Quantitative component analysis of the coarse fraction of surface sediments from the Persian Gulf

In the Persian Gulf and the Gulf of Oman marl forms the primary sediment cover, particularly on the Iranian side. A detailed quantitative description of the sediment components > 63 µ has been attempted in order to establish the regional distribution of the most important constituents as well as the criteria governing marl sedimentation in general. During the course of the analysis, the sand fraction from about 160 bottom-surface samples was split into 5 phi° fractions and 500 to 800 grains were counted in each individual fraction. The grains were cataloged in up to 40 grain type catagories. The gravel fraction was counted separately and the values calculated as weight percent. Basic for understanding the mode of formation of the marl sediment is the "rule" of independent availability of component groups. It states that the sedimentation of different component groups takes place independently, and that variation in the quantity of one component is independent of the presence or absence of other components. This means, for example, that different grain size spectrums are not necessarily developed through transport sorting. In the Persian Gulf they are more likely the result of differences in the amount of clay-rich fine sediment brought in to the restricted mouth areas of the Iranian rivers. These local increases in clayey sediment dilute the autochthonous, for the most part carbonate, coarse fraction. This also explains the frequent facies changes from carbonate to clayey marl. The main constituent groups of the coarse fraction are faecal pellets and lumps, the non carbonate mineral components, the Pleistocene relict sediment, the benthonic biogene components and the plankton. Faecal pellets and lumps are formed through grain size transformation of fine sediment. Higher percentages of these components can be correlated to large amounts of fine sediment and organic C. No discernable change takes place in carbonate minerals as a result of digestion and faecal pellet formation. The non-carbonate sand components originate from several unrelated sources and can be distinguished by their different grain size spectrum; as well as by other characteristics. The Iranian rivers supply the greatest amounts (well sorted fine sand). Their quantitative variations can be used to trace fine sediment transport directions. Similar mineral maxima in the sediment of the Gulf of Oman mark the path of the Persian Gulf outflow water. Far out from the coast, the basin bottoms in places contain abundant relict minerals (poorly sorted medium sand) and localized areas of reworked salt dome material (medium sand to gravel). Wind transport produces only a minimal "background value" of mineral components (very fine sand). Biogenic and non-biogenic relict sediments can be placed in separate component groups with the help of several petrographic criteria. Part of the relict sediment (well sorted fine sand) is allochthonous and was derived from the terrigenous sediment of river mouths. The main part (coarse, poorly sorted sediment), however, was derived from the late Pleistocene and forms a quasi-autochthonous cover over wide areas which receive little recent sedimentation. Bioturbation results in a mixing of the relict sediment with the overlying younger sediment. Resulting vertical sediment displacement of more than 2.5 m has been observed. This vertical mixing of relict sediment is also partially responsible for the present day grain size anomalies (coarse sediment in deep water) found in the Persian Gulf. The mainly aragonitic components forming the relict sediment show a finely subdivided facies pattern reflecting the paleogeography of carbonate tidal flats dating from the post Pleistocene transgression. Standstill periods are reflected at 110 -125m (shelf break), 64-61 m and 53-41 m (e.g. coare grained quartz and oolite concentrations), and at 25-30m. Comparing these depths to similar occurrences on other shelf regions (e. g. Timor Sea) leads to the conclusion that at this time minimal tectonic activity was taking place in the Persian Gulf. The Pleistocene climate, as evidenced by the absence of Iranian river sediment, was probably drier than the present day Persian Gulf climate. Foremost among the benthonic biogene components are the foraminifera and mollusks. When a ratio is set up between the two, it can be seen that each group is very sensitive to bottom type, i.e., the production of benthonic mollusca increases when a stable (hard) bottom is present whereas the foraminifera favour a soft bottom. In this way, regardless of the grain size, areas with high and low rates of recent sedimentation can be sharply defined. The almost complete absence of mollusks in water deeper than 200 to 300 m gives a rough sedimentologic water depth indicator. The sum of the benthonic foraminifera and mollusca was used as a relative constant reference value for the investigation of many other sediment components. The ratio between arenaceous foraminifera and those with carbonate shells shows a direct relationship to the amount of coarse grained material in the sediment as the frequence of arenaceous foraminifera depends heavily on the availability of sand grains. The nearness of "open" coasts (Iranian river mouths) is directly reflected in the high percentage of plant remains, and indirectly by the increased numbers of ostracods and vertebrates. Plant fragments do not reach their ultimate point of deposition in a free swimming state, but are transported along with the remainder of the terrigenous fine sediment. The echinoderms (mainly echinoids in the West Basin and ophiuroids in the Central Basin) attain their maximum development at the greatest depth reached by the action of the largest waves. This depth varies, depending on the exposure of the slope to the waves, between 12 to 14 and 30 to 35 m. Corals and bryozoans have proved to be good indicators of stable unchanging bottom conditions. Although bryozoans and alcyonarian spiculae are independent of water depth, scleractinians thrive only above 25 to 30 m. The beginning of recent reef growth (restricted by low winter temperatures) was seen only in one single area - on a shoal under 16 m of water. The coarse plankton fraction was studied primarily through the use of a plankton-benthos ratio. The increase in planktonic foraminifera with increasing water depth is here heavily masked by the "Adjacent sea effect" of the Persian Gulf: for the most part the foraminifera have drifted in from the Gulf of Oman. In contrast, the planktonic mollusks are able to colonize the entire Persian Gulf water body. Their amount in the plankton-benthos ratio always increases with water depth and thereby gives a reliable picture of local water depth variations. This holds true to a depth of around 400 m (corresponding to 80-90 % plankton). This water depth effect can be removed by graphical analysis, allowing the percentage of planktonic mollusks per total sample to be used as a reference base for relative sedimentation rate (sedimentation index). These values vary between 1 and > 1000 and thereby agree well with all the other lines of evidence. The "pteropod ooze" facies is then markedly dependent on the sedimentation rate and can theoretically develop at any depth greater than 65 m (proven at 80 m). It should certainly no longer be thought of as "deep sea" sediment. Based on the component distribution diagrams, grain size and carbonate content, the sediments of the Persian Gulf and the Gulf of Oman can be grouped into 5 provisional facies divisions (Chapt.19). Particularly noteworthy among these are first, the fine grained clayey marl facies occupying the 9 narrow outflow areas of rivers, and second, the coarse grained, high-carbonate marl facies rich in relict sediment which covers wide sediment-poor areas of the basin bottoms. Sediment transport is for the most part restricted to grain sizes < 150 µ and in shallow water is largely coast-parallel due to wave action at times supplemented by tidal currents. Below the wave base gravity transport prevails. The only current capable of moving sediment is the Persian Gulf outflow water in the Gulf of Oman.

