Accumulation rates and composition of organic matter in sediments off Peru

Deep-sea sediment samples from three Ocean Drilling Program (ODP) Leg 112 sites on the Peru continental margin were investigated, using a number of organic geochemical and organic petrographic techniques, for amounts and compositions of the organic matter preserved. Preliminary results include mass accumulation rates of organic carbon at Site 679 and characteristics of the organic facies for sediments from Sites 679, 681, and 684. Organic-carbon contents are high, with few exceptions. Particularly high values were determined in the Pliocene interval at Site 684 (4%-7.5%) and in the early Pliocene to Quaternary section of Hole 679D (2%-9%). Older sediments at this site have distinctively lower organic-carbon contents (0.2%-2.5%). Mass accumulation rates of organic matter at Site 679 are 0.02 to 0.07 g carbon/cm**2/k.y. for late Miocene to early Pliocene sediments and higher by a factor of 5 to 10 in the Quaternary sediments. The organic matter in all samples has a predominantly marine planktonic and bacterial origin, with minor terrigenous contribution. Organic particle sizes are strikingly small, so that only a minor portion is covered by visual maceral analysis. Molecular organic-geochemical data were obtained for nonaromatic hydrocarbons, aromatic hydrocarbons (including sulfur compounds), alcohols, ketones, esters, and carboxylic acids. Among the total extractable lipids, long-chain unsaturated ketones from Prymnesiophyte algae strongly predominate among the gas chromatography (GC) amenable components. Steroids are major constituents of the ketone and free- and bound-alcohol fractions. Perylene is the most abundant aromatic hydrocarbon, whereas in the nonaromatic hydrocarbon fractions, long-chain n-alkanes from higher land plants predominate, although the total terrigenous organic matter proportion in the sediments is small.

Stable isotope record and composition of planktonic foraminifera from ODP Site 172-1056

The stable isotopic composition of two planktonic foraminifer species (Globigerinoides sacculifer and Neogloboquadrina dutertrei) and two benthic foraminifer species (Cibicidoides wuellerstorfi and Uvigerina peregrina) was measured at sub-orbital resolution through the marine isotope stages (MISs) 10, 11, and 12 (345-460 ka) at Site 1056 on the Blake-Bahama Outer Ridge. Planktonic foraminifers were counted for the interval 405-450 ka at 2-4-kyr resolution. Site 1056 (32°29'N, 76°20'W) is located on the continental slope (water depth: 2167 m) beneath the Gulf Stream. The average rate of sediment accumulation through the interval is 11.4 cm/kyr, but sediment accumulation is much more rapid during glacial intervals (15-17 cm/kyr). The decline in percent carbonate during glacial intervals, and its rise during interglacials, indicates that the increased sediment supply is of terrigenous origin. Low carbonate values and low benthic delta13C, which are both associated with a weak Western Boundary Undercurrent and low North Atlantic Deep Water production, persist for 6 kyr after the benthic delta18O record indicates that ice volume has begun to decrease. Recovery of carbonate and benthic delta13C values is abrupt and rapid. Millennial-scale variation (~3-4 kyr) is apparent in the glacial intervals of the planktonic delta18O records and is more pronounced in a Delta delta18O record, which represents the temperature range in the photic zone. Semi-precessional (10-12-kyr) cycles are apparent in the planktonic deltadelta13C record. The millennial-scale cycles are largely caused by an increase in G. sacculifer delta18O and represent surface warming. They are interpreted as representing periodic increases in westward intensification of the gyre. The semi-precessional cycles are driven by changes in the N. dutertrei delta13C and represent fluctuations in the Gulf Stream itself and therefore likely have a tropical origin. Planktonic foraminifer census counts did not show an expected response to one of the largest glacial/interglacial transitions of the late Pleistocene. The most obvious change was an increase in faunal diversity during MIS 12.2, the interval of maximum delta18O values. This suggests that cool slope water and warm subtropical gyre water penetrated a more sluggish Gulf Stream with greater frequency at this time. The millennial-scale maxima in the Delta delta18O record are accompanied by decreases in diversity, which is consistent with the interpretation of surface warming during these events.

Description and composition iron-manganese concretions from the Pacific

One the most interesting features of ocean sedimentation is the manganese formations on the surface of the ocean floor in some areas. These are especially widespread in the Pacific Ocean as concretions, grains, and crusts on rock fragments and bedrock outcrops. Iron-manganese concretions are the most abundant as they completely cover about 10% of the bottom of the Pacific Ocean where there are ore concentrations. The concretions occupy from 20-50% of the bottom and up to 80-90% on separate submarine rises. Such concretions are found in different types of bottom deposits, from abyssal red clays to terrigenous muds, but they occur most widely in red clays and quite often in carbonate muds. Their shape and their dimensions are very diverse and change from place to place, from station to station, varying from 0.5-20 cm. They may be oval, globular, reniform, or slaggy and often they are fiat or isometric concretions of an indefinite shape. The concretions generally have nuclei of pumice, basalt fragments, clayey and tuffaceous material, sharks' teeth, whale ossicles, and fossil sponges. Most concretions have concentric layers, combined with dendritic ramifications of iron and manganese oxides.

