Geochemistry of Peru margin sediments

This data report tabulates results of chemical analyses of sediments from four sites (680, 682, 685, and 688) drilled during Leg 112 offshore Peru. These sediments were recovered from the forearc basins underlying the Peru upwelling area. They are equivalent in facies and age to the Pisco and Monterey formations, both of which are of considerable economic and geological interest as hydrocarbon source rocks deposited under conditions of coastal upwelling. Sediments recovered from the shelf (Site 680) and slope (Sites 682, 685, and 688) during Leg 112 are unconsolidated and are thermally immature. A lack of consolidation and thermal catagenesis makes these deposits ideal targets for chemical investigation into effects of early diagenesis in organic-carbon-rich siliceous muds.

Lithium sources in pore fluids of Peru slope

High Li concentrations, up to a maximum of 1155 µM are observed in the pore fluids of the Peru convergent margin slope sediments. At Ocean Drilling Program Sites 683 and 685 (ca. 9°S), the Li concentration depth gradients are twice as steep as at Site 682 and 688 (ca. 11°S). Within the sediments, the most important Li sources are from aluminosilicate minerals. Biogenic opal-A contains little Li and thus dilutes the Li concentration of the bulk sediments. The sediment compositions and the thermal regimes are similar at 9° and 11°S, suggesting there is an additional, non-sedimentary source for the observed high Li concentrations in the northern pore fluids. At 9°S, the 87Sr/86Sr ratios reach a maximum value of 0.709958. The observed radiogenic 87Sr/86Sr values in the pore fluids support the suggestion that the additional Li may derive from exchange reactions with underlying continental crust. The high concentrations of Li at 11°S may derive from basalt alteration at moderate to high temperatures, as suggested by the non-radiogenic 87Sr/86Sr ratios in these pore fluids, which reach a minimum value of 0.707218. Based on (1) Li concentrations in the pore fluids in slope sediments from Peru and several other margins, and (2) an approximate estimate of fluid flux from continental margins into the ocean, continental margins provide an estimated 1 to 3 * 10**10 moles Li/yr to the ocean. This source of oceanic Li, which has not been considered previously, is of the same order of magnitude as some estimates of hydrothermal and river Li fluxes and may have important consequences for the oceanic Li isotope budget. The sink is unknown for this newly discovered and possibly large Li source, but it may be more pervasive low-temperature alteration of oceanic basement than previously estimated, or burial of mineral phases, such as authigenic clay minerals, or metal oxyhydroxides which may be Li-rich.

The organic sea-surface microlayer in the upwelling region off the coast of Peru and potential implications for air-sea exchange processes

The sea-surface microlayer (SML) is at the upper- most surface of the ocean, linking the hydrosphere with the atmosphere. The presence and enrichment of organic compounds in the SML have been suggested to influence air- sea gas exchange processes as well as the emission of primary organic aerosols. Here, we report on organic matter components collected from an approximately 50µm thick SML and from the underlying water (ULW), ca. 20 cm below the SML, in December 2012 during the SOPRAN METEOR 91 cruise to the highly productive, coastal upwelling regime off the coast of Peru. Samples were collected at 37 stations including coastal upwelling sites and off-shore stations with less organic matter and were analyzed for total and dissolved high molecular weight (> 1 kDa) combined carbohydrates (TCCHO, DCCHO), free amino acids (FAA), total and dissolved hydrolyzable amino acids (THAA, DHAA), transparent exopolymer particles (TEP), Coomassie stainable particles (CSPs), total and dissolved organic carbon (TOC, DOC), total and dissolved nitrogen (TN, TDN), as well as bacterial and phytoplankton abundance. Our results showed a close coupling between organic matter concentrations in the water column and in the SML for almost all components except for FAA and DHAA that showed highest enrichment in the SML on average. Accumulation of gel particles (i.e., TEP and CSP) in the SML differed spatially. While CSP abundance in the SML was not related to wind speed, TEP abundance decreased with wind speed, leading to a depletion of TEP in the SML at about 5 m s-1 . Our study provides insight to the physical and biological control of organic matter enrichment in the SML, and discusses the potential role of organic matter in the SML for air-sea exchange processes.

Organic matter preservation in sediments of the Peru and Oman continental margin

Detailed petrographical and bulk geochemical investigations of organic matter (OM) have been performed on sediments deposited below or close to upwelling areas offshore Peru (ODP-Leg 112; Sites 679, 681, 688) and Oman (ODP-Leg 117; Sites 720, 723, 724) in order to obtain a quantitative understanding of its accumulation and degradation. Microscopical as well as nanoscopical investigations reveal that the OM in sediments affected by upwelling mechanisms mainly (up to 98%) consists of unstructured (amorphous) organic aggregates without any apparent biological structures. In sediments which are not or to a lesser extent affected by upwelling (Site 720) terrestrial OM predominates. Organic carbon (TOC) contents are highly variable and range between 9.8% in sediments deposited below upwelling cells and 0.2% in sediments outside the upwelling zone. The TOC/sulphur ratios of the sediments scatter widely. The samples from the deep-water locations (Sites 688 and 720), show C/S-ratios of "normal" marine sediments, whereas at the other locations no correlation or even a negative correlation between sulphur and TOC concentration exists. In most of the upwelling-influenced sediments OM contains a significant amount of sulphur. The incorporation of sulphur into the OM followed microbial sulphate reduction and occurred in the upper meters of the sedimentary column. Below, OM is still present in vast amounts and relatively hydrogen-rich, but is nevertheless non-metabolizable and becomes the limiting factor for bacterial sulphate reduction. According to mass balance calculations 90-99% of the OM produced in the photic zone was remineralized and 1-3% was consumed by microbial sulphate reduction. The aerobic and anaerobic processes have greatly affected degradation and conservation of OM.

