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.

The influence of temperature and seawater carbonate saturation state on 13C-18O bond ordering in bivalve mollusks

The shells of marine mollusks are widely used archives of past climate and ocean chemistry. Whilst the measurement of mollusk delta 18O to develop records of past climate change is a commonly used approach, it has proven challenging to develop reliable independent paleothermometers that can be used to deconvolve the contributions of temperature and fluid composition on molluscan oxygen isotope compositions. Here we investigate the temperature dependence of 13C-18O bond abundance, denoted by the measured parameter Delta 47, in shell carbonates of bivalve mollusks and assess its potential to be a useful paleothermometer. We report measurements on cultured specimens spanning a range in water temperatures of 5 to 25 °C, and field collected specimens spanning a range of -1 to 29 °C. In addition we investigate the potential influence of carbonate saturation state on bivalve stable isotope compositions by making measurements on both calcitic and aragonitic specimens that have been cultured in seawater that is either supersaturated or undersaturated with respect to aragonite. We find a robust relationship between Delta 47 and growth temperature. We also find that the slope of a linear regression through all the Delta 47 data for bivalves plotted against seawater temperature is significantly shallower than previously published inorganic and biogenic carbonate calibration studies produced in our laboratory and go on to discuss the possible sources of this difference. We find that changing seawater saturation state does not have significant effect on the Delta 47 of bivalve shell carbonate in two taxa that we examined, and we do not observe significant differences between Delta 47-temperature relationships between calcitic and aragonitic taxa.

Impact of elevated levels of CO2 on animal mediated ecosystem function: The modification of sediment nutrient fluxes by burrowing urchins

A mesocosm experiment was conducted to quantify the relationships between the presence and body size of two burrowing heart urchins (Brissopsis lyrifera and Echinocardium cordatum) and rates of sediment nutrient flux. Furthermore, the impact of seawater acidification on these relationships was determined during this 40-day exposure experiment. Using carbon dioxide (CO2) gas, seawater was acidified to pHNBS 7.6, 7.2 or 6.8. Control treatments were maintained in natural seawater (pH = 8.0). Under normocapnic conditions, burrowing urchins were seen to reduce the sediment uptake of nitrite or nitrate whilst enhancing the release of silicate and phosphate. In acidified (hypercapnic) treatments, the biological control of biogeochemical cycles by urchins was significantly affected, probably through the combined impacts of high CO2 on nitrifying bacteria, benthic algae and urchin behaviour. This study highlights the importance of considering biological interactions when predicting the consequences of seawater acidification on ecosystem function.

Seawater carbonate chemistry, survival rate, shell size, calcification rate of the planktonic foraminifer Neogloboquadrina pachyderma (sinistral) in a laboratory experiment

The present study investigated the effects of ocean acidification and temperature increase on Neogloboquadrina pachyderma (sinistral), the dominant planktonic foraminifer in the Arctic Ocean. Due to the naturally low concentration of [CO3] 2- in the Arctic, this foraminifer could be particularly sensitive to the forecast changes in seawater carbonate chemistry. To assess potential responses to ocean acidification and climate change, perturbation experiments were performed on juvenile and adult specimens by manipulating seawater to mimic the present-day carbon dioxide level and a future ocean acidification scenario (end of the century) under controlled (in situ) and elevated temperatures (1 and 4 °C, respectively). Foraminifera mortality was unaffected under all the different experiment treatments. Under low pH, N. pachyderma (s) shell net calcification rates decreased. This decrease was higher (30 %) in the juvenile specimens than decrease observed in the adults (21 %) ones. However, decrease in net calcification was moderated when both, pH decreased and temperature increased simultaneously. When only temperature increased, a net calcification rate for both life stages was not affected. These results show that forecast changes in seawater chemistry would impact calcite production in N. pachyderma (s), possibly leading to a reduction of calcite flux contribution and consequently a decrease in biologic pump efficiency.

