Seawater carbonate chemistry and buffer capacity of the coelomic fluid in echinoderms in a laboratory experiment

The increase in atmospheric CO2 due to anthropogenic activity results in an acidification of the surface waters of the oceans. The impact of these chemical changes depends on the considered organisms. In particular, it depends on the ability of the organism to control the pH of its inner fluids. Among echinoderms, this ability seems to differ significantly according to species or taxa. In the present paper, we investigated the buffer capacity of the coelomic fluid in different echinoderm taxa as well as factors modifying this capacity. Euechinoidea (sea urchins except Cidaroidea) present a very high buffer capacity of the coelomic fluid (from 0.8 to 1.8 mmol/kg SW above that of seawater), while Cidaroidea (other sea urchins), starfish and holothurians have a significantly lower one (from -0.1 to 0.4 mmol/kg SW compared to seawater). We hypothesize that this is linked to the more efficient gas exchange structures present in the three last taxa, whereas Euechinoidea evolved specific buffer systems to compensate lower gas exchange abilities. The constituents of the buffer capacity and the factors influencing it were investigated in the sea urchin Paracentrotus lividus and the starfish Asterias rubens. Buffer capacity is primarily due to the bicarbonate buffer system of seawater (representing about 63% for sea urchins and 92% for starfish). It is also partly due to coelomocytes present in the coelomic fluid (around 8% for both) and, in P. lividus only, a compound of an apparent size larger than 3 kDa is involved (about 15%). Feeding increased the buffer capacity in P. lividus (to a difference with seawater of about 2.3 mmol/kg SW compared to unfed ones who showed a difference of about 0.5 mmol/kg SW) but not in A. rubens (difference with seawater of about 0.2 for both conditions). In P. lividus, decreased seawater pH induced an increase of the buffer capacity of individuals maintained at pH 7.7 to about twice that of the control individuals and, for those at pH 7.4, about three times. This allowed a partial compensation of the coelomic fluid pH for individuals maintained at pH 7.7 but not for those at pH 7.4.

Euechinoidea and Cidaroidea respond differently to ocean acidification

The impact of the chemical changes in the ocean waters due to the increasing atmospheric CO2 depends on the ability of an organism to control extracellular pH. Among sea urchins, this seems specific to the Euechinoidea, sea urchins except Cidaroidea. However, Cidaroidea survived two ocean acidification periods: the Permian-Trias and the Cretaceous-Tertiary crises. We investigated the response of these two sea urchin groups to reduced seawater pH with the tropical cidaroid Eucidaris tribuloides, the sympatric euechinoid Tripneustes ventricosus and the temperate euechinoid Paracentrotus lividus. Both euechinoid showed a compensation of the coelomic fluid pH due to increased buffer capacity. This was linked to an increased concentration of DIC in the coelomic fluid and thus of bicarbonate ions (most probably originating from the surrounding seawater as isotopic signature of the carbon -delta 13C- was similar). On the other hand, the cidaroid showed no changes within the coelomic fluid. Moreover, the delta 13C of the coelomic fluid did not match that of the seawater and was not significantly different between the urchins from the different treatments. Feeding rate was not affected in any species. While euechinoids are able to regulate their extracellular acid-base balance, many questions are still unanswered on the costs of this capacity. On the contrary, cidaroids do not seem affected by a reduced seawater pH. Further investigations need to be undertaken to cover more species and physiological and metabolic parameters in order to determine if energy trade-offs occur and how this mechanism of compensation is distributed among sea urchins.

Influence of sediment acidification and water flow on sediment acceptance and dispersal of juvenile soft-shell clams (Mya arenaria L.)