Effects of pCO2 and iron on the elemental composition and cell geometry of the marine diatom Pseudo-nitzschia pseudodelicatissima//(Bacillariophyceae)

Partial pressure of CO2 (pCO2) and iron availability in seawater show corresponding changes due to biological and anthropogenic activities. The simultaneous change in these factors precludes an understanding of their independent effects on the ecophysiology of phytoplankton. In addition, there is a lack of data regarding the interactive effects of these factors on phytoplankton cellular stoichiometry, which is a key driving factor for the biogeochemical cycling of oceanic nutrients. Here, we investigated the effects of pCO2 and iron availability on the elemental composition (C, N, P, and Si) of the diatom Pseudo-nitzschia pseudodelicatissima (Hasle) Hasle by dilute batch cultures under 4 pCO2 (~200, ~380, ~600, and ~800 µatm) and five dissolved inorganic iron (Fe'; ~5, ~10, ~20, ~50, and ~100 pmol /L) conditions. Our experimental procedure successfully overcame the problems associated with simultaneous changes in pCO2 and Fe' by independently manipulating carbonate chemistry and iron speciation, which allowed us to evaluate the individual effects of pCO2 and iron availability. We found that the C:N ratio decreased significantly only with an increase in Fe', whereas the C:P ratio increased significantly only with an increase in pCO2. Both Si:C and Si:N ratios decreased with increasing pCO2 and Fe'. Our results indicate that changes in pCO2 and iron availability could influence the biogeochemical cycling of nutrients in future oceans with high- CO2 levels, and, similarly, during the time course of phytoplankton blooms. Moreover, pCO2 and iron availability may also have affected oceanic nutrient biogeochemistry in the past, as these conditions have changed markedly over the Earth's history.

