Seawater carbonate chemistry during experiments with Littorina littorea, 2007

We demonstrate that acidified seawater can have indirect biological effects by disrupting the capability of organisms to express induced defences, hence, increasing their vulnerability to predation. The intertidal gastropod Littorina littorea produced thicker shells in the presence of predation (crab) cues but this response was disrupted at low seawater pH. This response was accompanied by a marked depression in metabolic rate (hypometabolism) under the joint stress of high predation risk and reduced pH. However, snails in this treatment apparently compensated for a lack of morphological defence, by increasing their avoidance behaviour, which, in turn, could affect their interactions with other organisms. Together, these findings suggest that biological effects from ocean acidification may be complex and extend beyond simple direct effects.

Chemistry of peridotites from ODP 109-670A

During Leg 109 of the Ocean Drilling Program, about 100 m of serpentinized peridotites were drilled on the western wall of the M.A.R. axial rift valley, 45 km south of the Kane Fracture Zone. The present study reports petrological and mineralogical data obtained from 29 small pieces of these ultramafic rocks, including about 60% serpentinized harzburgites, 26% serpentinized lherzolites, 14% serpentinized dunites, and one sample of olivine websterite. Modal analyses show that all these rocks are plagioclase-free four-phase peridotites equilibrated in the spinel lherzolite facies. The estimated average modal composition of the sample set is about 80% olivine, 14% opx, 5% cpx, and 1% spinel, that is, a cpx-poor lherzolite. The well developed porphyroclastic structures and mineralogical characteristics of these rocks indicate their affinity with the group of residual mantle tectonites, among the abyssal peridotites. Features typical of magmatic cumulates are lacking. The high contents in Al2O3 of the cpx (average 5.4%) and of the opx (average 4.3%) porphyroclasts, the low Cr# of the spinels (average 22.9%), and the rather high content in modal cpx (about 5%), indicate a moderate percentage of melting, of the order of 10%-15%. Site 670 peridotites plot close to the least depleted mantle rocks collected in the oceans in most diagrams used to define the average trend of the ocean-floor peridotites. Microprobe traverses across the cores of the exsolved opx and cpx porphyroclasts permitted the recalculation of the magmatic compositions of these pyroxenes: the 'primitive' opx were equilibrated at about 1300°C, probably at the end of the main melting episodes, whereas the 'primitive' cpx show lower equilibration temperatures, at about 1200°C, reflecting a more complex thermal history. The subsolidus evolution is well recorded, from 1200°C to about 950CC, by the exsolved pyroxenes and the olivine and spinel phases. Unusually high blocking temperatures, close to 1000°C, indicate that the peridotite body was cooled very rapidly between 1000°C and the beginning of serpentinization. Oxygen fugacities, calculated for 10 kb and at the blocking temperatures indicated by the olivine/spinel geothermometer, are close to the usual fugacities calculated in oceanic peridotites and basalts (of the order of 10**-10 to 10**-11, on the QFM buffer). Site 670 peridotites have compositions close to those of the peridotites collected in the Kane Fracture Zone area, and obviously belong to the moderately depleted mantle peridotites which characterize abyssal peridotites collected away from mantle plumes and oceanic islands. In particular, they differ from the highly residual harzburgites collected along the M.A.R. over the Azores bulge.

Seawater carbonate chemistry and giant kelp Macrocystis pyrifera reproduction processes during experiments, 2011