Although ocean acidification is expected to reduce carbonate saturation and yield negative impacts on open-ocean calcifying organisms in the near future, acidification in coastal ecosystems may already be affecting these organisms. Few studies have addressed the effects of sedimentary saturation state on benthic invertebrates. Here, we investigate whether sedimentary aragonite saturation (Omega aragonite) and proton concentration ([H+]) affect burrowing and dispersal rates of juvenile soft-shell clams (Mya arenaria) in a laboratory flume experiment. Two size classes of juvenile clams (0.5-1.5 mm and 1.51-2.5 mm) were subjected to a range of sediment Omega aragonite and [H+] conditions within the range of typical estuarine sediments (Omega aragonite 0.21-1.87; pH 6.8-7.8; [H+] 1.58 × 10**-8-1.51 × 10**- 7) by the addition of varying amounts of CO2, while overlying water pH was kept constant ~ 7.8 (Omega aragonite ~ 1.97). There was a significant positive relationship between the percent of juvenile clams burrowed in still water and Omega aragonite and a significant negative relationship between burrowing and [H+]. Clams were subsequently exposed to one of two different flow conditions (flume; 11 cm/s and 23 cm/s) and there was a significant negative relationship between Omega aragonite and dispersal, regardless of clam size class and flow speed. No apparent relationship was evident between dispersal and [H+]. The results of this study suggest that sediment acidification may play an important role in soft-shell clam recruitment and dispersal. When assessing the impacts of open-ocean and coastal acidification on infaunal organisms, future studies should address the effects of sediment acidification to adequately understand how calcifying organisms may be affected by shifting pH conditions.

Seawater carbonate chemistry in Hog reef and calcification rate in the Bermuda reef community, 2010

Despite the potential impact of ocean acidification on ecosystems such as coral reefs, surprisingly, there is very limited field data on the relationships between calcification and seawater carbonate chemistry. In this study, contemporaneous in situ datasets of seawater carbonate chemistry and calcification rates from the high-latitude coral reef of Bermuda over annual timescales provide a framework for investigating the present and future potential impact of rising carbon dioxide (CO2) levels and ocean acidification on coral reef ecosystems in their natural environment. A strong correlation was found between the in situ rates of calcification for the major framework building coral species Diploria labyrinthiformis and the seasonal variability of [CO32-] and aragonite saturation state omega aragonite, rather than other environmental factors such as light and temperature. These field observations provide sufficient data to hypothesize that there is a seasonal "Carbonate Chemistry Coral Reef Ecosystem Feedback" (CREF hypothesis) between the primary components of the reef ecosystem (i.e., scleractinian hard corals and macroalgae) and seawater carbonate chemistry. In early summer, strong net autotrophy from benthic components of the reef system enhance [CO32-] and omega aragonite conditions, and rates of coral calcification due to the photosynthetic uptake of CO2. In late summer, rates of coral calcification are suppressed by release of CO2 from reef metabolism during a period of strong net heterotrophy. It is likely that this seasonal CREF mechanism is present in other tropical reefs although attenuated compared to high-latitude reefs such as Bermuda. Due to lower annual mean surface seawater [CO32-] and omega aragonite in Bermuda compared to tropical regions, we anticipate that Bermuda corals will experience seasonal periods of zero net calcification within the next decade at [CO32-] and omega aragonite thresholds of ~184 micro moles kg-1 and 2.65. However, net autotrophy of the reef during winter and spring (as part of the CREF hypothesis) may delay the onset of zero NEC or decalcification going forward by enhancing [CO32-] and omega aragonite. The Bermuda coral reef is one of the first responders to the negative impacts of ocean acidification, and we estimate that calcification rates for D. labyrinthiformis have declined by >50% compared to pre-industrial times.

Seawater carbonate chemistry and biological processes of coral Acropora muricata during experiments and observations in La Saline fringing reef, La Reunion Island, western Indian Ocean, 2011

