Net community production, Thorium-234 activity and particle flux during the Southern Ocean iron fertilization experiment LOHAFEX

A closed eddy core in the Subantarctic Atlantic Ocean was fertilized twice with two tons of iron (as FeSO4), and the 300 km**2 fertilized patch was studied for 39 days to test whether fertilization enhances downward particle flux into the deep ocean. Chlorophyll a and primary productivity doubled after fertilization, and photosynthetic quantum yield (FV/FM) increased from 0.33 to >0.40. Silicic acid (<2 µmol/L) limited diatoms, which contributed <10% of phytoplankton biomass. Copepods exerted high grazing pressure. This is the first study of particle flux out of an artificially fertilized bloom with very low diatom biomass. Net community production (NCP) inside the patch, estimated from O2:Ar ratios, averaged 21 mmol POC/m**2/d, probably ±20%. 234Th profiles implied constant export of ~6.3 mmol POC/m**2/d in the patch, similar to unfertilized waters. The difference between NCP and 234Th-derived export partly accumulated in the mixed layer and was partly remineralized between the mixed layer and 100 m. Neutrally buoyant sediment traps at 200 and 450 m inside and outside the patch caught mostly <1.1 mmol POC/m**2/d, predominantly of fecal origin; flux did not increase upon fertilization. Our data thus indicate intense flux attenuation between 100 and 200 m, and probably between the mixed layer and 100 m. We attribute the lack of fertilization-induced export to silicon limitation of diatoms and reprocessing of sinking particles by detritus feeders. Our data are consistent with the view that nitrate-rich but silicate-deficient waters are not poised for enhanced particle export upon iron addition.

Corrected index properties for ODP Leg 127 and 128 sites

During Legs 127 and 128, we found a systematic error in the index property measurements, in that the wet bulk density, grain density, and porosity did not satisfy well-established interrelationships. We have found that an almost constant difference exists between the weight of water lost during drying and the volume of water lost. This discrepancy is independent of volume or water content of the sample. The water losses should be equal because the density of water is close to 1.0 g/cm**3. The pycnometer wet volume measurement has been identified as the source of the systematic error. The wet volume on average is 0.2 cm**3 too low. For the rare cases when the water content is negligible, there is no offset. The source of the wet volume error results from the partial vapor pressure of water in the pycnometer cell. Newly corrected tables of index properties measured during Legs 127 and 128 are included. The corrected index properties are internally consistent. The data are in better agreement with theoretical models that relate the index properties to other physical properties, such as thermal conductivity and acoustic velocity. In future, a standard volume sampler should be used, or the wet volume should be calculated from the dry volume and the water loss by weight.

Organic carbon, reduced sulfur, and iron in Miocene to Holocene sediments from the Oman and Beguela upwelling systems

We examined sediments from Neogene and Quaternary sections of the Benguela and Oman upwelling systems (DSDP Site 532, ODP Sites 723 and 722) to determine environmental and geochemical factors which control and limit pyrite formation in organic-carbon-rich marine sediments. Those samples from the upwelling sites, which contained low to moderate concentrations of total organic carbon (0.7%-3%), had C/S ratios typical of normal marine sediments, i.e., around 2.8. In these sediments, TOC availability probably limited pyrite formation. Results that do not conform with accepted models were found for the sediments high in TOC (3^0-12.4%). The organic matter was of marine origin and contained considerable pyrolytic hydrocarbons, a fact that we take as a sign of low degradation, yet significant concentrations of dissolved sulfate coexisted with it (> 5 mmol/L in the case of Sites 532 and 723). Detrital iron was probably not limiting in either case, because the degree of pyritization was always less than 0.65. Therefore, controls on sulfate reduction and pyrite formation in the organic matter-rich sediments do not appear to conform simply to generally accepted diagenetic models. The data from these thermally immature, old, and organic-rich marine sediments imply that (1) the total reduced sulfur content of organic-rich marine upwelling sediments rarely exceeds an approximate boundary of 1.5% by weight, (2) the C/S ratio of these sediments is not constant and usually much higher than the empirical values proposed for marine sediments. We conclude that sedimentary pyrite formation in upwelling sediments is limited by an as yet unknown factor, and that caution is advised in using C/S ratios and C vs. S diagrams in paleoenvironmental reconstructions for organic-rich sediments.