The worldwide effects of ocean acidification (OA) on marine species are a growing concern. In temperate coastal seas, seaweeds are dominant primary producers that create complex habitats and supply energy to higher trophic levels. Studies on OA and macroalgae have focused on calcifying species and adult stages but, critically, they have overlooked the microscopic stages of the reproductive life cycle, which, for other anthropogenic stress e.g. UV-B radiation, are the most susceptible life-history phase. Also, environmental cues and stressors can cause changes in the sex ratio which has implications for the mating system and recruitment success. Here, we report the effects of pH (7.59-8.50) on meiospore germination and sex determination for the giant kelp, Macrocystis pyrifera (Laminariales), in the presence and absence of additional dissolved inorganic carbon (DIC). Lowered pH (7.59-7.60, using HCl-only) caused a significant reduction in germination, while added DIC had the opposite effect, indicating that increased CO2 at lower pH ameliorates physiological stress. This finding also highlights the importance of appropriate manipulation of seawater carbonate chemistry when testing the effects of ocean acidification on photosynthetic organisms. The proportion of male to female gametophytes did not vary significantly between treatments suggesting that pH was not a primary environmental modulator of sex. Relative to the baseline (pH 8.19), gametophytes were 32% larger under moderate OA (pH 7.86) compared to their size (10% increase) under extreme OA (pH 7.61). This study suggests that metabolically-active cells can compensate for the acidification of seawater. This homeostatic function minimises the negative effects of lower pH (high H+ ions) on cellular activity. The 6-9% reduction in germination success under extreme OA suggests that meiospores of M.pyrifera may be resistant to future ocean acidification.

Soil chemistry and particle size distribution of mountainous tundra soils in the Rai-Iz Massif

Gravelly clay loamy and clayey soils developed from the derivatives of ultramafic rocks of the dunite-harzburgite complex of the Rai-Iz massif in the Polar Urals have been studied. They are represented by raw-humus pelozems (weakly developed clayey soils) under conditions of perfect drainage on steep slopes and by the gleyzems (Gleysols) with vivid gley color patterns in the eluvial positions on leveled elements of the relief. The magnesium released from the silicates with the high content of this element (mainly from olivine) specifies the neutral-alkaline reaction in these soils. Cryoturbation, the accumulation of raw humus, the impregnation of the soil mass with humic substances, gleyzation, and the ferrugination of the gleyed horizons are also clearly pronounced in the studied soils. Despite the high pH values, the destruction of supergene smectites in the upper horizons and ferrugination (the accumulation of iron hydroxides) in the microfissures dissecting the grains of olivine, pyroxene, and serpentine, and in decomposing plant tissues take place. The development of these processes may be related to the local acidification (neutralization) of the soil medium under the impact of biota and carbonic acids. The specificity of gleyzation in the soils developing from ultra-mafic rocks is shown in the absence of iron depletion from the fine earth material against the background of the greenish blue gley color pattern.

Chemistry and mineralogy of ODP Leg 124 sediment samples

From X-ray mineralogical studies and chemical analyses of the whole rocks and the fine fractions (<2 µm) of ten to fifteen samples at each site of ODP Leg 124, two major sources were identified in the sedimentary components of the Celebes and Sulu basins: (1) a terrestrial and continental contribution; (2) a volcanic influx that gives way to well-defined volcanic units or to a dilute contamination, consisting of coarse-grained minerals (Plagioclase, pyroxene, olivine, spinel) or a smectitic-rich fraction produced by the alteration of volcanic glasses and ashes. The continental signature increases the amount of quartz in the rocks and the phyllitic association is complex: micas, kaolinite, disordered interstratified clay-minerals. The chemical compositions of the bulk rocks and the fractions <2 µm are more potassic and aluminum-rich. The volcanic imprint depends on the grain-size and chemical properties of the components. Ca/Na contents highly variable compared to the K content of the bulk composition are due to the presence of coarse-grained volcanic Plagioclase. The fractions <2 µm are more magnesian than in the continental regime. The diagenesis is revealed by the crystallization of zeolites, the fixation of magnesium into the smectites that depletes the pore fluids in this element. Smectitization of the disordered interstratified clay minerals enriches the alkalinity of the pore fluids. Some deep formations of the Sulu Basin are affected by a thermal event, but no thermal event was recognized in the Celebes Basin.

