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.

Macroalgal responses to ocean acidification depend on nutrient and light levels

Ocean acidification may benefit algae that are able to capitalize on increased carbon availability for photosynthesis, but it is expected to have adverse effects on calcified algae through dissolution. Shifts in dominance between primary producers will have knock-on effects on marine ecosystems and will likely vary regionally, depending on factors such as irradiance (light vs. shade) and nutrient levels (oligotrophic vs. eutrophic). Thus experiments are needed to evaluate interactive effects of combined stressors in the field. In this study, we investigated the physiological responses of macroalgae near a CO2 seep in oligotrophic waters off Vulcano (Italy). The algae were incubated in situ at 0.2 m depth using a combination of three mean CO2 levels (500, 700-800 and 1200 µatm CO2), two light levels (100 and 70% of surface irradiance) and two nutrient levels of N, P, and K (enriched vs. non-enriched treatments) in the non-calcified macroalga Cystoseira compressa (Phaeophyceae, Fucales) and calcified Padina pavonica (Phaeophyceae, Dictyotales). A suite of biochemical assays and in vivo chlorophyll a fluorescence parameters showed that elevated CO2 levels benefitted both of these algae, although their responses varied depending on light and nutrient availability. In C. compressa, elevated CO2 treatments resulted in higher carbon content and antioxidant activity in shaded conditions both with and without nutrient enrichment-they had more Chla, phenols and fucoxanthin with nutrient enrichment and higher quantum yield (Fv/Fm) and photosynthetic efficiency (alpha ETR) without nutrient enrichment. In P. pavonica, elevated CO2 treatments had higher carbon content, Fv/Fm, alpha ETR, and Chla regardless of nutrient levels-they had higher concentrations of phenolic compounds in nutrient enriched, fully-lit conditions and more antioxidants in shaded, nutrient enriched conditions. Nitrogen content increased significantly in fertilized treatments, confirming that these algae were nutrient limited in this oligotrophic part of the Mediterranean. Our findings strengthen evidence that brown algae can be expected to proliferate as the oceans acidify where physicochemical conditions, such as nutrient levels and light, permit.

Effects of elevated pCO2 on the post-settlement development of Pocillopora damicornis

Ocean acidification represents a key threat to the recruitment of scleractinian corals. Here, we investigated the effect of increased partial pressure of carbon dioxide (pCO2) on the early development of Pocillopora damicornis by rearing the recruits for 12 days at 3 pCO2 levels (446, 896 and 1681 µatm). Results showed that increased pCO2 exerted minor effects on symbiont density and maximum quantum yield (Fv/Fm), while significantly enhanced the relative electron transport through photosystem II (PSII) of Symbiodinium. Notably, calcification and biomass of recruits decreased sharply by 34% and 24% respectively in 896 µatm, and tended to remain constant as pCO2 was raised from 896 to 1681 µatm. Furthermore, recruits in 1681 ?atm, with comparable surface area as those in 896 µatm, produced fewer buds. These findings indicated that juvenile P. damicornis under high pCO2 would enhance electron transport rate and suppress asexual budding to favor skeletal and tissue growths, which are more critical for their persistence and survival in a high pCO2 environment. This work suggested the physiological plasticity of juvenile corals under short-term exposure to elevated pCO2.

The response of Antarctic sea ice algae to changes in pH and CO2

Ocean acidification substantially alters ocean carbon chemistry and hence pH but the effects on sea ice formation and the CO2 concentration in the enclosed brine channels are unknown. Microbial communities inhabiting sea ice ecosystems currently contribute 10-50% of the annual primary production of polar seas, supporting overwintering zooplankton species, especially Antarctic krill, and seeding spring phytoplankton blooms. Ocean acidification is occurring in all surface waters but the strongest effects will be experienced in polar ecosystems with significant effects on all trophic levels. Brine algae collected from McMurdo Sound (Antarctica) sea ice was incubated in situ under various carbonate chemistry conditions. The carbon chemistry was manipulated with acid, bicarbonate and bases to produce a pCO2 and pH range from 238 to 6066 µatm and 7.19 to 8.66, respectively. Elevated pCO2 positively affected the growth rate of the brine algal community, dominated by the unique ice dinoflagellate, Polarella glacialis. Growth rates were significantly reduced when pH dropped below 7.6. However, when the pH was held constant and the pCO2 increased, growth rates of the brine algae increased by more than 20% and showed no decline at pCO2 values more than five times current ambient levels. We suggest that projected increases in seawater pCO2, associated with OA, will not adversely impact brine algal communities.