The effect of decreasing aragonite saturation state (Omega Arag) of seawater (elevated pCO2) on calcification rates of Acropora muricata was studied using nubbins prepared from parent colonies located at two sites of La Saline reef (La Réunion Island, western Indian Ocean): a back-reef site (BR) affected by nutrient-enriched groundwater discharge (mainly nitrate), and a reef flat site (RF) with low terrigenous inputs. Protein and chlorophyll a content of the nubbins, as well as zooxanthellae abundance, were lower at RF than BR. Nubbins were incubated at ~27°C over 2 h under sunlight, in filtered seawater manipulated to get differing initial pCO2 (1,440-340 µatm), Omega Arag (1.4-4.0), and dissolved inorganic carbon (DIC) concentrations (2,100-1,850 µmol/kg). Increasing DIC concentrations at constant total alkalinity (AT) resulted in a decrease in Omega Arag and an increase in pCO2. AT at the beginning of the incubations was kept at a natural level of 2,193 ± 6 µmol/kg (mean ± SD). Net photosynthesis (NP) and calcification were calculated from changes in pH and AT during the incubations. Calcification decrease in response to doubling pCO2 relative to preindustrial level was 22% for RF nubbins. When normalized to surface area of the nubbins, (1) NP and calcification were higher at BR than RF, (2) NP increased in high pCO2 treatments at BR compared to low pCO2 treatments, and (3) calcification was not related to Omega Arag at BR. When normalized to NP, calcification was linearly related to Omega Arag at both sites, and the slopes of the relationships were not significantly different. The increase in NP at BR in the high pCO2 treatments may have increased calcification and thus masked the negative effect of low Omega Arag on calcification. Removing the effect of NP variations at BR showed that calcification declined in a similar manner with decreased Omega Arag (increased pCO2) whatever the nutrient loading.

Seawater carbonate chemistry and maximum growth rates of Skeletonema marinoi and Alexandrium ostenfeldii, toxin composition of Alexandrium ostenfeldii in a laboratory experiment

Phytoplankton populations can display high levels of genetic diversity that, when reflected by phenotypic variability, may stabilize a species response to environmental changes. We studied the effects of increased temperature and CO2 availability as predicted consequences of global change, on 16 genetically different isolates of the diatom Skeletonema marinoi from the Adriatic Sea and the Skagerrak (North Sea), and on eight strains of the PST (paralytic shellfish toxin)-producing dinoflagellate Alexandrium ostenfeldii from the Baltic Sea. Maximum growth rates were estimated in batch cultures of acclimated isolates grown for five to 10 generations in a factorial design at 20 and 24 °C, and present day and next century applied atmospheric pCO2, respectively. In both species, individual strains were affected in different ways by increased temperature and pCO2. The strongest response variability, buffering overall effects, was detected among Adriatic S. marinoi strains. Skagerrak strains showed a more uniform response, particularly to increased temperature, with an overall positive effect on growth. Increased temperature also caused a general growth stimulation in A. ostenfeldii, despite notable variability in strain-specific response patterns. Our data revealed a significant relationship between strain-specific growth rates and the impact of pCO2 on growth-slow growing cultures were generally positively affected, while fast growing cultures showed no or negative responses to increased pCO2. Toxin composition of A. ostenfeldii was consistently altered by elevated temperature and increased CO2 supply in the tested strains, resulting in overall promotion of saxitoxin production by both treatments. Our findings suggest that phenotypic variability within populations plays an important role in the adaptation of phytoplankton to changing environments, potentially attenuating short-term effects and forming the basis for selection. In particular, A. ostenfeldii blooms may expand and increase in toxicity under increased water temperature and atmospheric pCO2 conditions, with potentially severe consequences for the coastal ecosystem.

Growth, respiration and photophysiology of coral massive Porites spp. in the experiment of Moorea

I tested the hypothesis that high pCO2 (76.6 Pa and 87.2 Pa vs. 42.9 Pa) has no effect on the metabolism of juvenile massive Porites spp. after 11 days at 28 °C and 545 µmol quanta/m**2/s. The response was assessed as aerobic dark respiration, skeletal weight (i.e., calcification), biomass, and chlorophyll fluorescence. Corals were collected from the shallow (3-4 m) back reef of Moorea, French Polynesia (17°28.614'S, 149°48.917'W), and experiments conducted during April and May 2011. An increase in pCO2 to 76.6 Pa had no effect on any dependent variable, but 87.2 Pa pCO2 reduced area-normalized (but not biomass-normalized) respiration 36 %, as well as maximum photochemical efficiency (Fv/Fm) of open RCIIs and effective photochemical efficiency of RCIIs in actinic light (Delta F/F'm ); neither biomass, calcification, nor the energy expenditure coincident with calcification (J/g) was effected. These results do not support the hypothesis that high pCO2 reduces coral calcification through increased metabolic costs and, instead, suggest that high pCO2 causes metabolic depression and photochemical impairment similar to that associated with bleaching. Evidence of a pCO2 threshold between 76.6 and 87.2 Pa for inhibitory effects on respiration and photochemistry deserves further attention as it might signal the presence of unpredictable effects of rising pCO2.