Characterization of sorbed volatile hydrocarbons from the Peru margin

Bacterial and thermogenic hydrocarbons are present in the sorbed-gas fraction of Peru margin sediments. At Ocean Drilling Program (ODP) Sites 681, 682, 684, and 686, bacterial gases are restricted to the early diagenetic zones, where dissolved sulfate has been exhausted and methanogenesis occurs. Methane migrating into the sulfate zone at Sites 681, 684, 686, and possibly 682, has been consumed anaerobically by methanotrophs, maintaining the low concentrations and causing an isotope shift in d13C(CH4) to more positive values. Significant amounts of C2+ hydrocarbons occur at the shelf Sites 680/681, 684, and 686/687, where these hydrocarbons may be associated with hypersaline fluids. There is evidence at Site 679 that sorbed C2+ hydrocarbons may also have been transported by hypersaline fluids. This characteristic C2+ hydrocarbon signature in the sorbed-gas fractions of sediments at Site 679 is not reflected in data obtained using the conventional "free-," "canned-," or "headspace-gas" procedures. The molecular and isotope compositions of the sorbed-gas fraction indicate that this gas may have a thermogenic source and may have spilled over with the hypersaline fluids from the Salaverry Basin into the Lima Basin. These traces of thermogenic hydrocarbon gases are over-mature (about 1.5% Ro) and are discordant with the less-mature sediments in which they are found. This observation supports the migration of these hydrocarbons, possibly from continental sources. Sorbed-gas analyses may provide important geochemical information, in addition to that of the free-gases. Sorbed-gases are less sensitive to activities in the interstitial fluids, such as methanogenesis and methanotrophy, and may faithfully record the migration of hydrocarbons associated with hypersaline fluids.

Chemical composition of phosphorite nodules off Peru

Phosphorite nodules collected during Cruise 8 of R/V Dmitry Mendeleev off the Peruvian coast are represented by three lithologic types: friable, compacted, and solid. As the nodules are progressively compacted, contents of phosphate components increase and of non-phosphate components decrease. Isotope composition of uranium in the friable nodules is the same as in ocean water, and diatoms contained in the nodules are represented by recent species indicating Late Quaternary age of the nodules.

Clay mineraology and grain size composition of surface sediments from South Pacific Ocean

The reconstruction of low-latitude ocean-atmosphere interactions is one of the major issues of (paleo-)environmental studies. The trade winds, extending over 20° to 30° of latitude in both hemispheres, between the subtropical highs and the intertropical convergence zone, are major components of the atmospheric circulation and little is known about their long-term variability on geological time-scales, in particular in the Pacific sector. We present the modern spatial pattern of eolian-derived marine sediments in the eastern equatorial and subtropical Pacific (10°N to 25°S) as a reference data set for the interpretation of SE Pacific paleo-dust records. The terrigenous silt and clay fractions of 75 surface sediment samples have been investigated for their grain-size distribution and clay-mineral compositions, respectively, to identify their provenances and transport agents. Dust delivered to the southeast Pacific from the semi- to hyper-arid areas of Peru and Chile is rather fine-grained (4-8 µm) due to low-level transport within the southeast trade winds. Nevertheless, wind is the dominant transport agent and eolian material is the dominant terrigenous component west of the Peru-Chile Trench south of ~ 5°S. Grain-size distributions alone are insufficient to identify the eolian signal in marine sediments due to authigenic particle formation on the sub-oceanic ridges and abundant volcanic glass around the Galapagos Islands. Together with the clay-mineral compositions of the clay fraction, we have identified the dust lobe extending from the coasts of Peru and Chile onto Galapagos Rise as well as across the equator into the doldrums. Illite is a very useful parameter to identify source areas of dust in this smectite-dominated study area.

Radiolarian biostratigraphy in sediments of ODP Site 202-1237

Site 1237 is located on Nazca Ridge ~140 km off the coast of Peru and thus within the offshore region of the Peru-Chile Current. A total of 83 samples were used to provide an initial radiolarian biostratigraphic framework for Site 1237; radiolarians are present to Sample 202-1237B-19H-2, 58-60 cm (186.45 meters composite depth [mcd]) and are of good to fair abundance and preservation. Site 1237 is influenced by both subtropical and northward-transported southern latitude waters, has 55 ash layers within the uppermost 166 m, and has minimal to gross reworking. Shipboard paleomagnetic results showed that the upper 200 m spanned the last 12 m.y., and in the upper 100 mcd, the paleomagnetic inclination pattern could be directly correlated to the geomagnetic polarity timescale (GPTS). Tropical biostratigraphy was used to establish the zonal boundaries for Site 1237, and the paleomagnetic and radiolarian stratigraphy were well correlated.