Ocean acidification has no effect on thermal bleaching in the coral Seriatopora caliendrum

The objective of this study was to test whether elevated pCO2 predicted for the year 2100 (85.1 Pa) affects bleaching in the coral Seriatopora caliendrum (Ehrenberg 1834) either independently or interactively with high temperature (30.5 °C). Response variables detected the sequence of events associated with the onset of bleaching: reduction in the photosynthetic performance of symbionts as measured by maximum photochemical efficiency (F v/F m) and effective photochemical efficiency (delta F/F m') of PSII, declines in net photosynthesis (P net) and photosynthetic efficiency (alpha), and finally, reduced chlorophyll a and symbiont concentrations. S. caliendrum was collected from Nanwan Bay, Taiwan, and subjected to combinations of temperature (27.7 vs. 30.5 °C) and pCO2 (45.1 vs. 85.1 Pa) for 14 days. High temperature reduced values of all dependent variables (i.e., bleaching occurred), but high pCO2 did not affect Symbiodinium photophysiology or productivity, and did not cause bleaching. These results suggest that short-term exposure to 81.5 Pa pCO2, alone and in combination with elevated temperature, does not cause or affect coral bleaching.

Properties of seawater and particulate matter (fluorescence) from a WETLabs Eco-FL sensor mounted on the continuous surface water sampling system during the Tara Oceans expedition 2009-2013

The Tara Oceans Expedition (2009-2013) sampled the world oceans on board a 36 m long schooner, collecting environmental data and organisms from viruses to planktonic metazoans for later analyses using modern sequencing and state-of-the-art imaging technologies. Tara Oceans Data are particularly suited to study the genetic, morphological and functional diversity of plankton. The present data set provides continuous measurements made with a WETLabs Eco-FL sensor mounted on the flowthrough system between June 4th, 2011 and March 30th, 2012. Data was recorded approximately every 10s. Two issues affected the data: 1. Periods when the water 0.2µm filtered water were used as blanks and 2. Periods where fluorescence was affected by non-photochemical quenching (NPQ, chlorophyll fluorescence is reduced when cells are exposed to light, e.g. Falkowski and Raven, 1997). Median data and their standard deviation were binned to 5min bins with period of light/dark indicated by an added variable (so that NPQ affected data could be neglected if the user so chooses). Data was first calibrated using HPLC data collected on the Tara (there were 36 data within 30min of each other). Fewer were available when there was no evident NPQ and the resulting scale factor was 0.0106 mg Chl m-3/count. To increase the calibration match-ups we used the AC-S data which provided a robust estimate of Chlorophyll (e.g. Boss et al., 2013). Scale factor computed over a much larger range of values than HPLC was 0.0088 mg Chl m-3/count (compared to 0.0079 mg Chl m-3/count based on manufacturer). In the archived data the fluorometer data is merged with the TSG, raw data is provided as well as manufacturer calibration constants, blank computed from filtered measurements and chlorophyll calibrated using the AC-S. For a full description of the processing of the Eco-FL please see Taillandier, 2015.

Solar UV irradiances modulate effects of ocean acidification on the Coccolithophorid Emiliania huxleyi

Emiliania huxleyi, the most abundant coccolithophorid in the oceans, is naturally exposed to solar UV radiation (UVR, 280-400 nm) in addition to photosynthetically active radiation (PAR). We investigated the physiological responses of E. huxleyi to the present day and elevated CO2 (390 vs 1000 µatm; with pH(NBS) 8.20 vs 7.86) under indoor constant PAR and fluctuating solar radiation with or without UVR. Enrichment of CO2 stimulated the production rate of particulate organic carbon (POC) under constant PAR, but led to unchanged POC production under incident fluctuating solar radiation. The production rates of particulate inorganic carbon (PIC) as well as PIC/POC ratios were reduced under the elevated CO2, ocean acidification (OA) condition, regardless of PAR levels, and the presence of UVR. However, moderate levels of UVR increased PIC production rates and PIC/POC ratios. OA treatment interacted with UVR to influence the alga's physiological performance, leading to reduced specific growth rate in the presence of UVA (315-400 nm) and decreased quantum yield, along with enhanced nonphotochemical quenching, with addition of UVB (280-315 nm). The results clearly indicate that UV radiation needs to be invoked as a key stressor when considering the impacts of ocean acidification on E. huxleyi.