Table 3.1 Content and composition of air in an ice profile from Camp III i Greenland

The air trapped in freshly formed ice gives information concerning the ice formation processes as weH as concerning severa,l environmental parameters at the time of ice formation. Air arnount, air composition, and the size and form of bubbles may change with time. Possible processes responsible for such changes are discussed. In very cold ice air content and air composition remain almost unchanged. Samples of ancient atmospheric air are therefore very weH preserved in cold ice. In temperate ice changes of the air amount and air composition depend on the intergranular water fiow through the glacier. This waterfiow can be estimated by measuring air amount and air composition in ice sampIes.

Table 3.5 Content and composition of air in fresh ice

Natural ice is formed by freezing of water or by sintering of dry or wet snow. Each of these processes causes atmospheric air to be enclosed in ice as bubbles. The air amount and composition as well as the bubble sizes and density depend not only on the kind of process but also on several environmental conditions. The ice in the deepest layers of the Greenland and thc Antarctic ice sheet was formed more than 100 000 years ago. In the bubbles of this ice, samples of atmospheric air from that time are preserved. The enclosure of air is discussed for each of the three processes. Of special interest are the parameters which control the amount and composition of the enclosed air. If the ice is formed by sintering of very cold dry snow, the air composition in the bubbles corresponds with good accuracy to the composition of atmospheric air.

Stable carbon and oxygen isotope composition of Recent, Tertiary and Cretaceous foraminifera (Table III)

Oxygen isotope analyses of Tertiary and Cretaceous planktic foraminifera indicate that species have been stratified with respect to depth in the water column at least since Albian time. There is a relationship between morphology and depth habitat. Species with globigerine morphology have consistently occupied shallower depths than have species with globorotalid morphology. Biserially arranged species occupied both shallow and deep levels in the water column. On the average, it appears that ancient species with shallow habitats have been more susceptible to dissolution and have been preserved less well than species dwelling in deeper habitats. This relationship is similar to that observed for Recent planktic foraminifera. Comparison of carbon isotope ratios of adult and juvenile forms indicates that either the source of the carbon found in the shell or the carbon isotopic fractionations which occur during calcite secretion change during the development of individual foraminifera. The carbon isotopic ratios do not provide a reliable means for reconstructing the depth habitats of ancient species. Temperature-depth profiles for tropical Tertiary oceans have been reconstructed from the isotopic temperatures of planktic and benthic foraminifera. The vertical thermal structure of Oligocene oceans resembled that of modern oceans most closely. Those of Paleocene and Maastrichtian times differed most from that of modern oceans.

Seawater carbonate chemistry and elemental composition of purple sea urchin (Strongylocentrotus purpuratus) calcite in a laboratory experiment

Ocean acidification will likely have negative impacts on invertebrates producing skeletons composed of calcium carbonate. Skeletal solubility is partly controlled by the incorporation of "foreign" ions (e.g. magnesium) into the crystal lattice of these skeletal structures, a process that is sensitive to a variety of biological and environmental factors. Here we explore effects of life stage, oceanographic region of origin, and changes in the partial pressure of carbon dioxide in seawater (pCO2) on trace elemental composition in the purple sea urchin (Strongylocentrotus purpuratus). We show that, similar to other urchin taxa, adult purple sea urchins have the ability to precipitate skeleton composed of a range of biominerals spanning low- to high-Mg calcites. Mg / Ca and Sr / Ca ratios were substantially lower in adult spines compared to adult tests. On the other hand, trace elemental composition was invariant among adults collected from four oceanographically distinct regions spanning a range of carbonate chemistry conditions (Oregon, Northern California, Central California, and Southern California). Skeletons of newly settled juvenile urchins that originated from adults from the four regions exhibited intermediate Mg / Ca and Sr / Ca between adult spine and test endmembers, indicating that skeleton precipitated during early life stages is more soluble than adult spines and less soluble than adult tests. Mean skeletal Mg / Ca or Sr / Ca of juvenile skeleton did not vary with source region when larvae were reared under present-day, global-average seawater carbonate conditions (400 µatm; pHT = 8.02 ± 0.03 1 SD; Omega calcite = 3.3 ± 0.2 1 SD). However, when reared under elevated pCO2 (900 µatm; pHT = 7.73 ± 0.03; Omega calcite = 1.8 ± 0.1), skeletal Sr / Ca in juveniles exhibited increased variance across the four regions. Although larvae from the northern populations (Oregon, Northern California, Central California) did not exhibit differences in Mg or Sr incorporation under elevated pCO2 (Sr / Ca = 2.10 ± 0.06 mmol/mol; Mg / Ca = 67.4 ± 3.9 mmol/mol), juveniles of Southern California origin partitioned ~8% more Sr into their skeletons when exposed to higher pCO2 (Sr / Ca = 2.26 ± 0.08 vs. 2.09 ± 0.005 mmol/mol 1 SD). Together these results suggest that the diversity of carbonate minerologies present across different skeletal structures and life stages in purple sea urchins does not translate into an equivalent geochemical plasticity of response associated with geographic variation or temporal shifts in seawater properties. Rather, composition of S. purpuratus skeleton precipitated during both early and adult life history stages appears relatively robust to spatial gradients and predicted future changes in carbonate chemistry. An exception to this trend may arise during early life stages, where certain populations of purple sea urchins may alter skeletal mineral precipitation rates and composition beyond a given pCO2 threshold. This potential for geochemical plasticity during early development in contrast to adult stage geochemical resilience adds to the growing body of evidence that ocean acidification can have differing effects across organismal life stages.