Effects of light and elevated pCO2 on the growth and photochemical efficiency of Acropora cervicornis

The effects of light and elevated pCO2 on the growth and photochemical efficiency of the critically endangered staghorn coral, Acropora cervicornis, were examined experimentally. Corals were subjected to high and low treatments of CO2 and light in a fully crossed design and monitored using 3D scanning and buoyant weight methodologies. Calcification rates, linear extension, as well as colony surface area and volume of A. cervicornis were highly dependent on light intensity. At pCO2 levels projected to occur by the end of the century from ocean acidification (OA), A. cervicornis exhibited depressed calcification, but no change in linear extension. Photochemical efficiency (F v /F m ) was higher at low light, but unaffected by CO2. Amelioration of OA-depressed calcification under high-light treatments was not observed, and we suggest that the high-light intensity necessary to reach saturation of photosynthesis and calcification in A. cervicornis may limit the effectiveness of this potentially protective mechanism in this species. High CO2 causes depressed skeletal density, but not linear extension, illustrating that the measurement of extension by itself is inadequate to detect CO2 impacts. The skeletal integrity of A. cervicornis will be impaired by OA, which may further reduce the resilience of the already diminished populations of this endangered species.

Vanishing coccolith vital effects with alleviated carbon limitation

By recreating a range of geologically relevant concentrations of dissolved inorganic carbon (DIC) in the laboratory, we demonstrate that the magnitude of the vital effects in both carbon and oxygen isotopes of coccolith calcite of multiple species relates to ambient DIC concentration. Under high DIC levels, all the examined coccoliths exhibit significantly reduced isotopic offsets from inorganic calcite compared to the substantial vital effects expressed at low (preindustrial and present-day) DIC concentrations. The supply of carbon to the cell exerts a primary control on biological fractionation in coccolith calcite via the modulation of coccolithophore growth rate, cell size and carbon utilisation by photosynthesis and calcification, altogether accounting for the observed interspecific differences between coccolith species. These laboratory observations support the recent hypothesis from field observations that the appearance of interspecific vital effect in coccolithophores coincides with the long-term Neogene decline of atmospheric CO2 concentrations and bring further valuable constraints by demonstrating a convergence of all examined species towards inorganic values at high pCO2 regimes. This study provides palaeoceanographers with a biogeochemical framework that can be utilised to further develop the use of calcareous nannofossils in palaeoceanography to derive sea surface temperature and pCO2 levels, especially during periods of relatively elevated pCO2 concentrations, as they prevailed during most of the Meso-Cenozoic.

Lack of evidence for elevated CO2-induced bottom-up effects on marine copepods: a dinoflagellate-calanoid prey-predator pair

Rising levels of atmospheric CO2 are responsible for a change in the carbonate chemistry of seawater with associated pH drops (acidification) projected to reach 0.4 units from 1950 to 2100. We investigated possible indirect effects of seawater acidification on the feeding, fecundity, and hatching success of the calanoid copepod Acartia grani, mediated by potential CO2-induced changes in the nutritional characteristics of their prey. We used as prey the autotrophic dinoflagellate Heterocapsa sp., cultured at three distinct pH levels (control: 8.17, medium: 7.96, and low: 7.75) by bubbling pure CO2 via a computer automated system. Acartia grani adults collected from a laboratory culture were acclimatized for 3 d at food suspensions of Heterocapsa from each pH treatment (ca. 500 cells/ml; 300 ?g C/l). Feeding and egg production rates of the preconditioned females did not differ significantly among the three Heterocapsa diets. Egg hatching success, monitored once per day for the 72 h, did not reveal significant difference among treatments. These results are in agreement with the lack of difference in the cellular stoichiometry (C : N, C : P, and N : P ratios) and fatty acid concentration and composition encountered between the three tested Heterocapsa treatments. Our findings disagree with those of other studies using distinct types of prey, suggesting that this kind of indirect influence of acidification on copepods may be largely associated with interspecific differences among prey items with regard to their sensitivity to elevated CO2 levels.