Experiment: Influence of CO2 and nitrogen limitation on the coccolith volume of Emiliania huxleyi (Haptophyta)

Coccolithophores, a key phytoplankton group, are one of the most studied organisms regarding their physiological response to ocean acidification/carbonation. The biogenic production of calcareous coccoliths has made coccolithophores a promising group for paleoceanographic research aiming to reconstruct past environmental conditions. Recently, geochemical and morphological analyses of fossil coccoliths have gained increased interest in regard to changes in seawater carbonate chemistry. The cosmopolitan coccolithophore Emiliania huxleyi (Lohm.) Hay and Mohler was cultured over a range of pCO2 levels in controlled laboratory experiments under nutrient replete and nitrogen limited conditions. Measurements of photosynthesis and calcification revealed, as previously published, an increase in particulate organic carbon production and a moderate decrease in calcification from ambient to elevated pCO2. The enhancement in particulate organic carbon production was accompanied by an increase in cell diameter. Changes in coccolith volume were best correlated with the coccosphere/cell diameter and no significant correlation was found between the coccolith volume and the particulate inorganic carbon production. The conducted experiments revealed that the coccolith volume of E. huxleyi is variable with aquatic CO2 concentration but its sensitivity is rather small in comparison with its sensitivity to nitrogen limitation. Comparing coccolith morphological and geometrical parameters like volume, mass and size to physiological parameters under controlled laboratory conditions is an important step to understand variations in fossil coccolith geometry.

(Supplement) Groundwater quality in Lahore Pakistan: emphasis on Arsenic and Fluoride levels

The dataset provides detailed information on the study that was conducted in Lahore's 7 major towns. The sample was taken from 472 tubewells and analyzed for major cations and anions using APHA 2012 techniques as explained herein. Besides, E.coli determination was done to check for microbial contamination. The data includes results from PHREEQC modeling of As(III)/ As(V) species and saturation indices as well as Aquachem's computed hydrochemical water facies. The WHO (2011) and EPA standards included in Aquachem identified the parameters that where in violation. Bicarbonates dominated the groundwater types with 50.21% of the samples exceeding the EPA maximum permissible limit of 250 mg/L in drinking water. Similarly, 30.51% of the samples had TDS values greater than 500 mg/L while 85.38 % of the samples exceed 10 µg/L threshold limit value of arsenic. Also, instances of high magnesium hazard values were observed which requires constant assessment if the groundwater is used for irrigation. Higher than 50% MH values are detrimental to crops which may reduce the expected yields. The membrane filtration technique using m-Endo Agar indicated that 3.59% samples had TNC (too numerous to count) values for E.coli while 5.06% showed values higher than 0 cfu/ 100 ml acceptable value in drinking water. Any traces of E-coli in a groundwater sample indicate recent fecal contamination. Such outcomes signify presence of enteric pathogens. If the groundwater is not properly dosed with disinfectants it may cause harm to human health. It is concluded that more studies are needed and proper groundwater management implement to safeguard the lives of communities that depend solely on groundwater in the city.

Seawater carbonate chemistry and calcification during tropical reef studies at Moorea (French Polynesia), 1997

Community metabolism and air-sea carbon dioxide (CO2) fluxes were investigated in July 1992 on a fringing reef at Moorea (French Polynesia). The benthic community was dominated by macroalgae (85% substratum cover) and comprised of Phaeophyceae Padina tenuis (Bory), Turbinaria ornata (Turner) J. Agardh, and Hydroclathrus clathratus Bory (Howe); Chlorophyta Halimeda incrassata f. ovata J. Agardh (Howe); and Ventricaria ventricosa J. Agardh (Olsen et West), as well as several Rhodophyta (Actinotrichia fragilis Forskál (Børgesen) and several species of encrusting coralline algae). Algal biomass was 171 g dry weight/m**2. Community gross production (Pg), respiration (R), and net calcification (G) were measured in an open-top enclosure. Pg and R were respectively 248 and 240 mmol Co2/m**2/d, and there was a slight net dissolution of CaCO3 (0.8 mmol/m**2/d). This site was a sink for atmospheric CO2 (10 ± 4 mmol CO2/m**2/d), and the analysis of data from the literature suggests that this is a general feature of algal-dominated reefs. Measurement of air-sea CO2 fluxes in open water close to the enclosure demonstrated that changes in small-scale hydrodynamics can lead to misleading conclusions. Net CO2 evasion to the atmosphere was measured on the fringing reef due to changes in the current pattern that drove water from the barrier reef (a C02 source) to the study site.

