Carbon Dioxide (CO₂) sequestration requires that the injected CO₂ be permanently trapped in the subsurface and not leak from the target location. To accomplish this, it is important to understand the main mechanisms associated with CO₂ flow and transport in the subsurface once CO₂ is injected. In this work CO₂ seeps at the Crystal Geyser site were studied using modeling and simulation to determine how CO₂ geochemically reacts with formation brines and how these interactions impact the migration of CO₂. Furthermore different scenarios for CO₂ migration and seepage along the Grand Wash fault are studied and the possible outcomes for these different scenarios are documented. The GEM (Generalized Equation-of-State Model) from CMG Ltd. was used to perform the simulation studies. A 2-D model was built without geochemical reactions to mainly study the mechanism associated with dissolution of CO₂ gas. The process of CO₂ release from the brine as the fluid mixture flows up along the fault was modeled. Then, 3-D models with geochemical reactions were built for CO₂ migration corresponding to two different sources of CO₂ - deep crustal ₂ and CO₂-dissolved in groundwater. In both these cases, CO₂ reacted with the aqueous components and minerals of the formation and caused carbonate mineralization. In the case of deep crustal CO₂ source, there were vertical patterns of calcite mineralization simulated along the fault that indicated that calcite mineralization might be localized to isolated vertical flow paths due to vertical channeling of CO₂ from the crust. In the case of CO₂-dissolved groundwater flowing along the sandstone layers, calcite mineralization is spread over the entire fault surface. In this case, the groundwater flow is interrupted by the fault and there is vertical flow along the fault until a permeable sandstone layer is encountered on the other side of the fault. This vertical migration of CO₂-saturated brine causes a release in pressure and subsequent ex-solution of CO₂. As a result, modeling allowed us to establish difference in surface expression of CO₂ leakage due to two different CO₂ migrations scenarios along the fault and helped develop a scheme for selecting appropriate model for CO₂ leakage based on surface observation of travertine mounds. A key observation at the Crystal Geyser site is the lateral migration of CO₂ seep sites over time. These migrations have been confirmed by isotope studies. In this modeling study, the mechanism for migration of seep sites was studied. A model for permeability reduction due to precipitation of calcite was developed. It is shown using percolation calculations that flow re-routing due to permeability alterations can result in lateral migration of CO₂ seeps at rates comparable to those established by isotope dating. / text

Rising carbon dioxide (CO2) concentrations in the atmosphere will increase the average pCO2 level in the world oceans, which will have a knock-on effect on the marine ecosystem. Coastal seagrass communities one of the most productive marine ecosystems are predicted to benefit from the increase in CO2 levels, but long-term effects of elevated CO2 on seagrass communities are less understood. Population reconstruction techniques was used to investigate the population dynamics of Cymodocea nodosa meadows, exposed to long term elevated CO2 at volcanic seeps off Greece and Italy. Effect of elevated CO2 was noticed on the growth, morphometry, density, biomass and age structure at CO2 seeps. Above to below ground biomass ratio of C. nodosa were higher at CO2 seeps than at reference sites. The plastochrome interval were similar at all CO2 seeps. The shoot age and shoot longevity of plants were lower at seeps than reference sites. The present recruitment (sampled year) of the seagrass were higher than long-term average recruitment of the communities near the seeps. Carbon to nitrogen ratios (%DW) of C. nodosa were higher in leaves at seeps. Annual leaf production was higher near the seeps. This study suggests increased production of C. nodosa under elevated CO2 levels, but other co-factors such as nutrients, trace metal toxicity must also be taken into consideration while predicting effects of future CO2 concentrations. Volcanic CO2 seeps are now being used as natural analogues for ocean acidification studies although these areas can be affected by trace element input and may alter ecosystem responses to gradient in carbonate chemistry. Here Fe and a range of trace elements (Cd, Co, Cu, Hg, Mn, Pb, Ni and Zn) were analysed from sediments and from the roots, rhizomes and leaves of seagrass at six CO2 seeps and reference sites off Greece and Italy. There were higher metal levels in sediment and seagrasses at all CO2 seeps than