Dramatic variability of the carbonate system at a temperate coastal ocean site (Beaufort, North Carolina, USA) is regulated by physical and biogeochemical processes on multiple timescales.

Increasing atmospheric carbon dioxide (CO2) from anthropogenic sources is acidifying marine environments resulting in potentially dramatic consequences for the physical, chemical and biological functioning of these ecosystems. If current trends continue, mean ocean pH is expected to decrease by ~0.2 units over the next ~50 years. Yet, there is also substantial temporal variability in pH and other carbon system parameters in the ocean resulting in regions that already experience change that exceeds long-term projected trends in pH. This points to short-term dynamics as an important layer of complexity on top of long-term trends. Thus, in order to predict future climate change impacts, there is a critical need to characterize the natural range and dynamics of the marine carbonate system and the mechanisms responsible for observed variability. Here, we present pH and dissolved inorganic carbon (DIC) at time intervals spanning 1 hour to >1 year from a dynamic, coastal, temperate marine system (Beaufort Inlet, Beaufort NC USA) to characterize the carbonate system at multiple time scales. Daily and seasonal variation of the carbonate system is largely driven by temperature, alkalinity and the balance between primary production and respiration, but high frequency change (hours to days) is further influenced by water mass movement (e.g. tides) and stochastic events (e.g. storms). Both annual (~0.3 units) and diurnal (~0.1 units) variability in coastal ocean acidity are similar in magnitude to 50 year projections of ocean acidity associated with increasing atmospheric CO2. The environmental variables driving these changes highlight the importance of characterizing the complete carbonate system rather than just pH. Short-term dynamics of ocean carbon parameters may already exert significant pressure on some coastal marine ecosystems with implications for ecology, biogeochemistry and evolution and this shorter term variability layers additive effects and complexity, including extreme values, on top of long-term trends in ocean acidification.

Efects of mineral suspension and dissolution on strength and compressibility of soft carbonate rocks

© 2014 Elsevier B.V.Calcarenites are highly porous soft rocks formed of mainly carbonate grains bonded together by calcite bridges. The above characteristics make them prone to water-induced weathering, frequently featuring large caverns and inland natural underground cavities. This study is aimed to determine the main physical processes at the base of the short- and long-term weakening experienced by these rocks when interacting with water. We present the results of microscale experimental investigations performed on calcarenites from four different sites in Southern Italy. SEM, thin sections, X-ray CT observations and related analyses are used for both the interpretation-definition of the structure changes, and the identification-quantification of the degradation mechanisms. Two distinct types of bonding have been identified within the rock: temporary bonding (TB) and persistent bonding (PB). The diverse mechanisms linked to these two types of bonding explain both the observed fast decrease in rock strength when water fills the pores (short-term effect of water), identified with a short-term debonding (STD), and a long-term weakening of the material, when the latter is persistently kept in water-saturated conditions (long-term effect of water), identified with a long-term debonding (LTD). To highlight the micro-hydro-chemo-mechanical processes of formation and annihilation of the TB bonds and their role in the evolution of the mechanical strength of the material, mechanical tests on samples prepared by drying partially saturated calcarenite powder, or a mix of glass ballotini and calcarenite powder were conducted. The long-term debonding processes have also been investigated, using acid solutions in order to accelerate the reaction rates. This paper attempts to identify and quantify differences between the two types of bonds and the relative micro-scale debonding processes leading to the macro-scale material weakening mechanisms.

Seasonal dynamics of the carbonate system in the Western English Channel

We present over 900 carbonate system observations collected over four years (2007–2010) in the Western English Channel (WEC). We determined CO2 partial pressure (pCO2), Total Alkalinity (TA) and Dissolved Inorganic Carbon (DIC) along a series of 40 km transects, including two oceanographic stations (L4 and E1) within a sustained coastal observatory. Our data follow a seasonal pattern of CO2 undersaturation from January to August, followed by supersaturation in September–October and a return to near-equilibrium thereafter. This pattern is explained by the interplay of thermal and biological sinks in winter and spring–summer, respectively, followed by the breakdown of stratification and mixing with deeper, high-CO2 water in autumn. The drawdown of DIC and inorganic N between March and June with a C:N ratio of 8.7–9.5 was consistent with carbon over-consumption during phytoplankton growth. Monthly mean surface pCO2 was strongly correlated with depth integrated chlorophyll a highlighting the importance of subsurface chlorophyll a maxima in controlling C-fluxes in shelf seas. Mixing of seawater with riverine freshwater in near-shore samples caused a reduction in TA and the saturation state of calcite minerals, particularly in winter. Our data show that the L4 and E1 oceanographic stations were small, net sinks for atmospheric CO2 over an annual cycle (−0.52±0.66 mol C m−2 y−1 and −0.62±0.49 mol C m−2 y−1, respectively).