(Table T1) Geochemical composition of tochilinite and related minerals of ODP Hole 173-1068A

Tochilinite (approximately FeS(Mg,Fe)(OH)2) is locally abundant in Hole 1068A serpentinites from Cores 173-1068A-21R and 22R. It occurs in veins, as fillings in void space, and in intergrowths with serpentine and andradite. An apparently related mineral, but with Ca and Al largely replacing Mg, occurs in association with, and possibly as a replacement of, pyrrhotite in serpentinite breccias from the bottom of Core 173-1068A-20R. The transition from Mg-Fe-rich brucite tochilinites to Ca- and S-rich carbonate tochilinites is consistent with increasing sulfur and oxygen activity upsection. Tochilinite has been reported at other sites on the Iberia Abyssal Plain and is abundant to the point of being a rock-forming mineral in several samples from Site 1068. Rather than being a mineralogical curiosity, tochilinite appears to be common and a major sink for sulfur in the upper serpentinites of the Iberia Abyssal Plain.

Description and chemical and mineral composition of iron oxide samples from two Finnish lakes

Fifteen iron oxide accumulations from the bottoms of two Finnish lakes ("lake ores") were found to contain as much as 50% Fe. Differential X-ray powder diffraction and selective dissolution by oxalate showed that the samples consisted of poorly crystallized goethite and ferrihydrite. The crust ores of one lake had higher ferrihydrite to goethite ratios than the nodular ores of the other lake. The higher ferrihydrite proportion was attributed to a higher rate of Fe2+ supply from the ground water and/or a higher rate of oxidation as a function of water depth and bottom-sediment permeability. Values of Al-for-Fe substitution of the goethites determined from unit-cell dimensions agreed with those obtained from chemical extraction if the unit-cell volume rather than the c dimension was used. In very small goethite crystals a slight expansion of the a unit-cell dimension is probaby compensated by a corresponding contraction of the c dimension, so that a contraction of the c dimension need not necessarily be caused by Al substitution. The goethites of the two lakes differed significantly in their Al-for-Fe substitutions and hence in their unit-cell sizes, OH-bending characteristics, dehydroxylation temperatures, dissolution kinetics, and Mössbauer parameters. The difference in Al substitution (0 vs. 7 mole %) is attributed to the Al-supplying power of the bottom sediments: the silty-clayey sediments in one lake appear to have supplied A1 during goethite formation, whereas the gravelly-sandy sediments in the other lake did not. The compositions of the goethites thus reflect their environments of formation.

(Table 1) Water column biogenic silica concentrations and Si isotopic composition during Marion Dufresne cruise MD166 off South Africa

Southern Ocean biogeochemical processes have an impact on global marine primary production and global elemental cycling, e.g. by likely controlling glacial-interglacial pCO2 variation. In this context, the natural silicon isotopic composition (d30Si) of sedimentary biogenic silica has been used to reconstruct past Si-consumption:supply ratios in the surface waters. We present a new dataset in the Southern Ocean from a IPY-GEOTRACES transect (Bonus-GoodHope) which includes for the first time summer d30Si signatures of suspended biogenic silica (i) for the whole water column at three stations and (ii) in the mixed layer at seven stations from the subtropical zone up to the Weddell Gyre. In general, the isotopic composition of biogenic opal exported to depth was comparable to the opal leaving the mixed layer and did not seem to be affected by any diagenetic processes during settling, even if an effect of biogenic silica dissolution cannot be ruled out in the northern part of the Weddell Gyre. We develop a mechanistic understanding of the processes involved in the modern Si-isotopic balance, by implementing a mixed layer model. We observe that the accumulated biogenic silica (sensu Rayleigh distillation) should satisfactorily describe the d30Si composition of biogenic silica exported out of the mixed layer, within the limit of the current analytical precision on the d30Si. The failures of previous models (Rayleigh and steady state) become apparent especially at the end of the productive period in the mixed layer, when biogenic silica production and export are low. This results from (1) a higher biogenic silica dissolution:production ratio imposing a lower net fractionation factor and (2) a higher Si-supply:Si-uptake ratio supplying light Si-isotopes into the mixed layer. The latter effect is especially expressed when the summer mixed layer becomes strongly Si-depleted, together with a large vertical silicic acid gradient, e.g. in the Polar Front Zone and at the Polar Front.