Concentrations and isotopic compositions of low molecular weight hydrocarbons in hydrothermal fluids from ODP Field, Middle Valley, northern Juan de Fuca Ridge

The presence of sedimentary organic matter blanketing midocean ridge crests has a potentially strong impact on metal transport in hydrothermal vent fluids. To constrain the role of organic matter in metal mobility during hydrothermal sediment alteration, we reacted organic-rich diatomaceous ooze from Guaymas Basin, Gulf of California, and organic-poor hemipelagic mud from Middle Valley, northern Juan de Fuca Ridge, with seawater and a Na-Ca-K-Cl fluid of seawater chlorinity, at 275° to 400°C, 350 to 500 bars, and initial fluid: sediment mass ratios ranging from 1.6 to 9.8. Reaction of these fluids with both sediment types released CO2 and high concentrations of ore-forming metals (Fe, Mn, Zn, Pb) to solution. Relatively low concentrations of Cu were observed in solution and likely reflect the reducing conditions that resulted from the presence of sedimentary organic matter. Both the concentrations of CO2 and dissolved metals were lower in fluids reacted with Middle Valley sediment compared with aqueous concentrations in fluids reacted with Guaymas Basin sediment. During alteration of both sediment types, metal concentrations varied strongly as a function of temperature, increasing by up to an order of magnitude over the 75°C range of each experiment. Major element fluid chemistry and observed alteration assemblages suggest that during hydrothermal alteration of organic-lean sediment from Middle Valley a feldspar-quartz-illite mineral assemblage buffered in situ pH. In contrast, data from the experimental alteration of organic-rich Guaymas Basin sediment suggest that a calcite-plagioclase-quartz assemblage regulated in situ pH. Fluid speciation calculations suggest that in situ pH during Guaymas Basin sediment alteration was lower than during alteration of Middle Valley sediment and accounts for the substantially greater metal mobility at a given temperature and pressure during the former experiment. Comparison of our results with the results of basalt alteration experiments indicate that except for Cu, hydrothermal sediment alteration results in equal or greater concentrations of ore-forming metals at a given temperature and pressure. Accordingly, the presence of ore-forming metals in fluids currently venting from sediment-covered hydrothermal systems at concentrations substantially lower than in fluids from bare-rock systems may reflect chemical reequilibration during subsurface cooling within the sediment pile.

Seawater carbonate chemistry and skeletal development, size, weight, total lipid and symbiont density of coral Favia fragum in a laboratory experiment

Ocean acidification (OA) threatens the existence of coral reefs by slowing the rate of calcium carbonate (CaCO3) production of framework-building corals thus reducing the amount of CaCO3 the reef can produce to counteract natural dissolution. Some evidence exists to suggest that elevated levels of dissolved inorganic nutrients can reduce the impact of OA on coral calcification. Here, we investigated the potential for enhanced energetic status of juvenile corals, achieved via heterotrophic feeding, to modulate the negative impact of OA on calcification. Larvae of the common Atlantic golf ball coral, Favia fragum, were collected and reared for 3 weeks under ambient (421 µatm) or significantly elevated (1,311 µatm) CO2 conditions. The metamorphosed, zooxanthellate spat were either fed brine shrimp (i.e., received nutrition from photosynthesis plus heterotrophy) or not fed (i.e., primarily autotrophic). Regardless of CO2 condition, the skeletons of fed corals exhibited accelerated development of septal cycles and were larger than those of unfed corals. At each CO2 level, fed corals accreted more CaCO3 than unfed corals, and fed corals reared under 1,311 µatm CO2 accreted as much CaCO3 as unfed corals reared under ambient CO2. However, feeding did not alter the sensitivity of calcification to increased CO2; Delta calcification/Delta Omega was comparable for fed and unfed corals. Our results suggest that calcification rates of nutritionally replete juvenile corals will decline as OA intensifies over the course of this century. Critically, however, such corals could maintain higher rates of skeletal growth and CaCO3 production under OA than those in nutritionally limited environments.

