Structural and functional vulnerability to elevated pCO2 in marine benthic communities

The effect of elevated pCO(2)/low pH on marine invertebrate benthic biodiversity, community structure and selected functional responses which underpin ecosystem services (such as community production and calcification) was tested in a medium-term (30 days) mesocosm experiment in June 2010. Standardised intertidal macrobenthic communities, collected (50.3567A degrees N, 4.1277A degrees W) using artificial substrate units (ASUs), were exposed to one of seven pH treatments (8.05, 7.8. 7.6, 7.4, 7.2, 6.8 and 6.0). Community net calcification/dissolution rates, as well as changes in biomass, community structure and diversity, were measured at the end of the experimental period. Communities showed significant changes in structure and reduced diversity in response to reduced pH: shifting from a community dominated by calcareous organisms to one dominated by non-calcareous organisms around either pH 7.2 (number of individuals and species) or pH 7.8 (biomass). These results were supported by a reduced total weight of CaCO3 structures in all major taxa at lowered pH and a switch from net calcification to net dissolution around pH 7.4 (a"broken vertical bar(calc) = 0.78, a"broken vertical bar(ara) = 0.5). Overall community soft tissue biomass did not change with pH and high mortality was observed only at pH 6.0, although molluscs and arthropods showed significant decreases in soft tissue. This study supports and refines previous findings on how elevated pCO(2) can induce changes in marine biodiversity, underlined by differential vulnerability of different phyla. In addition, it shows significant elevated pCO(2)-/low pH-dependent changes in fundamental community functional responses underpinning changes in ecosystem services.

Particulate and dissolved aluminum and titanium in the upper water column of the Atlantic Ocean

This study investigates the oceanic behavior of the lithogenic trace elements Al and Ti in the upper 200 m of the Atlantic Ocean. The distribution of both metals in the dissolved and particulate phases was assessed along an E-W transect in the eastern tropical North Atlantic (December 2009) and along a meridional Atlantic transect (April-May 2010). The surface water concentrations of particulate and dissolved Al and Ti reflected the previously observed pattern of atmospheric inputs into the Atlantic Ocean. Subsurface minima at stations with pronounced fluorescence maxima were observed, suggesting a link between biological productivity and the removal of both dissolved and particulate Al and Ti. This may include uptake mechanisms, adsorption and aggregation processes on biogenic particle surfaces and the formation of large, fast sinking biogenic particles, e.g., fecal pellets. Residence times in the upper water column (100 m) of the tropical and subtropical North Atlantic were estimated to range in the order of days to weeks in the particulate phases (Al: 3-22 days, Ti: 4-37 days) and were 0.9-3.8 years for Al and 10-31 years for Ti in the dissolved phases. Longer residence times in both phases in the South Atlantic are consistent with lower biological productivity and decreased removal rates. In the upper water column, Al was predominantly present in the dissolved form, whereas Ti mostly occurred in the particulate form. Largest deviations in the partition coefficients between the particulate and dissolved phases were found in the surface waters, together with excess dissolved Al over Ti compared to the crustal source. This likely reflects elevated dissolution of Al compared to Ti from atmospheric mineral particles.

Long-term responses of North Atlantic calcifying plankton to climate change

The global increase in atmospheric carbon dioxide concentration is potentially threatening marine biodiversity in two ways. First, carbon dioxide and other greenhouse gases accumulating in the atmosphere are causing global warming1. Second, carbon dioxide is altering sea water chemistry, making the ocean more acidic2. Although temperature has a cardinal influence on all biological processes from the molecular to the ecosystem level3, acidification might impair the process of calcification or exacerbate dissolution of calcifying organisms4. Here, we show however that North Atlantic calcifying plankton primarily responded to climate-induced changes in temperatures during the period 1960–2009, overriding the signal from the effects of ocean acidification. We provide evidence that foraminifers, coccolithophores, both pteropod and nonpteropod molluscs and echinoderms exhibited an abrupt shift circa 1996 at a time of a substantial increase in temperature5 and that some taxa exhibited a poleward movement in agreement with expected biogeographical changes under sea temperature warming6,7. Although acidification may become a serious threat to marine calcifying organisms, our results suggest that over the study period the primary driver of North Atlantic calcifying planktonwas oceanic temperature.

Organ damage in Atlantic herring larvae as a result of ocean acidification

The dissolution of anthropogenically emitted excess carbon dioxide lowers the pH of the world's ocean water. The larvae of mass spawning marine fishes may be particularly vulnerable to such ocean acidification (OA), yet the generality of earlier results is unclear. Here we show the detrimental effects of OA on the development of a commercially important fish species, the Atlantic herring (Clupea harengus). Larvae were reared at three levels of CO2: today (0.0385 kPa), end of next century (0.183 kPa), and a coastal upwelling scenario (0.426 kPa), under near-natural conditions in large outdoor tanks. Exposure to elevated CO2 levels resulted in stunted growth and development, decreased condition, and severe tissue damage in many organs, with the degree of damage increasing with CO2 concentration. This complements earlier studies of OA on Atlantic cod larvae that revealed similar organ damage but at increased growth rates and no effect on condition.