Seagrass ecosystem response to long-term high CO2 in a Mediterranean volcanic vent

We examined the long-term effect of naturally acidified water on a Cymodocea nodosa meadow growing at a shallow volcanic CO2 vent in Vulcano Island (Italy). Seagrass and adjacent unvegetated habitats growing at a low pH station (pH = 7.65 ± 0.02) were compared with corresponding habitats at a control station (pH = 8.01 ± 0.01). Density and biomass showed a clear decreasing trend at the low pH station and the below- to above-ground biomass ratio was more than 10 times lower compared to the control. C content and delta 13C of leaves and epiphytes were significantly lower at the low pH station. Photosynthetic activity of C. nodosa was stimulated by low pH as seen by the significant increase in Chla content of leaves, maximum electron transport rate and compensation irradiance. Seagrass community metabolism was intense at the low pH station, with significantly higher net community production, respiration and gross primary production than the control community, whereas metabolism of the unvegetated community did not differ between stations. Productivity was promoted by the low pH, but this was not translated into biomass, probably due to nutrient limitation, grazing or poor environmental conditions. The results indicate that seagrass response in naturally acidified conditions is dependable upon species and geochemical characteristics of the site and highlight the need for a better understanding of complex interactions in these environments.

Elevated pCO2 from late summer coastal upwellings in the western Baltic Sea enhances vegetative growth in the brown algae Fucus serratus: a laboratory assessment

The brown algae Fucus serratus is one of the major meadow forming algae of the Western Baltic Sea nearshore ecosystem. At the end of summer, those meadows are exposed to local upwelling suddenly increasing the pCO2 and DIC up to 2500 µatm and 2250 µmol/kg resp., for period of days to weeks. This study investigates the growth response of summer's vegetative Fucus serratus to elevated pCO2 (1350 and 4080 µatm) during a 40 days laboratory incubation. After 10 days, increases of growth rates of 20 % and 47 % of the control were observed in the 1350 and 4080 µatm pCO2 treatments respectively. Beyond 20 days, the growth rates collapsed in all treatments due to nutrients shortage, as demonstrated by high C:N ratios (95:1) and low N tissue content (0.04 % of dry weight). The collapse occurs faster at higher pCO2. On day 30, growth rates were reduced by 40 % and 100 % relative to the control at 1350 and 4080 µatm respectively. These results are consistent with a fertilizing effect of elevated pCO2 on Fucus serratus presumably linked to the transition from active HCO3- to passive CO2(aq) uptake. This positive effect is limited by nutrients resources, low seawater dissolved inorganic N and P and shortage of the nutrients reserves accumulated over the previous autumn and winter.

Photophysiological responses of Southern Ocean phytoplankton to changes in CO2 concentrations: Short-term versus acclimation effects

The present study examines how different pCO2 acclimations affect the CO2- and light-dependence of photophysiological processes and O2 fluxes in four Southern Ocean (SO) key phytoplankton species. We grew Chaetoceros debilis (Cleve), Pseudo-nitzschia subcurvata (Hasle), Fragilariopsis kerguelensis (O'Meara) and Phaeocystis antarctica (Karsten) under low (160 µatm) and high (1000 ?atm) pCO2. The CO2- and light-dependence of fluorescence parameters of photosystem II (PSII) were determined by means of a fluorescence induction relaxation system (FIRe). In all tested species, nonphotochemical quenching (NPQ) is the primary photoprotection strategy in response to short-term exposure to high light or low CO2 concentrations. In C. debilis and P. subcurvata, PSII connectivity (p) and functional absorption cross-sections of PSII in ambient light (sigma PSII') also contributed to photoprotection while changes in re-oxidation times of Qa acceptor (tQa) were more significant in F. kerguelensis. The latter was also the only species being responsive to high acclimation pCO2, as these cells had enhanced relative electron transport rates (rETRs) and sigma PSII' while tQa and p were reduced under short-term exposure to high irradiance. Low CO2-acclimated cells of F. kerguelensis and all pCO2 acclimations of C. debilis and P. subcurvata showed dynamic photoinhibition with increasing irradiance. To test for the role and presence of the Mehler reaction in C. debilis and P. subcurvata, the light-dependence of O2 fluxes was estimated using membrane inlet mass spectrometry (MIMS). Our results show that the Mehler reaction is absent in both species under the tested conditions. We also observed that dark respiration was strongly reduced under high pCO2 in C. debilis while it remained unaltered in P. subcurvata. Our study revealed species-specific differences in the photophysiological responses to pCO2, both on the acclimation as well as the short-term level.