Interstitial water chemistry of ODP Leg 110 holes

Major-element compositions (Cl-, SO4[2-], Ca2+, Mg2+ , Li+ , K+, Na+ , Sr2+) of interstitial waters obtained from sediment cores along the ODP Leg 110 transect across the Northern Barbados accretionary prism have shown that a complex set of geochemical processes are of importance in this area. In the volcanic ash-rich Pleistocene-Pliocene sediments, alteration reactions involving volcanic ash lead to depletions of Mg2+ and K+. This process is confirmed by the much lower than contemporaneous seawater values of the 87Sr/86Sr ratios of dissolved strontium. In the deeper sediments recovered below the zone of decollement (Sites 671 and 672) large increases in Ca2+ and gradual decreases in Mg2+ , Na+, and d18O (H2O) indicate a potential contribution to the interstitial water chemistry by exchange with underlying basement rocks. This process has been hard to confirm because the drill holes were terminated well short of reaching basement. However, the concentration gradient pattern is consistent with observations in a large number of DSDP drill holes. Finally, but most importantly, low Cl- concentrations in the decollement zone and underlying sand layers, as well as in fault zones at Sites 673 and 674, indicate dilution of interstitial waters. The potential origins of the low Cl- concentrations are discussed, though we are not able to distinguish any mechanism in particular. Our evidence supports the concept of water migration along the decollement and through the underlying sandstones as well as along recent fault zones in the accretionary complex. Interstitial water concentration depth profiles are affected by faulting, thrusting, and overturn processes in the accretionary prism. These processes have caused a diminished diffusive exchange with the overlying ocean, thus explaining increased depletions in Mg2+ and SO4[2-] in sites farther onto the accretionary prism.

Whole transcriptome analysis of the coral Acropora millepora reveals complex responses to CO2-driven acidification during the initiation of calcification

The impact of ocean acidification (OA) on coral calcification, a subject of intense current interest, is poorly understood in part because of the presence of symbionts in adult corals. Early life history stages of Acropora spp. provide an opportunity to study the effects of elevated CO(2) on coral calcification without the complication of symbiont metabolism. Therefore, we used the Illumina RNAseq approach to study the effects of acute exposure to elevated CO(2) on gene expression in primary polyps of Acropora millepora, using as reference a novel comprehensive transcriptome assembly developed for this study. Gene ontology analysis of this whole transcriptome data set indicated that CO(2) -driven acidification strongly suppressed metabolism but enhanced extracellular organic matrix synthesis, whereas targeted analyses revealed complex effects on genes implicated in calcification. Unexpectedly, expression of most ion transport proteins was unaffected, while many membrane-associated or secreted carbonic anhydrases were expressed at lower levels. The most dramatic effect of CO(2) -driven acidification, however, was on genes encoding candidate and known components of the skeletal organic matrix that controls CaCO(3) deposition. The skeletal organic matrix effects included elevated expression of adult-type galaxins and some secreted acidic proteins, but down-regulation of other galaxins, secreted acidic proteins, SCRiPs and other coral-specific genes, suggesting specialized roles for the members of these protein families and complex impacts of OA on mineral deposition. This study is the first exhaustive exploration of the transcriptomic response of a scleractinian coral to acidification and provides an unbiased perspective on its effects during the early stages of calcification.

Hidden impacts of ocean acidification to live and dead coral framework

Cold-water corals, such as Lophelia pertusa, are key habitat-forming organisms found throughout the world's oceans to 3000 m deep. The complex three-dimensional framework made by these vulnerable marine ecosystems support high biodiversity and commercially important species. Given their importance, a key question is how both the living and the dead framework will fare under projected climate change. Here, we demonstrate that over 12 months L. pertusa can physiologically acclimate to increased CO2, showing sustained net calcification. However, their new skeletal structure changes and exhibits decreased crystallographic and molecular-scale bonding organization. Although physiological acclimatization was evident, we also demonstrate that there is a negative correlation between increasing CO2 levels and breaking strength of exposed framework (approx. 20-30% weaker after 12 months), meaning the exposed bases of reefs will be less effective 'load-bearers', and will become more susceptible to bioerosion and mechanical damage by 2100.