Colloidal stability of nanoparticles derived from simulated cloud-processed mineral dusts

Laboratory simulation of cloud processing of three model dust types with distinct Fe-content (Moroccan dust, Libyan dust and Etna ash) and reference goethite and ferrihydrite were conducted in order to gain a better understanding of natural nanomaterial inputs and their environmental fate and bioavailability. The resulting nanoparticles (NPs) were characterised for Fe dissolution kinetics, aggregation/size distribution, micromorphology and colloidal stability of particle suspensions using a multi-method approach. We demonstrated that the: (i) acid-leachable Fe concentration was highest in volcanic ash (1 m Mg(-1) dust) and was followed by Libyan and Moroccan dust with an order of magnitude lower levels; (ii) acid leached Fe concentration in the<20 nm fraction was similar in samples processed in the dark with those under artificial sunlight, but average hydrodynamic diameter of NPs after cloud-processing (pH~6) was larger in the former; iii) NPs formed at pH~6 were smaller and less poly-disperse than those at low pH, whilst unaltered zeta potentials indicated colloidal instability; iv) relative Fe percentage in the finer particles derived from cloud processing does not reflect Fe content of unprocessed dusts (e.g. volcanic ash>Libyan dust). The common occurrence of Fe-rich "natural nanoparticles" in atmospheric dust derived materials may indicate their more ubiquitous presence in the marine environment than previously thought.

Chemical interaction of atmospheric mineral dust-derived nanoparticles with natural seawater — EPS and sunlight-mediated changes

Laboratory studies were conducted to investigate the interactions of nanoparticles (NPs) formed via simulated cloud processing of mineral dust with seawater under environmentally relevant conditions. The effect of sunlight and the presence of exopolymeric substances (EPS) were assessed on the: (1) colloidal stability of the nanoparticle aggregates (i.e. size distribution, zeta potential, polydispersity); (2) micromorphology and (3) Fe dissolution from particles. We have demonstrated that: (i) synthetic nano-ferrihydrite has distinct aggregation behaviour from NPs formed from mineral dusts in that the average hydrodynamic diameter remained unaltered upon dispersion in seawater (~1500 nm), whilst all dust derived NPs increased about three fold in aggregate size; (ii) relatively stable and monodisperse aggregates of NPs formed during simulated cloud processing of mineral dust become more polydisperse and unstable in contact with seawater; (iii) EPS forms stable aggregates with both the ferrihydrite and the dust derived NPs whose hydrodynamic diameter remains unchanged in seawater over 24h; (iv) dissolved Fe concentration from NPs, measured here as <3 kDa filter-fraction, is consistently >30% higher in seawater in the presence of EPS and the effect is even more pronounced in the absence of light; (v) micromorphology of nanoparticles from mineral dusts closely resemble that of synthetic ferrihydrite in MQ water, but in seawater with EPS they form less compact aggregates, highly variable in size, possibly due to EPS-mediated steric and electrostatic interactions. The larger scale implications on real systems of the EPS solubilising effect on Fe and other metals with the additional enhancement of colloidal stability of the resulting aggregates are discussed.

Detection and impacts of leakage from sub-seafloor deep geological carbon dioxide storage

Fossil fuel power generation and other industrial emissions of carbon dioxide are a threat to global climate1, yet many economies will remain reliant on these technologies for several decades2. Carbon dioxide capture and storage (CCS) in deep geological formations provides an effective option to remove these emissions from the climate system3. In many regions storage reservoirs are located offshore4, 5, over a kilometre or more below societally important shelf seas6. Therefore, concerns about the possibility of leakage7, 8 and potential environmental impacts, along with economics, have contributed to delaying development of operational CCS. Here we investigate the detectability and environmental impact of leakage from a controlled sub-seabed release of CO2. We show that the biological impact and footprint of this small leak analogue (<1 tonne CO2 d−1) is confined to a few tens of metres. Migration of CO2 through the shallow seabed is influenced by near-surface sediment structure, and by dissolution and re-precipitation of calcium carbonate naturally present in sediments. Results reported here advance the understanding of environmental sensitivity to leakage and identify appropriate monitoring strategies for full-scale carbon storage operations.

