(Table 1) Spacing of diatom abundance index and opal index at ODP Site 175-1084

An important discovery during Ocean Drilling Program Leg 175, when investigating the record of upwelling off Namibia, was the finding of a distinct Late Pliocene diatom maximum spanning the lower half of the Matuyama reversed polarity chron (MDM, Matuyama Diatom Maximum) and centered around 2.6-2.0 Ma. This maximum was observed at all sites off southwestern Africa between 20°S and 30°S, and is most strongly represented in sediments of Site 1084, off Lüderitz, Namibia. The MDM is characterized by high biogenic opal content, high numbers of diatom valves, and a diatom flora rich in Southern Ocean representatives (with Thalassiothrix antarctica forming diatom mats) as well as coastal upwelling components. Before MDM time, diatoms are rare until ca. 3.6 Ma. After the MDM, in the Pleistocene, the composition of the diatom flora points to increased importance of coastal upwelling toward the present, but is accompanied by a general decrease in opal and diatom deposition. Here we present a simple conceptual model as a first step in formalizing a possible forcing mechanism responsible for the record of opal deposition in the upwelling system off Namibia. The model takes into account Southern Ocean oceanography, and a link with deepwater circulation and deepwater nutrient chemistry which, in turn, are coupled to the evolution of North Atlantic Deep Water (NADW). The model proposes that between the MDM and the Mid-Pleistocene climate revolution, opal deposition off Namibia is not directly tied to glacial-interglacial fluctuations (as seen in the global d18O record), but that, instead, a strong deepwater link exists with increased NADW production (as seen in the deepwater d13C record) accounting for higher supply of silicate to the thermocline waters that feed the upwelling process. The opal record of Site 1084 shows affinity to eccentricity on the 400-kyr scale but not for the 100-kyr scale. This points toward long-term geologic processes for delivery of silica to the ocean.

Sea-suface microlayer (SML) and underlying water (ULW) samples focusing on CDOM spectral characteristics during METEOR cruise M91

The coastal upwelling system off the coast of Peru is characterized by high biological activity and a pronounced subsurface oxygen minimum zone, as well as associated emissions of atmospheric trace gases such as N2O, CH4 and CO2. From 3 to 23 December 2012, R/V Meteor (M91) cruise took place in the Peruvian upwelling system between 4.59 and 15.4°S, and 82.0 to 77.5°W. During M91 we investigated the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like chromophoric dissolved organic matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. We analyzed SML and underlying water (ULW) samples at 38 stations focusing on CDOM spectral characteristics as indicator of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slope (S) values and excitation-emission matrix fluorescence (EEMs), which allow us to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources and sinks. Spectral slope S varied between 0.012 to 0.043 1 nm-1 and was quite similar between SML and ULW, with no significant differences between the two compartments. Higher S values were observed in the ULW of the southern stations below 15°S. By EEMs, we identified five fluorescent components (F1-5) of the CDOM pool, of which two had excitation/emission characteristics of amino-acid-like fluorophores (F1, F4) and were highly enriched in the SML, with a median ratio SML : ULW of 1.5 for both fluorophores. In the study region, values for CDOM absorption ranged from 0.07 to 1.47 m-1. CDOM was generally highly concentrated in the SML, with a median enrichment with respect to the ULW of 1.2. CDOM composition and changes in spectral slope properties suggested a local microbial release of DOM directly in the SML as a response to light exposure in this extreme environment. In a conceptual model of the sources and modifications of optically active DOM in the SML and underlying seawater (ULW), we describe processes we think may take place (Fig. 1); the production of CDOM of higher MW by microbial release through growth, exudation and lysis in the euphotic zone, includes the identified fluorophores (F1, F2, F3, F4, F5). Specific amino-acid-like fluorophores (F1, F4) accumulate in the SML with respect to the ULW, as photochemistry may enhance microbial CDOM release by (a) photoprotection mechanisms and (b) cell-lysis processes. Microbial and photochemical degradation are potential sinks of the amino-acid-like fluorophores (F1, F4), and potential sources of reworked and more refractory humic-like components (F2, F3, F5). In the highly productive upwelling region along the Peruvian coast, the interplay of microbial and photochemical processes controls the enrichment of amino-acid-like CDOM in the SML. We discuss potential implications for air-sea gas exchange in this area.

Seawater carbonate chemistry, nutrients and growth rate during experiments with coral Astrangia poculata, 2010

Zooxanthellate colonies of the scleractinian coral Astrangia poculata were grown under combinations of ambient and elevated nutrients (5 µM NO, 0.3 µM PO4, and 2nM Fe) and CO2 (780 ppmv) treatments for a period of 6 months. Coral calcification rates, estimated from buoyant weights, were not significantly affected by moderately elevated nutrients at ambient CO2 and were negatively affected by elevated CO2 at ambient nutrient levels. However, calcification by corals reared under elevated nutrients combined with elevated CO2 was not significantly different from that of corals reared under ambient conditions, suggesting that CO2 enrichment can lead to nutrient limitation in zooxanthellate corals. A conceptual model is proposed to explain how nutrients and CO2 interact to control zooxanthellate coral calcification. Nutrient limited corals are unable to utilize an increase in dissolved inorganic carbon (DIC) as nutrients are already limiting growth, thus the effect of elevated CO2 on saturation state drives the calcification response. Under nutrient replete conditions, corals may have the ability to utilize more DIC, thus the calcification response to CO2 becomes the product of a negative effect on saturation state and a positive effect on gross carbon fixation, depending upon which dominates, the calcification response can be either positive or negative. This may help explain how the range of coral responses found in different studies of ocean acidification can be obtained.