reference sites. Sediment Quality Guideline Quotient, a commonly used pollution index, indicated that some of the metals (Cd, Cu, Hg, Ni) were in high enough concentrations to have adverse biological effects, such as Cu at Ischia site and Hg at Vulcano. Higher accumulation of elements from sediments in roots and leaves at CO2 seeps were found from Bio Sediment Accumulation Factor index. There were higher levels of Cu, Fe, Mn and Zn in leaves and rhizomes for P. oceanica and higher levels of Cd, Co, Cu, Fe and Zn in C. nodosa compartments at CO2 seeps. Fe and Mn were found with positive correlation within sediment-roots and sediment-rhizomes, whereas Cd, Co and Pb were found with positive correlation in compartments of C. nodosa. In P. oceanica positive correlation were only observed for Cd within sediment-roots and plant compartments. Low pH and ocean acidification increased the concentration of elements at CO2 seeps than reference sites. Thus, caution is needed, when using volcanic seep systems as analogue for the effects of rising CO2, as metals can reach levels that are toxic to seagrass, masking any potential benefits of increased levels of carbon dioxide for seagrass productivity. Net community production (NCP) and community respiration (CR) were measured under air exposed and CO2 enriched conditions for intertidal Z. noltei meadows and unvegetated sediment communities during emersion in summer and winter seasons. Community production and respiration were measured in-situ using benthic chambers. CO2 flux under air and CO2 enriched conditions were measured over a series of short term incubations (30min) using an infra-red gas analyser. Incident photosynthetic active radiation (PAR) was recorded during the incubations covering the daily and seasonal variation. Linear regression model was used to test the effects of irradiance on net community production. NCP of Z. noltei community were higher under CO2 enriched conditions than air exposed conditions in both summer and winter seasons. There was no effect of CO2 on the CR rate of Z. noltei community in summer season. NCP of sediment community were higher in summer season and winter season under CO2 enriched conditions. Sediment CR rates were higher in winter than summer season. The light compensation point of Z. noltei and sediment community were lower in both seasons under CO2 enriched conditions. Seasonal budget of community production was higher in Z. noltei than sediment communities. A clear effect of PAR was noticed on the net community production of both communities. Higher PAR intensities resulted in higher NCP under CO2 enriched conditions for both communities. CO2 enrichment will have a positive effect on the intertidal communities during emersion.

Ocean acidification may cause biodiversity loss, alter ecosystems and impact food security, yet uncertainty over ecological responses to ocean acidification remains considerable. Most work on the impact of ocean acidification on foraminifera has been short-term laboratory experiments on single species. To expand this, benthic foraminiferal assemblages were examined across shallow water CO2 gradients in the Gulf of California, off the islands of Ischia and Vulcano in Italy and off Papua New Guinea. Living assemblages from the Gulf of California did not appear to show a response across a pH range of 7.55 – 7.88, although the species assemblage was impoverished in all locations and the dead assemblage was less diverse at the lowest pH sites where there was evidence of post mortem dissolution. At Vulcano, the small macroalga, Padina pavonica, did not protect calcareous foraminifera from the adverse effects of ocean acidification. Calcareous taxa disappeared from the assemblage and were replaced by agglutinated foraminifera as mean pH reduced from 8.19 to 7.71. Settlement of benthic foraminifera onto artificial collectors off Vulcano was adversely affected in the acidified water, with few species as pCO2 increased and evidence of post-mortem dissolution. The foraminiferal tests, collected off Papua New Guinea, had lower δ11B as mean pH decreased from 7.99 – 7.82 for small (250 – 500 µm) Amphistegina lessonii, but not for A. lessonii or Calcarina spengleri >500 µm. In the larger foraminifera, photosynthetic activity by symbionts may begin to dominate the boron isotopic signature. Overall, the responses of foraminiferal assemblages to ocean acidification are complex, but there was an overall reduction in species diversity in infaunal, epifaunal and epiphytic assemblages as pCO2 increased. This raises serious concerns for the survival of shallow water calcareous benthic foraminifera as the oceans continue to acidify, with implications for benthic ecosystems and inorganic carbon cycling.