The carbonate system of the NW European shelf: sensitivity and model validation

The ocean plays an important role in regulating the climate, acting as a sink for carbon dioxide, perturbing the carbonate system and resulting in a slow decrease of seawater pH. Understanding the dynamics of the carbonate system in shelf sea regions is necessary to evaluate the impact of Ocean Acidification (OA) in these societally important ecosystems. Complex hydrodynamic and ecosystem coupled models provide a method of capturing the significant heterogeneity of these areas. However rigorous validation is essential to properly assess the reliability of such models. The coupled model POLCOMS–ERSEM has been implemented in the North Western European shelf with a new parameterization for alkalinity explicitly accounting for riverine inputs and the influence of biological processes. The model has been validated in a like with like comparison with North Sea data from the CANOBA dataset. The model shows good to reasonable agreement for the principal variables, physical (temperature and salinity), biogeochemical (nutrients) and carbonate system (dissolved inorganic carbon and total alkalinity), but simulation of the derived variables, pH and pCO2, are not yet fully satisfactory. This high uncertainty is attributed mostly to riverine forcing and primary production. This study suggests that the model is a useful tool to provide information on Ocean Acidification scenarios, but uncertainty on pH and pCO2 needs to be reduced, particularly when impacts of OA on ecosystem functions are included in the model systems.

Fine-scale nutrient and carbonate system dynamics around cold-water coral reefs in the northeast Atlantic.

Ocean acidification has been suggested as a serious threat to the future existence of cold-water corals (CWC). However, there are few fine-scale temporal and spatial datasets of carbonate and nutrients conditions available for these reefs, which can provide a baseline definition of extant conditions. Here we provide observational data from four different sites in the northeast Atlantic that are known habitats for CWC. These habitats differ by depth and by the nature of the coral habitat. At depths where CWC are known to occur across these sites the dissolved inorganic carbon ranged from 2088 to 2186 μmol kg−1, alkalinity ranged from 2299 to 2346 μmol kg−1, and aragonite Ω ranged from 1.35 to 2.44. At two sites fine-scale hydrodynamics caused increased variability in the carbonate and nutrient conditions over daily time-scales. The observed high level of variability must be taken into account when assessing CWC sensitivities to future environmental change.

Variation in elemental stoichiometry of the marine diatomThalassiosira weissflogii(Bacillariophyceae) in response to combined nutrient stress and changes in carbonate chemistry

The combined consequences of the multi-stressors of pH and nutrient availability upon the growth of a marine diatom were investigated. Thalassiosira weissflogii was grown in N- or P-limited batch culture in sealed systems, with pH commencing at 8.2 (extant conditions) or 7.6 (ocean acidification [OA] conditions), and then pH was allowed to either drift with growth, or was held fixed. Results indicated that within the pH range tested, the stability of environmental pH rather than its value (i.e., OA vs. extant) fundamentally influenced biomass accumul-ation and C:N:P stoichiometry. Despite large changes in total alkalinity in the fixed pH systems, final biomass production was consistently greater in these systems than that in drifting pH systems. In drift systems, pH increased to exceed pH 9.5, a level of alkalinity that was inhibitory to growth. No statis-tically significant differences between pH treatments were measured for N:C, P:C or N:P ratios during nutrient-replete growth, although the diatom expre-ssed greater plasticity in P:C and N:P ratios than in N:C during this growth phase. During nutrient-deplete conditions, the capacity for uncoupled carbon fixa-tion at fixed pH was considerably greater than that measured in drift pH systems, leading to strong contrasts in C:N:P stoichiometry between these treatments. Whether environmental pH was stable or drifted directly influenced the extent of physiological stress. In contrast, few distinctions could be drawn between extant versus OA conditions for cell physiology.