The effects of short-term acidification on the intertidal macroalgae Palmaria palmate and Saccharina latissima

Ocean acidification, the result of increased dissolution of carbon dioxide (CO2) in seawater, is a leading subject of current research. The effects of acidification on non-calcifying macroalgae are, however, still unclear. The current study reports two 1-month studies using two different macroalgae, the red alga Palmaria palmata (Rhodophyta) and the kelp Saccharina latissima (Phaeophyta), exposed to control (pHNBS = ∼8.04) and increased (pHNBS = ∼7.82) levels of CO2-induced seawater acidification. The impacts of both increased acidification and time of exposure on net primary production (NPP), respiration (R), dimethylsulphoniopropionate (DMSP) concentrations, and algal growth have been assessed. In P. palmata, although NPP significantly increased during the testing period, it significantly decreased with acidification, whereas R showed a significant decrease with acidification only. S. latissima significantly increased NPP with acidification but not with time, and significantly increased R with both acidification and time, suggesting a concomitant increase in gross primary production. The DMSP concentrations of both species remained unchanged by either acidification or through time during the experimental period. In contrast, algal growth differed markedly between the two experiments, in that P. palmata showed very little growth throughout the experiment, while S. latissima showed substantial growth during the course of the study, with the latter showing a significant difference between the acidified and control treatments. These two experiments suggest that the study species used here were resistant to a short-term exposure to ocean acidification, with some of the differences seen between species possibly linked to different nutrient concentrations between the experiments.

Response of the ammonia oxidation activity of microorganisms in surface sediment to a controlled sub-seabed release of CO2

The impact of a sub-seabed CO2 leak from geological sequestration on the microbial process of ammonia oxidation was investigated in the field. Sediment samples were taken before, during and after a controlled sub-seabed CO2 leak at four zones differing in proximity to the CO2 source (epicentre, and 25m, 75m, and 450m distant). The impact of CO2 release on benthic microbial ATP levels was compared to ammonia oxidation rates and the abundance of bacterial and archaeal ammonia amoA genes and transcripts, and also to the abundance of nitrite oxidize (nirS) and anammox hydrazine oxidoreductase (hzo) genes and transcripts. The major factor influencing measurements was seasonal: only minor differences were detected at the zones impacted by CO2 (epicentre and 25m distant). This included a small increase to ammonia oxidation after 37daysof CO2 release which was linked to an increase in ammonia availability as a result of mineral dissolution. A CO2 leak on the scale used within this study (<1tonneday−1) would have very little impact to ammonia oxidation within coastal sediments. However, seawater containing 5% CO2 did reduce rates of ammonia oxidation. This was linked to the buffering capacity of the sediment, suggesting that the impact of a sub-seabed leak of stored CO2 on ammonia oxidation would be dependent on both the scale of the CO2 release and sediment type.

Ocean acidification with (de)eutrophication will alter future phytoplankton growth and succession.

Human activity causes ocean acidification (OA) though the dissolution of anthropogenically generated CO2 into seawater, and eutrophication through the addition of inorganic nutrients. Eutrophication increases the phytoplankton biomass that can be supported during a bloom, and the resultant uptake of dissolved inorganic carbon during photosynthesis increases water-column pH (bloom-induced basification). This increased pH can adversely affect plankton growth. With OA, basification commences at a lower pH. Using experimental analyses of the growth of three contrasting phytoplankton under different pH scenarios, coupled with mathematical models describing growth and death as functions of pH and nutrient status, we show how different conditions of pH modify the scope for competitive interactions between phytoplankton species. We then use the models previously configured against experimental data to explore how the commencement of bloom-induced basification at lower pH with OA, and operating against a background of changing patterns in nutrient loads, may modify phytoplankton growth and competition. We conclude that OA and changed nutrient supply into shelf seas with eutrophication or de-eutrophication (the latter owing to pollution control) has clear scope to alter phytoplankton succession, thus affecting future trophic dynamics and impacting both biogeochemical cycling and fisheries.

Detection and impacts of leakage from sub-seafloor deep geological carbon dioxide storage

Fossil fuel power generation and other industrial emissions of carbon dioxide are a threat to global climate1, yet many economies will remain reliant on these technologies for several decades2. Carbon dioxide capture and storage (CCS) in deep geological formations provides an effective option to remove these emissions from the climate system3. In many regions storage reservoirs are located offshore4, 5, over a kilometre or more below societally important shelf seas6. Therefore, concerns about the possibility of leakage7, 8 and potential environmental impacts, along with economics, have contributed to delaying development of operational CCS. Here we investigate the detectability and environmental impact of leakage from a controlled sub-seabed release of CO2. We show that the biological impact and footprint of this small leak analogue (<1 tonne CO2 d−1) is confined to a few tens of metres. Migration of CO2 through the shallow seabed is influenced by near-surface sediment structure, and by dissolution and re-precipitation of calcium carbonate naturally present in sediments. Results reported here advance the understanding of environmental sensitivity to leakage and identify appropriate monitoring strategies for full-scale carbon storage operations.