Seawater carbonate chemistry and weight of two Atlantic corals Favia fragum and Porites astreoides during experiments, 2011

Rising concentrations of atmospheric CO2 are changing the carbonate chemistry of the oceans, a process known as ocean acidification (OA). Absorption of this CO2 by the surface oceans is increasing the amount of total dissolved inorganic carbon (DIC) and bicarbonate ion (HCO3) available for marine calcification yet is simultaneously lowering the seawater pH and carbonate ion concentration ([CO3]), and thus the saturation state of seawater with respect to aragonite. We investigated the relative importance of [HCO3] versus [CO3] for early calcification by new recruits (primary polyps settled from zooxanthellate larvae) of two tropical coral species, Favia fragum and Porites astreoides. The polyps were reared over a range of ?ar values, which were manipulated by both acid-addition at constant pCO2 (decreased total [HCO3] and [CO3]) and by pCO2 elevation at constant alkalinity (increased [HCO3], decreased [CO3]). Calcification after 2 weeks was quantified by weighing the complete skeleton (corallite) accreted by each polyp over the course of the experiment. Both species exhibited the same negative response to decreasing [CO3] whether ?ar was lowered by acid-addition or by pCO2 elevation-calcification did not follow total DIC or [HCO3]. Nevertheless, the calcification response to decreasing [CO3] was nonlinear. A statistically significant decrease in calcification was only detected between Omega aragonite = <2.5 and Omega aragonite = 1.1-1.5, where calcification of new recruits was reduced by 22-37% per 1.0 decrease in Omega aragonite. Our results differ from many previous studies that report a linear coral calcification response to OA, and from those showing that calcification increases with increasing [HCO3]. Clearly, the coral calcification response to OA is variable and complex. A deeper understanding of the biomineralization mechanisms and environmental conditions underlying these variable responses is needed to support informed predictions about future OA impacts on corals and coral reefs.

GDGT-based proxies of sediment core YD0903

We reconstruct the environmental evolution of the East China Sea in the past 14 kyr based on glycerol dialkyl glycerol tetraethers (GDGTs) in a sediment core from the subaqueous Yangtze River Delta. Two primary phases are recognized. Phase I (13.8-8 cal kyr BP) reflects a predominantly continental influence, showing distinctly higher concentrations of branched GDGTs (averaged 143 ng/g dry sediment weight, dsw) than isoprenoid GDGTs (averaged 36 ng/g dsw), high BIT index (branched vs. isoprenoid tetraethers) values (>0.78) and a fluctuating GDGT-0/crenarchaeol ratio (R0/5, varied from 0.52 to 3.81). Within this interval, temporal increases of terrestrial and marine influence are attributed to Younger Dryas (YD) (ca. 12.9-12.2 cal kyr BP) cold event and melt-water pulse (MWP) -1B (11.5-11.1 cal kyr BP), respectively. The prominent transition from 8 to 7.9 cal kyr BP shows a sharp decrease in BIT index value (<0.4) and increase in crenarchaeol, which marks the beginning of phase II. Afterwards, the proxies remain relatively constant, which indicates that phase II (7.9 cal kyr BP-present) is a shelf sedimentary environment with high stand of sea level. Overall, the BIT index in our record serves as a good marker for terrestrial influence at the site, and likely reflects the flooding history of the region. The TEX86 (TetraEther Index of tetraethers consisting of 86 carbons) proxy is not applicable in phase I because of an excess terrestrial influence; but it seems to be valid for revealing the annual SST in phase II (21.6±0.9°C, n=49). In contrast, the MBT'/CBT (Methylation of Branched Tetraethers and Cyclization of Branched Tetraethers) proxy appears to faithfully record the annual mean air temperature (MAT) (14.3±0.63°C, n=68) and presents an integrated signal over the middle and lower Yangtze River drainage basin.