Impact of elevated pCO2 on paralytic shellfish poisoning toxin content and composition in Alexandrium tamarense

Ocean acidification is considered a major threat to marine ecosystems and may particularly affect primary producers. Here we investigated the impact of elevated pCO2 on paralytic shellfish poisoning toxin (PST) content and composition in two strains of Alexandrium tamarense, Alex5 and Alex2. Experiments were carried out as dilute batch to keep carbonate chemistry unaltered over time. We observed only minor changes with respect to growth and elemental composition in response to elevated pCO2. For both strains, the cellular PST content, and in particular the associated cellular toxicity, was lower in the high CO2 treatments. In addition, Alex5 showed a shift in its PST composition from a nonsulfated analogue towards less toxic sulfated analogues with increasing pCO2. Transcriptomic analyses suggest that the ability of A. tamarense to maintain cellular homeostasis is predominantly regulated on the post-translational level rather than on the transcriptomic level. Furthermore, genes associated to secondary metabolite and amino acid metabolism in Alex5 were down-regulated in the high CO2 treatment, which may explain the lower PST content. Elevated pCO2 also induced up-regulation of a putative sulfotransferase sxtN homologue and a substantial down-regulation of several sulfatases. Such changes in sulfur metabolism may explain the shift in PST composition towards more sulfated analogues. All in all, our results indicate that elevated pCO2 will have minor consequences for growth and elemental composition, but may potentially reduce the cellular toxicity of A. tamarense.

Seawater carbonate chemistry and biological processes during experiments with four strains of Emiliania huxleyi

Four strains of the coccolithophore E. huxleyi (RCC1212, RCC1216, RCC1238, RCC1256) were grown in dilute batch culture at four CO2 levels ranging from ~200 µatm to ~1200 µatm. Growth rate, particulate organic carbon content, and particulate inorganic carbon content were measured, and organic and inorganic carbon production calculated. The four strains did not show a uniform response to carbonate chemistry changes in any of the analysed parameters and none of the four strains displayed a response pattern previously described for this species. We conclude that the sensitivity of different strains of E. huxleyi to acidification differs substantially and that this likely has a genetic basis. We propose that this can explain apparently contradictory results reported in the literature.

Seawater carbonate chemistry and processes during experiments with Emiliania huxleyi (PML B92/11), 2000

We have measured the stable carbon isotopic composition of bulk organic matter (POC), alkenones, sterols, fatty acids, and phytol in the coccolithophorid Emiliania huxleyi grown in dilute batch cultures over a wide range of CO2 concentrations (1.1-53.5 micromol L-1). The carbon isotope fractionation of POC (POC) varied by ca. 7 per mil and was positively correlated with aqueous CO2 concentration [CO2aq]. While this result confirms general trends observed for the same alga grown in nitrogen-limited chemostat cultures, considerable differences were obtained in absolute values of POC and in the slope of the relationship of POC with growth rate and [CO2aq]. Also, a significantly greater offset was obtained between the delta13C of alkenones and bulk organic matter in this study compared with previous work (5.4, cf. 3.8 per mil). This suggests that the magnitude of the isotope offset may depend on growth conditions. Relative to POC, individual fatty acids were depleted in 13C by 2.3 per mil to 4.1 per mil, phytol was depleted in 13C by 1.9 per mil, and the major sterol 24-methylcholesta-5,22E-dien-3beta-ol was depleted in 13C by 8.5 per mil. This large spread of delta13C values for different lipid classes in the same alga indicates the need for caution in organic geochemical studies when assigning different sources to lipids that might have delta13C values differing by just a few per mil. Increases in [CO2aq] led to dramatic increases in the alkenone contents per cell and as a proportion of organic carbon, but there was no systematic effect on values of U37k- used for reconstructions of paleo sea surface temperature.

Chemistry and mineralogy of ODP Leg 124 sediment samples

From X-ray mineralogical studies and chemical analyses of the whole rocks and the fine fractions (<2 µm) of ten to fifteen samples at each site of ODP Leg 124, two major sources were identified in the sedimentary components of the Celebes and Sulu basins: (1) a terrestrial and continental contribution; (2) a volcanic influx that gives way to well-defined volcanic units or to a dilute contamination, consisting of coarse-grained minerals (Plagioclase, pyroxene, olivine, spinel) or a smectitic-rich fraction produced by the alteration of volcanic glasses and ashes. The continental signature increases the amount of quartz in the rocks and the phyllitic association is complex: micas, kaolinite, disordered interstratified clay-minerals. The chemical compositions of the bulk rocks and the fractions <2 µm are more potassic and aluminum-rich. The volcanic imprint depends on the grain-size and chemical properties of the components. Ca/Na contents highly variable compared to the K content of the bulk composition are due to the presence of coarse-grained volcanic Plagioclase. The fractions <2 µm are more magnesian than in the continental regime. The diagenesis is revealed by the crystallization of zeolites, the fixation of magnesium into the smectites that depletes the pore fluids in this element. Smectitization of the disordered interstratified clay minerals enriches the alkalinity of the pore fluids. Some deep formations of the Sulu Basin are affected by a thermal event, but no thermal event was recognized in the Celebes Basin.