Chemistry and fluid inclusions of the sheeted dike comples of ODP Holes 137-504B and 140-504B

Fluid inclusions in variably altered diabase recovered from Ocean Drilling Program Legs 137 and 140 at Hole 504B, Costa Rica Rift, exhibit fluid salinities up to 3.7 times that of seawater values (11.7 wt% NaCl equivalent) and exhibit uncorrected homogenization temperatures of 125°C to 202°C. The liquid-dominated inclusions commonly are entrapped in zones of secondary plagioclase and may be primary in origin. Fluid salinities are similar to compositions of fluids venting on the seafloor (0.4-7.0 wt% NaCl) and overlap with those measured in metabasalt samples recovered from near the Kane Fracture Zone on the Mid-Atlantic Ridge and from the Troodos ophiolite, Cyprus. The salinity variations may reflect hydration reactions involving formation of secondary mineral assemblages under rock-dominated conditions, which modify the ionic strength of hydrothermal fluids by consuming or liberating water and chloride ion. Rare CO2-CH4-bearing inclusions, subjacent to zones where talc after olivine becomes an important secondary mineral phase (1700 mbsf), may have formed due to local interaction of seawater and olivine at low water to rock ratios. Corrected average fluid inclusion homogenization temperatures exhibit a gradient from 159°C at a depth of 1370 mbsf to 183°C at a depth of 1992 mbsf and are in apparent equilibrium with the present conductive downhole temperatures. These data indicate that fluid inclusions may be used to estimate downhole temperatures if logging data are unavailable. The compositional and thermal evolution of the diabase-hosted fluids may reflect late-stage, off-axis circulation and conductive heating of compositionally modified seawater in the sheeted dike complex at Hole 504B.

Seawater carbonate chemistry and weight of two Atlantic corals Favia fragum and Porites astreoides during experiments, 2011

Rising concentrations of atmospheric CO2 are changing the carbonate chemistry of the oceans, a process known as ocean acidification (OA). Absorption of this CO2 by the surface oceans is increasing the amount of total dissolved inorganic carbon (DIC) and bicarbonate ion (HCO3) available for marine calcification yet is simultaneously lowering the seawater pH and carbonate ion concentration ([CO3]), and thus the saturation state of seawater with respect to aragonite. We investigated the relative importance of [HCO3] versus [CO3] for early calcification by new recruits (primary polyps settled from zooxanthellate larvae) of two tropical coral species, Favia fragum and Porites astreoides. The polyps were reared over a range of ?ar values, which were manipulated by both acid-addition at constant pCO2 (decreased total [HCO3] and [CO3]) and by pCO2 elevation at constant alkalinity (increased [HCO3], decreased [CO3]). Calcification after 2 weeks was quantified by weighing the complete skeleton (corallite) accreted by each polyp over the course of the experiment. Both species exhibited the same negative response to decreasing [CO3] whether ?ar was lowered by acid-addition or by pCO2 elevation-calcification did not follow total DIC or [HCO3]. Nevertheless, the calcification response to decreasing [CO3] was nonlinear. A statistically significant decrease in calcification was only detected between Omega aragonite = <2.5 and Omega aragonite = 1.1-1.5, where calcification of new recruits was reduced by 22-37% per 1.0 decrease in Omega aragonite. Our results differ from many previous studies that report a linear coral calcification response to OA, and from those showing that calcification increases with increasing [HCO3]. Clearly, the coral calcification response to OA is variable and complex. A deeper understanding of the biomineralization mechanisms and environmental conditions underlying these variable responses is needed to support informed predictions about future OA impacts on corals and coral reefs.

Pore-water chemistry of ODP Leg 114 holes

Pore-water samples were recovered at five sites from ODP Leg 114 in the subantarctic South Atlantic Ocean and analyzed for pH, alkalinity, chloride, sulfate, fluoride, silica, magnesium, calcium, strontium, potassium, lithium, and barium. At sites in the East Georgia Basin and on the Islas Orcadas Rise, Ca increases and Mg decreases linearly downhole with a DeltaMg/DeltaCa ratio reflecting conservative diffusive exchange and basalt basement reactions. At sites on the west flank of the Mid-Atlantic Ridge and on the Meteor Rise, Ca gradients are nonlinear, and nonconservative DeltaMg/DeltaCa ratios reflect alteration reactions of abundant silicic volcanic ash in the sediment. K decreases linearly downhole at all sites, reflecting uptake by basement and the absence of significant sediment-hosted reactions. SO4 decreases and alkalinity increases downhole are due to a slight sulfate reduction at all sites except at Site 701. Sr increases downhole at all sites except Site 701, with DeltaSr/DeltaCa ratios reflecting diffusive exchange with basement. At Site 704 on the Meteor Rise, there is intense Sr production during carbonate recrystallization in the upper 200 mbsf. Below 200 mbsf at Site 704, the ion concentration product of SrSO4 is constant, suggesting Sr control by celestite solubility. Li and F concentrations display complex behavior related to sedimentary reactions, probably calcite recrystallization (Li uptake and F release).