Seawater carbonate chemistry and community calcification during Shiraha coral reef (Ishigaki Island, Japan) studies, 1995

Only about half of all the CO_2 that has been produced by the burning of fossil fuels now remains in the atmosphere. The CO_2 "missing" from the atmosphere is the subject of an important debate. It was thought that the great majority of the missing CO_2 has invaded the ocean, for this system naturally acts as a giant chemical regulator of the atmosphere. Although it is clear that ocean processes have a major role in the regulation of the carbon dioxide content of the atmosphere through air-sea exchange processes, recent studies of the oceanic carbon cycle and air-sea interaction indicate that oceanic carbon is in a quasi-steady state via the system of biological and physical processes in the ocean interior. It is difficult to determine whether the ocean has the capacity to take up the increasing air-born CO_2 released by human activities over the past five or six decades. To understand this enigma, we need a better understanding of the natural variability of the oceanic carbon cycle.

Seawater carbonate chemistry and calcification during a study of barrier reef flat in Moorea, French Polynesia, 1998

The relative contribution of soft bottoms to the community metabolism (primary production, respiration and net calcification) of a barrier reef flat has been investigated at Moorea (French Polynesia). Community metabolism of the sedimentary area was estimated using in situ incubations in perspex chambers, and compared with estimates of community metabolism of the whole reef flat obtained using a Lagrangian technique (Gattuso et al., 1996. Carbon flux in coral reefs. 1. Lagrangian measurement of community metabolism and resulting air-sea CO2 disequilibrium. Mar. Ecol. Prog. Ser. 145, 109-121). Net organic carbon production (E), respiration (R) and net calcification (G) of sediments were measured by seven incubations performed in triplicate at different irradiance. Respiration and environmental parameters were also measured at four randomly selected additional stations. A model of Photosynthesis-irradiance allowed to calculate oxygen (O2), organic carbon (CO2) and calcium carbonate (CaCO3) evolution from surface irradiance during a diel cycle. As chlorophyll a content of the sediment was not significantly different between stations, primary production of the sediment was considered as homogeneous for the whole lagoon. Thus, carbon production at the test station can be modelled from surface light irradiance. The modelled respiration was two times higher at the test station than the mean respiration of the barrier reef, and thus underestimated sediment contribution to excess production. Sediments cover 40-60% of the surface and accounted for 2.8-4.1% of organic carbon excess production estimated with the modelled R and 21-32% when mean R value was considered. The sedimentary CaCO3 budget was a very minor component of the whole reef budget.

Grain size distribution, carbon content and wet bulk density of sediment cores in the equatorial Atlantic and the Norwegian Sea

Near-surface sediments from the equatorial east Atlantic and the Norwegian Sea exhibit pronounced shear strength maxima in profiles from the peak Holocene and Pleistocene. These semi-indurated layers start to occur at 8-102 cm below the sediment surface and can be explained neither by the modal composition nor by the effective overburden pressure of the sediments. However, scanning electron microscope and microprobe data exhibit micritic crusts and crystal carpets, which are clearly restricted to (undisturbed) samples from indurated layers and form a manifest explanation for their origin. The minerals precipitated comprise calcite, aragonite, and in samples more proximal to the African continent SiO2 needles, and needles of as yet unidentified K-Mg-Fe-Al silicates, crusts of which dominate the indurated layers in the Norwegian Sea. By their stratigraphic position in deep-sea sediments the carbonate-based shear strength maxima are tentatively ascribed to dissolved adjacent pteropod layers from the early Holocene and hence to short-lived no-analogue events of early diagenesis. Possibly, they have been controlled by a reduced organic carbon flux, leading to increased aragonite preservation in the deep sea.