Seawater carbonate chemistry and combined mechanistic effects of CO2 and light on the N2-fixing cyanobacterium Trichodesmium IMS101, 2010

The marine diazotrophic cyanobacterium Trichodesmium responds to elevated atmospheric CO2 partial pressure (pCO2) with higher N2 fixation and growth rates. To unveil the underlying mechanisms, we examined the combined influence of pCO2(150 and 900 µatm) and light (50 and 200 µmol photons m-2 s-1) on TrichodesmiumIMS101. We expand on a complementary study that demonstrated that while elevated pCO2 enhanced N2 fixation and growth, oxygen evolution and carbon fixation increased mainly as a response to high light. Here, we investigated changes in the photosynthetic fluorescence parameters of photosystem II, in ratios of the photosynthetic units (photosystem I:photosystem II), and in the pool sizes of key proteins involved in the fixation of carbon and nitrogen as well as their subsequent assimilation. We show that the combined elevation in pCO2 and light controlled the operation of the CO2-concentrating mechanism and enhanced protein activity without increasing their pool size. Moreover, elevated pCO2 and high light decreased the amounts of several key proteins (NifH, PsbA, and PsaC), while amounts of AtpB and RbcL did not significantly change. Reduced investment in protein biosynthesis, without notably changing photosynthetic fluxes, could free up energy that can be reallocated to increase N2 fixation and growth at elevated pCO2 and light. We suggest that changes in the redox state of the photosynthetic electron transportchain and posttranslational regulation of key proteins mediate the high flexibility in resources and energy allocation in Trichodesmium. This strategy should enableTrichodesmium to flourish in future surface oceans characterized by elevated pCO2, higher temperatures, and high light.

Interactive effects of light, nitrogen source, and carbon dioxide on energy metabolism in the diatom Thalassiosira pseudonana

Due to the ongoing effects of climate change, phytoplankton are likely to experience enhanced irradiance, more reduced nitrogen, and increased water acidity in the future ocean. Here, we used Thalassiosira pseudonana as a model organism to examine how phytoplankton adjust energy production and expenditure to cope with these multiple, interrelated environmental factors. Following acclimation to a matrix of irradiance, nitrogen source, and CO2 levels, the diatom's energy production and expenditures were quantified and incorporated into an energetic budget to predict how photosynthesis was affected by growth conditions. Increased light intensity and a shift from inline image to inline image led to increased energy generation, through higher rates of light capture at high light and greater investment in photosynthetic proteins when grown on inline image. Secondary energetic expenditures were adjusted modestly at different culture conditions, except that inline image utilization was systematically reduced by increasing pCO2. The subsequent changes in element stoichiometry, biochemical composition, and release of dissolved organic compounds may have important implications for marine biogeochemical cycles. The predicted effects of changing environmental conditions on photosynthesis, made using an energetic budget, were in good agreement with observations at low light, when energy is clearly limiting, but the energetic budget over-predicts the response to inline image at high light, which might be due to relief of energetic limitations and/or increased percentage of inactive photosystem II at high light. Taken together, our study demonstrates that energetic budgets offered significant insight into the response of phytoplankton energy metabolism to the changing environment and did a reasonable job predicting them.

Ocean acidification accelerates reef bioerosion

In the recent discussion how biotic systems may react to ocean acidification caused by the rapid rise in carbon dioxide partial pressure (pCO2) in the marine realm, substantial research is devoted to calcifiers such as stony corals. The antagonistic process-biologically induced carbonate dissolution via bioerosion- has largely been neglected. Unlike skeletal growth, we expect bioerosion by chemical means to be facilitated in a high-CO2 world. This study focuses on one of the most detrimental bioeroders, the sponge Cliona orientalis, which attacks and kills live corals on Australia's Great Barrier Reef. Experimental exposure to lowered and elevated levels of pCO2 confirms a significant enforcement of the sponges' bioerosion capacity with increasing pCO2 under more acidic conditions. Considering the substantial contribution of sponges to carbonate bioerosion, this finding implies that tropical reef ecosystems are facing the combined effects of weakened coral calcification and accelerated bioerosion, resulting in critical pressure on the dynamic balance between biogenic carbonate build-up and degradation.