken down by sulfur reducing bacteria to low molecular weight monomers. These monomers are either remineralized to CO2 or polymerize to form dissolved, fluorescent, high molecular weight molecules. The few exceptions to this model involve hydrothermally generated hydrocarbons that are formed in situ in the Guaymas Basin or are horizontally advected along the decollement in the Nankai Trench.

Graphs of experimental results given in concentration of trace metals versus time in days

The impact of CO2 leakage on solubility and distribution of trace metals in seawater and sediment has been studied in lab scale chambers. Seven metals (Al, Cr, Ni, Pb, Cd, Cu, and Zn) were investigated in membrane-filtered seawater samples, and DGT samplers were deployed in water and sediment during the experiment. During the first phase (16 days), "dissolved" (<0.2 µm) concentrations of all elements increased substantially in the water. The increase in dissolved fractions of Al, Cr, Ni, Cu, Zn, Cd and Pb in the CO2 seepage chamber was respectively 5.1, 3.8, 4.5, 3.2, 1.4, 2.3 and 1.3 times higher than the dissolved concentrations of these metals in the control. During the second phase of the experiment (10 days) with the same sediment but replenished seawater, the dissolved fractions of Al, Cr, Cd, and Zn were partly removed from the water column in the CO2 chamber. DNi and DCu still increased but at reduced rates, while DPb increased faster than that was observed during the first phase. DGT-labile fractions (MeDGT) of all metals increased substantially during the first phase of CO2 seepage. DGT-labile fractions of Al, Cr, Ni, Cu, Zn, Cd and Pb were respectively 7.9, 2.0, 3.6, 1.7, 2.1, 1.9 and 2.3 times higher in the CO2 chamber than that of in the control chamber. AlDGT, CrDGT, NiDGT, and PbDGT continued to increase during the second phase of the experiment. There was no change in CdDGT during the second phase, while CuDGT and ZnDGT decreased by 30% and 25%, respectively in the CO2 chamber. In the sediment pore water, DGT labile fractions of all the seven elements increased substantially in the CO2 chamber. Our results show that CO2 leakage affected the solubility, particle reactivity and transformation rates of the studied metals in sediment and at the sediment-water interface. The metal species released due to CO2 acidification may have sufficiently long residence time in the seawater to affect bioavailability and toxicity of the metals to biota.

Organic matter and sediment properties of samples from site GeoB15105 from the Black Sea

Dissolved organic matter (DOM) in marine sediments is a complex mixture of thousands of individual constituents that participate in biogeochemical reactions and serve as substrates for benthic microbes. Knowledge of the molecular composition of DOM is a prerequisite for a comprehensive understanding of the biogeochemical processes in sediments. In this study, interstitial water DOM was extracted with Rhizon samplers from a sediment core from the Black Sea and compared to the corresponding water-extractable organic matter fraction (<0.4 µm) obtained by Soxhlet extraction, which mobilizes labile particulate organic matter and DOM. After solid phase extraction (SPE) of DOM, samples were analyzed for the molecular composition by Fourier Transform Ion-Cyclotron Resonance Mass Spectrometry (FT-ICR MS) with electrospray ionization in negative ion mode. The average SPE extraction yield of the dissolved organic carbon (DOC) in interstitial water was 63%, whereas less than 30% of the DOC in Soxhlet-extracted organic matter was recovered. Nevertheless, Soxhlet extraction yielded up to 4.35% of the total sedimentary organic carbon, which is more than 30-times the organic carbon content of the interstitial water. While interstitial water DOM consisted primarily of carbon-, hydrogen- and oxygen-bearing compounds, Soxhlet extracts yielded more complex FT-ICR mass spectra with more peaks and higher abundances of nitrogen- and sulfur-bearing compounds. The molecular composition of both sample types was affected by the geochemical conditions in the sediment; elevated concentrations of HS- promoted the early diagenetic sulfurization of organic matter. The Soxhlet extracts from shallow sediment contained specific three- and four-nitrogen-bearing molecular formulas that were also detected in bacterial cell extracts and presumably represent proteinaceous molecules. These compounds decreased with increasing sediment depth while one- and two-nitrogen-bearing molecules increased, resulting in a higher similarity of both sample types in the deep sediment. In summary, Soxhlet extraction of sediments accessed a larger and more complex pool of organic matter than present in interstitial water DOM.