Organic carbon, calcium carbonate and carbon/nitrogen ratio at DSDP Leg 93 sites

A large number of samples of nonlithified and lithified sediments from Leg 93 sites were analyzed for their contents of organic carbon and calcium carbonate. An average of two samples was selected from every core for carbonate determination; organic carbon was measured in most of these samples. Nearly all of these analyses were performed on board Glomar Challenger for samples from Sites 603 and 604. Site 605 samples, plus some of the deeper samples from Hole 603B, were analyzed at the University of Michigan. The procedures used in both cases were virtually the same, and their results compared well. Organic carbon analyses were done using a Hewlett- Packard 185-B CHN Analyzer. Portions of samples selected for calcium carbonate determinations were treated with dilute HC1 to remove carbonate, washed with deionized water, and dried at 110°C. A Cahn Electrobalance was used to weight 20-mg samples of sediment for CHN analysis. Samples were combusted at 1050°C in the presence of an oxidant, and the volumes of the evolved gases determined as measures of the C, H, and N contents of sediment organic matter. Areas of gas peaks were determined and compared to those of rock standards of known carbon and nitrogen contents. These values were used to standardize instrument response so that C/N atomic ratios could be reported. Organic carbon concentrations were calculated on the basis of sediment dry weight. Hydrogen elemental analysis with the procedure used is untrustworthy because of the variable amounts of clay minerals and their hydrates, hence hydrogen values are not reported for samples analyzed by this method.

Fe isotopic composition in continental iron cycle (Table 1)

The effect of continental weathering on the iron isotope compositions of natural materials is investigated. Unweathered igneous rocks, pelagic clay, and dust fall within the range delta56Fe=0 +/- 0.3 per mil. Rivers with large suspended loads also have delta56Fe values near zero. Dilute streams have delta56Fe values that trend towards lower delta56Fe (~-1) suggesting that dissolved riverine iron is isotopically light relative to igneous rocks. Bulk soil and soil leaches display systematically different delta56Fe profiles, indicating that isotopically distinct Fe pools are generated during pedogenesis. Nannofossil ooze, which contains Fe scavenged from the ocean water column, has delta56Fe c. 0, but is consistent with seawater dissolved Fe having negative delta56Fe. It is inferred that continental weathering under modern oxidizing Earth surface conditions preferentially releases dissolved Fe with negative delta56Fe, which is transported in rivers to the ocean. A preliminary analysis of the marine Fe budget suggests that riverine Fe has a substantial role in determining the delta56Fe of both the modern and ancient oceans, but other inputs, particularly that from diagenesis of marine sediments, may also be important. Since the chemical pathways of Fe processing during weathering are dependent on oxidation state and biological activity, Fe isotopes may prove useful for detecting changes in these parameters in the geologic past.

(Table 1, page 171) Thorium and cobalt content of the total aggregate of manganese nodules from various locations

A criterion is suggested for discrimination between ferromanganese oxide minerals, deposited after the introduction of manganese and associated elements in sea water solution at submarine vulcanism, and minerals which are slowly formed from dilute solution, largely of continental origin. The simlultaneous injection of thorium into the ocean by submarine vulcanism is indicated, and its differentiation from continental thorium introduced into the ocean by runoff is discussed.