Seawater carbonate chemistry, and Lithophyllum sp. and Feldmannia spp. coverage and dry weight during experiments, 2009

Climate-driven change represents the cumulative effect of global through local-scale conditions, and understanding their manifestation at local scales can empower local management. Change in the dominance of habitats is often the product of local nutrient pollution that occurs at relatively local scales (i.e. catchment scale), a critical scale of management at which global impacts will manifest. We tested whether forecasted global-scale change [elevated carbon dioxide (CO2) and subsequent ocean acidification] and local stressors (elevated nutrients) can combine to accelerate the expansion of filamentous turfs at the expense of calcifying algae (kelp understorey). Our results not only support this model of future change, but also highlight the synergistic effects of future CO2 and nutrient concentrations on the abundance of turfs. These results suggest that global and local stressors need to be assessed in meaningful combinations so that the anticipated effects of climate change do not create the false impression that, however complex, climate change will produce smaller effects than reality. These findings empower local managers because they show that policies of reducing local stressors (e.g. nutrient pollution) can reduce the effects of global stressors not under their governance (e.g. ocean acidification). The connection between research and government policy provides an example whereby knowledge (and decision making) across local through global scales provides solutions to some of the most vexing challenges for attaining social goals of sustainability, biological conservation and economic development.

Seawater carbonate chemistry and protein sports of barnicle Balanus amphitrite during experiments, 2011

The majority of benthic marine invertebrates have a complex life cycle, during which the pelagic larvae select a suitable substrate, attach to it, and then metamorphose into benthic adults. Anthropogenic ocean acidification (OA) is postulated to affect larval metamorphic success through an altered protein expression pattern (proteome structure) and post-translational modifications. To test this hypothesis, larvae of an economically and ecologically important barnacle species Balanus amphitrite, were cultured from nauplius to the cyprid stage in the present (control) and in the projected elevated concentrations of CO2 for the year 2100 (the OA treatment). Cyprid response to OA was analyzed at the total proteome level as well as two protein post-translational modification (phosphorylation and glycosylation) levels using a 2-DE based proteomic approach. The cyprid proteome showed OA-driven changes. Proteins that were differentially up or down regulated by OA come from three major groups, namely those related to energy-metabolism, respiration, and molecular chaperones, illustrating a potential strategy that the barnacle larvae may employ to tolerate OA stress. The differentially expressed proteins were tentatively identified as OA-responsive, effectively creating unique protein expression signatures for OA scenario of 2100. This study showed the promise of using a sentinel and non-model species to examine the impact of OA at the proteome level.

Water chemistry, carbonate system parameters, and macro-organism biomass of vent and off-vent sites in the Columbretes Islands Marine Reserve

Ocean acidification is receiving increasing attention because of its potential to affect marine ecosystems. Rare CO2 vents offer a unique opportunity to investigate the response of benthic ecosystems to acidification. However, the benthic habitats investigated so far are mainly found at very shallow water (less than or equal to 5 m depth) and therefore are not representative of the broad range of continental shelf habitats. Here, we show that a decrease from pH 8.1 to 7.9 observed in a CO2 vent system at 40 m depth leads to a dramatic shift in highly diverse and structurally complex habitats. Forests of the kelp Laminaria rodriguezii usually found at larger depths (greater than 65 m) replace the otherwise dominant habitats (i.e. coralligenous outcrops and rhodolith beds), which are mainly characterized by calcifying organisms. Only the aragonite-calcifying algae are able to survive in acidified waters, while high-magnesium-calcite organisms are almost completely absent. Although a long-term survey of the venting area would be necessary to fully understand the effects of the variability of pH and other carbonate parameters over the structure and functioning of the investigated mesophotic habitats, our results suggest that in addition of significant changes at species level, moderate ocean acidification may entail major shifts in the distribution and dominance of key benthic ecosystems at regional scale, which could have broad ecological and socio-economic implications.