(Table 1) Summary of low-molecular-weight hydrocarbon concentrations, organic carbon contents, Rock-Eval pyrolysis and lithology at DSDP Leg 79 Holes

A series of core samples taken during Cruise 79 of Glomar Challenger, drilling offshore Morocco (Mazagan Plateau), is analyzed for their low-molecular-weight hydrocarbon contents. Fifty-four samples from DSDP Holes 544A, 545, 547A, and 547B, deep frozen on board immediately after recovery, are studied by a hydrogen-stripping/thermovaporization technique combined with capillary gas chromatography. Thirty-eight compounds in the C2-C8 molecular range, including saturated, olefinic, and aromatic hydrocarbons, are identified. Because of large differences in organic carbon contents, the total C2-C8 hydrocarbon concentrations vary from about 20 to 1500 ng/g dry sediment weight in the whole sample series. Organic-carbon normalized values are about 3.2 x 10**4 ng/g Corg for Lithologic Subunits IIIA and IIIB at Site 545 (Cenomanian to Aptian) and 1.0 x 10**5 ng/g Corg for Unit V at Site 547 (Cenomanian to Albian) reflecting the slightly more advanced maturity stage at the latter site. Values exceeding 10**5 ng/g Corg (Site 545) and 2 x 10**5 ng/g Corg (Site 547) are associated with samples that are very lean in organic carbon and are generally rich in carbonate. These samples are enriched by small amounts of gaseous hydrocarbons. A detailed study of individual hydrocarbon concentrations, plotted against depth, reveal additional indications for migration phenomena. At Site 547, for instance, the most mobile hydrocarbons studied (e.g., ethane) appear to migrate by diffusion or a related process from more than 700 m depth toward the surface.

(Table 1) Low molecular weight hydrocarbon concentrations and organic carbon contents at DSDP Hole 71-511

C2-C8 hydrocarbons (36 compounds identified) from 56 shipboard sealed, deep-frozen core samples of DSDP Leg 71, Site 511, Falkland Plateau, South Atlantic, were analyzed by a combined hydrogen stripping-thermovaporization method. Concentrations, which represent hydrocarbons dissolved in the pore water and adsorbed to the mineral surfaces of the sediment, vary from 24 ng/g of dry weight sediment in Lithologic Unit 4 to 17,400 ng/g in Lithologic Unit 6 ("black shale" unit). Likewise, the organic carbon normalized C2-C8 hydrocarbon concentrations range from 104 to 3.5 x 105 ng/g Corg. The latter value is more than one order of magnitude lower than expected for petroleum source beds in the main phase of oil generation. The low maturity at 600 meters depth is further supported by light hydrocarbon concentration ratios. The change of the kerogen type from Lithologic Unit 5 (Type III) to 6 (Type II) is evidenced by changes in the C6 and C7 hydrocarbon composition. Redistribution phenomena are observed close to the Tertiary-Cretaceous unconformity and at the contact between the "black shale" unit and the overlying Cretaceous chalks and claystones. Otherwise, the low molecular weight hydrocarbons in Hole 511 are formed in situ and remain at their place of formation. The core samples turned out to be contaminated by large quantities of acetone, which is routinely used as a solvent during sampling procedures onboard Glomar Challenger.