Impact of CO2 enrichment on organic matter dynamics during nutrient induced coastal phytoplankton blooms

A mesocosm experiment was conducted to investigate the impact of rising fCO2 on the build-up and decline of organic matter during coastal phytoplankton blooms. Five mesocosms (~38 m³ each) were deployed in the Baltic Sea during spring (2009) and enriched with CO2 to yield a gradient of 355-862 µatm. Mesocosms were nutrient fertilized initially to induce phytoplankton bloom development. Changes in particulate and dissolved organic matter concentrations, including dissolved high-molecular weight (>1 kDa) combined carbohydrates, dissolved free and combined amino acids as well as transparent exopolymer particles (TEP), were monitored over 21 days together with bacterial abundance, and hydrolytic extracellular enzyme activities. Overall, organic matter followed well-known bloom dynamics in all CO2 treatments alike. At high fCO2, higher dPOC:dPON during bloom rise, and higher TEP concentrations during bloom peak, suggested preferential accumulation of carbon-rich components. TEP concentration at bloom peak was significantly related to subsequent sedimentation of particulate organic matter. Bacterial abundance increased during the bloom and was highest at high fCO2. We conclude that increasing fCO2 supports production and exudation of carbon-rich components, enhancing particle aggregation and settling, but also providing substrate and attachment sites for bacteria. More labile organic carbon and higher bacterial abundance can increase rates of oxygen consumption and may intensify the already high risk of oxygen depletion in coastal seas in the future.

Comparison of fecal indicators with pathogenic bacteria and rotavirus in rural Bangladesh groundwater

Groundwater is routinely analyzed for fecal indicators but direct comparisons of fecal indicators to the presence of bacterial and viral pathogens are rare. This study was conducted in rural Bangladesh where the human population density is high, sanitation is poor, and groundwater pumped from shallow tubewells is often contaminated with fecal bacteria. Five indicator microorganisms (E. coli, total coliform, F+RNA coliphage, Bacteroides and human-associated Bacteroides (HuBacteroides)) and various environmental parameters were compared to the direct detection of waterborne pathogens by quantitative PCR in groundwater pumped from 50 tubewells. Rotavirus was detected in groundwater filtrate from the largest proportion of tubewells (40%), followed by Shigella (10%), Vibrio (10%), and pathogenic E. coli (8%). Spearman rank correlations and sensitivity-specificity calculations indicate that some, but not all, combinations of indicators and environmental parameters can predict the presence of pathogens. Culture-dependent fecal indicator bacteria measured on a single date did not predict bacterial pathogens, but annually averaged monthly measurements of culturable E. coli did improve prediction for total bacterial pathogens. F+RNA coliphage were neither correlated nor sufficiently sensitive towards rotavirus, but were predictive of bacterial pathogens. A qPCR-based E. coli assay was the best indicator for the bacterial pathogens, rotavirus and all pathogens combined. Since groundwater cannot be excluded as a significant source of diarrheal disease in Bangladesh and neighboring countries with similar characteristics, the need to develop more effective methods for screening tubewells with respect to microbial contamination is necessary.

Contents and isotopic speciation of sedimentary carbon and nitrogen in sediment core MD01-2404, the Okinawa Trough

Total organic carbon to total nitrogen ratio (C/N) and their isotopic composition (d13CTOC vs. d15NTN) are oft-applied proxies to discern terrigenous from marine sourced organics and to unravel the ancient environmental information. In high depositional Asian marginal seas, matrixes, including N-bearing minerals, dilution leads to illusive and even contradictive interpretations. We use KOH-KOBr to separate operationally defined total organic matter into oxidizable (labile) and residual fractions for content and isotope measurements. In a sediment core in the Okinawa Trough, significant amounts of carbon and nitrogen existed in the residual phase, in which the C/N ratio was ~9 resembling most documented sedimentary bulk C/N ratios in the China marginal seas. Such similarity creates a pseudo-C/N interrupting the application of bulk C/N. The residual carbon, though composition unknown, it displayed a d13C range (-22.7 to -18.9 per mil, mean -20.7 per mil) similar to black carbon (-24.0 to -22.8 per mil) in East China Sea surface sediments. After removing residual fraction, we found the temporal pattern of d13CLOC in labile fraction (LOC) was more variable but broadly agreed with the atmospheric pCO2-induced changes in marine endmember d13C. Thus, we suggested adding pCO2-induced endmember modulation into two-endmember mixing model for paleo-environment reconstruction. Meanwhile, the residual nitrogen revealed an intimate association with illite content suggesting its terrestrial origin. Additionally, d15N in residual fraction likely carried the climate imprint from land. Further studies are required to explore the controlling factors for carbon and nitrogen isotopic speciation and to retrieve the information locked in the residual fraction.