(Table S1) Geochemistry for sediment core MD02-2515

A high-resolution, 55-kyr long record of chalcophile and redox-sensitive trace element accumulation (Ag, Cd, Re, Mo) from MD02-2515, western Guaymas Basin, is investigated in conjunction with patterns in stratigraphy and productivity. High opal concentrations (~58 wt. %), representing increased diatom production, coincide with laminated sediments, and dilute the concentrations of organic carbon (Corg) and metals. A similarity between opal and normalized Corg, Ag and Cd concentrations suggests delivery to the sediments by diatom export production, while patterns in normalized Re and Mo accumulation suggest a different emplacement mechanism. Although Mo enrichment in organic-rich, laminated sediments typically represents anoxic conditions at other locations, Mo (and Re) in Guaymas Basin is enriched in nonlaminated and bioturbated sediments that are representative of oxygenated conditions. Adsorption onto Fe- and/or Mn-oxyhydroxide surfaces during oxygenation inadequately explains both the Re and Mo enrichments. Thus, recently published mechanisms invoking direct Re and Mo removal from the water column and bioturbation-assisted irrigation of Re into the sediments are used to explain the counterintuitive observations in Guaymas Basin. The MD02-2515 stratigraphic and proxy records are also different from other records in the northeast Pacific in that there is little correspondence with Greenland Dansgaard-Oeschger interstadials. There is some correlation with Heinrich events, suggesting that ventilation of intermediate waters and/or reduced productivity may be important in controlling stratigraphy and trace element accumulation. The results question whether MD02-2515 records can be compared to northeast Pacific open-margin records, especially before 17 kyr BP.

The morphological response of Emiliania huxleyi to seawater carbonate chemistry changes: an inter-strain comparison

Four strains of the coccolithophore Emiliania huxleyi (RCC1212, RCC1216, RCC1238, RCC1256) were grown in dilute batch culture at four CO2 levels ranging from ~200 µatm to ~1200 µatm. Coccolith morphology was analyzed based on scanning electron micrographs. Three of the four strains did not exhibit a change in morphology over the CO2 range tested. One strain (RCC1256) displayed an increase in the percentage of malformed coccoliths with increasing CO2 concentration. We conclude that the sensitivity of the coccolith-shaping machinery to carbonate chemistry changes is strain-specific. Although it has been shown before that carbonate chemistry related changes in growth- and calcification rate are strain-specific, there seems to be no consistent correlation between coccolith morphology and growth or calcification rate. We did not observe an increase in the percentage of incomplete coccoliths in RCC1256, indicating that the coccolith-shaping machinery per se is affected by acidification and not the signalling pathway that produces the stop-signal for coccolith growth.

Seawater carbonate chemistry, growth rate and morphology of Calcidiscus leptoporus (RCC1135) during experiments, 2011

The coccolithophore Calcidiscus leptoporus (strain RCC1135) was grown in dilute batch culture at CO2 levels ranging from ~200 to ~1600 µatm. Increasing CO2 concentration led to an increased percentage of malformed coccoliths and eventually (at ~1500 µatm CO2) to aggregation of cells. Carbonate chemistry of natural seawater was manipulated in three ways: first, addition of acid; second, addition of a HCO3/CO3 solution; and third, addition of both acid and HCO3/CO3 solution. The data set allowed the disentangling of putative effects of the different parameters of the carbonate system. It is concluded that CO2 is the parameter of the carbonate system which causes both aberrant coccolithogenesis and aggregation of cells.

Combined effects of ocean acidification and light or nitrogen availabilities on 13C fractionation in marine dinoflagellates

Along with increasing oceanic CO2 concentrations, enhanced stratification constrains phytoplankton to shallower upper mixed layers with altered light regimes and nutrient concentrations. Here, we investigate the effects of elevated pCO2 in combination with light or nitrogen-limitation on 13C fractionation (epsilon p) in four dinoflagellate species. We cultured Gonyaulax spinifera and Protoceratium reticulatum in dilute batches under low-light (LL) and high-light (HL) conditions, and grew Alexandrium fundyense and Scrippsiella trochoidea in nitrogen-limited continuous cultures (LN) and nitrogen-replete batches (HN). The observed CO2-dependency of epsilon p remained unaffected by the availability of light for both G. spinifera and P. reticulatum, though at HL epsilon p was consistently lower by about 2.7 per mil over the tested CO2 range for P. reticulatum. This may reflect increased uptake of (13C-enriched) bicarbonate fueled by increased ATP production under HL conditions. The observed CO2-dependency of epsilon p disappeared under LN conditions in both A. fundyense and S. trochoidea. The generally higher epsilon p under LN may be associated with lower organic carbon production rates and/or higher ATP:NADPH ratios. CO2-dependent epsilon p under non-limiting conditions has been observed in several dinoflagellate species, showing potential for a new CO2-proxy. Our results however demonstrate that light- and nitrogen-limitation also affect epsilon p, thereby illustrating the need to carefully consider prevailing environmental conditions.