Foraminifera Mg/Ca, test weight and XDX for sediment core WIND28K

A record of deep-sea calcite saturation (D[CO3**-2]), derived from X-ray computed tomography-based foraminifer dissolution index, XDX, was constructed for the past 150 ka for a core from the deep (4157 m) tropical western Indian Ocean. G. sacculifer and N. dutertrei recorded a similar dissolution history, consistent with the process of calcite compensation. Peaks in calcite saturation (~15 µmol/kg higher than the present-day value) occurred during deglaciations and early in MIS 3. Dissolution maxima coincided with transitions to colder stages. The mass record of G. sacculifer better indicated preservation than did that of N. dutertrei or G. ruber. Dissolution-corrected Mg/Ca-derived SST records, like other SST records from marginal Indian Ocean sites, showed coolest temperatures of the last 150 ka in early MIS 3, when mixed layer temperatures were ~4°C lower than present SST. Temperatures recorded by N. dutertrei showed the thermocline to be ~4°C colder in MIS 3 compared to the Holocene (8 ka B.P.).

Biogenic particle and biomarker flux from a mooring time-series at AWI HAUSGARTEN

Since 2000 long-term measurements of vertical particle flux have been performed with moored sediment traps at the long-term observatory HAUSGARTEN in the eastern Fram Strait (79°N/4°E). The study area, which is seasonally covered with ice, is located in the confluence zone of the northward flowing warm saline Atlantic water with cold, low salinity water masses of Arctic origin. Current projections suggest that this area is particularly vulnerable to global warming. Total matter fluxes and components thereof (carbonate, particulate organic carbon and nitrogen, biogenic silica, biomarkers) revealed a bimodal seasonal pattern showing elevated sedimentation rates during May/June and August/September. Annual total matter flux (dry weight, DW) at ~ 300 m depth varied between 13 and 32 g/m**2/a during 2000 and 2005. Of this total flux 6-13 % was due to CaCO3, 4-21 % to refractory particulate organic carbon (POC), and 3-8 % to biogenic particulate silica (bPSi). The annual flux of all biogenic components together was almost constant during the period studied (8.5-8.8 g/m**2/a), although this varied from 27 to 67 % of the total annual flux. The fraction was lowest in a year characterized by the longest duration of ice coverage (91 and 70 days for the calendar year and summer season, May-September, respectively). Biomarker analyses revealed that organic matter originating from marine sources was present in excess of terrigenious material in the sedimented matter throughout most of the study period. Fluxes of recognizable phyto- and protozooplankton cells amounted up to 60x106 m**2/d. Diatoms and coccolithophorids were the most abundant organisms. Diatoms, mainly pennate species, dominated during the first years of the investigation. A shift in the composition occurred during the last year when numbers of diatoms declined considerably, leading to a dominance of coccolithoporids. This was also reflected in a decrease in the sedimentation of bPSi. The sedimentation of biogenic matter, however, did not differ from the amount observed during the previous years. Among the larger organisms, pteropods at times contributed significantly to both the total matter and CaCO3, fluxes.

Geochemistry of tetrapyrrole, carotenoid, and perylene pigments in sediments at DSDP Holes 63-467 and 63-471

Twenty-one core samples from DSDP/IPOD Leg 63 were analyzed for products of chlorophyll diagenesis. In addition to the tetrapyrrole pigments, perylene and carotenoid pigments were isolated and identified. The 16 core samples from the San Miguel Gap site (467) and the five from the Baja California borderland location (471) afforded the unique opportunity of examining tetrapyrrole diagenesis in clay-rich marine sediments that are very high in total organic matter. The chelation reaction, whereby free-base porphyrins give rise to metalloporphyrins (viz., nickel), is well documented within the downhole sequence of sediments from the San Miguel Gap (Site 467). Recognition of unique arrays of highly dealkylated copper and nickel ETIO-porphyrins, exhibiting nearly identical carbonnumber homologies (viz., C-23 to C-30; mode = C-26), enabled subtraction of this component (thought to be derived from an allochthonous source) and thus permitted description of the actual in situ diagenesis of autochthonous chlorophyll derivatives.