scholarly journals Ocean Alkalinity Enhancement – Avoiding runaway CaCO<sub>3</sub> precipitation during quick and hydrated lime dissolution

2021 ◽  
Author(s):  
Charly Andre Moras ◽  
Lennart Thomas Bach ◽  
Tyler Cyronak ◽  
Renaud Joannes-Boyau ◽  
Kai Georg Schulz

Abstract. Ocean Alkalinity Enhancement (OAE) has been proposed as a method to remove carbon dioxide (CO2) from the atmosphere and to counteract ocean acidification. It involves the dissolution of alkaline minerals such as quick lime, CaO, and hydrated lime, Ca(OH)2. However, a critical knowledge gap exists regarding their dissolution in natural seawater. Particularly, how much can be dissolved before secondary precipitation of calcium carbonate (CaCO3) occurs is yet to be established. Secondary precipitation should be avoided as it reduces the atmospheric CO2 uptake potential of OAE. Here we show that both CaO and Ca(OH)2 powders (> 63 µm of diameter) dissolved in seawater within a few hours. However, CaCO3 precipitation, in the form of aragonite, occurred at a saturation (ΩAr) threshold of about 5. This limit is much lower than what would be expected for typical pseudo-homogeneous precipitation in the presence of colloids and organic materials. Secondary precipitation at unexpectedly low ΩAr was the result of so-called heterogeneous precipitation onto mineral phases, most likely onto CaO and Ca(OH)2 prior to full dissolution. Most importantly, this led to runaway CaCO3 precipitation by which significantly more alkalinity (TA) was removed than initially added, until ΩAr reached levels below 2. Such runaway precipitation would reduce the CO2 uptake efficiency from about 0.8 moles of CO2 per mole of TA down to only 0.1 mole of CO2 per mole of TA. Runaway precipitation appears to be avoidable by dilution below the critical ΩAr threshold of 5, ideally within hours of the addition to minimise initial CaCO3 precipitation. Finally, model considerations suggest that for the same ΩAr threshold, the amount of TA that can be added to seawater would be more than three times higher at 5 °C than at 30 °C, and that equilibration to atmospheric CO2 levels during mineral dissolution would further increase it by a factor of ~6 and ~3 respectively.

2010 ◽  
Vol 6 (6) ◽  
pp. 827-841 ◽  
Author(s):  
A. M. de Boer ◽  
A. J. Watson ◽  
N. R. Edwards ◽  
K. I. C. Oliver

Abstract. The canonical question of which physical, chemical or biological mechanisms were responsible for oceanic uptake of atmospheric CO2 during the last glacial is yet unanswered. Insight from paleo-proxies has led to a multitude of hypotheses but none so far have been convincingly supported in three dimensional numerical modelling experiments. The processes that influence the CO2 uptake and export production are inter-related and too complex to solve conceptually while complex numerical models are time consuming and expensive to run which severely limits the combinations of mechanisms that can be explored. Instead, an intermediate inverse box model approach of the soft tissue pump is used here in which the whole parameter space is explored. The glacial circulation and biological production states are derived from these using proxies of glacial export production and the need to draw down CO2 into the ocean. We find that circulation patterns which explain glacial observations include reduced Antarctic Bottom Water formation and high latitude upwelling and mixing of deep water and to a lesser extent reduced equatorial upwelling. The proposed mechanism of CO2 uptake by an increase of eddies in the Southern Ocean, leading to a reduced residual circulation, is not supported. Regarding biological mechanisms, an increase in the nutrient utilization in either the equatorial regions or the northern polar latitudes can reduce atmospheric CO2 and satisfy proxies of glacial export production. Consistent with previous studies, CO2 is drawn down more easily through increased productivity in the Antarctic region than the sub-Antarctic, but that violates observations of lower export production there. The glacial states are more sensitive to changes in the circulation and less sensitive to changes in nutrient utilization rates than the interglacial states.


SPE Journal ◽  
2014 ◽  
Vol 19 (06) ◽  
pp. 1058-1068 ◽  
Author(s):  
P.. Bolourinejad ◽  
R.. Herber

Summary Depleted gas fields are among the most probable candidates for subsurface storage of carbon dioxide (CO2). With proven reservoir and qualified seal, these fields have retained gas over geological time scales. However, unlike methane, injection of CO2 changes the pH of the brine because of the formation of carbonic acid. Subsequent dissolution/precipitation of minerals changes the porosity/permeability of reservoir and caprock. Thus, for adequate, safe, and effective CO2 storage, the subsurface system needs to be fully understood. An important aspect for subsurface storage of CO2 is purity of this gas, which influences risk and cost of the process. To investigate the effects of CO2 plus impurities in a real case example, we have carried out medium-term (30-day) laboratory experiments (300 bar, 100°C) on reservoir and caprock core samples from gas fields in the northeast of the Netherlands. In addition, we attempted to determine the maximum allowable concentration of one of the possible impurities in the CO2 stream [hydrogen sulfide (H2S)] in these fields. The injected gases—CO2, CO2+100 ppm H2S, and CO2+5,000 ppm H2S—were reacting with core samples and brine (81 g/L Na+, 173 g/L Cl−, 22 g/L Ca2+, 23 g/L Mg2+, 1.5 g/L K+, and 0.2 g/L SO42−). Before and after the experiments, the core samples were analyzed by scanning electron microscope (SEM) and X-ray diffraction (XRD) for mineralogical variations. The permeability of the samples was also measured. After the experiments, dissolution of feldspars, carbonates, and kaolinite was observed as expected. In addition, we observed fresh precipitation of kaolinite. However, two significant results were obtained when adding H2S to the CO2 stream. First, we observed precipitation of sulfate minerals (anhydrite and pyrite). This differs from results after pure CO2 injection, where dissolution of anhydrite was dominant in the samples. Second, severe salt precipitation took place in the presence of H2S. This is mainly caused by the nucleation of anhydrite and pyrite, which enabled halite precipitation, and to a lesser degree by the higher solubility of H2S in water and higher water content of the gas phase in the presence of H2S. This was confirmed by the use of CMG-GEM (CMG 2011) modeling software. The precipitation of halite, anhydrite, and pyrite affects the permeability of the samples in different ways. After pure CO2 and CO2+100 ppm H2S injection, permeability of the reservoir samples increased by 10–30% and ≤3%, respectively. In caprock samples, permeability increased by a factor of 3–10 and 1.3, respectively. However, after addition of 5,000 ppm H2S, the permeability of all samples decreased significantly. In the case of CO2+100 ppm H2S, halite, anhydrite, and pyrite precipitation did balance mineral dissolution, causing minimal variation in the permeability of samples.


2011 ◽  
Vol 8 (11) ◽  
pp. 3203-3218 ◽  
Author(s):  
A. Lohila ◽  
K. Minkkinen ◽  
M. Aurela ◽  
J.-P. Tuovinen ◽  
T. Penttilä ◽  
...  

Abstract. Drainage for forestry purposes increases the depth of the oxic peat layer and leads to increased growth of shrubs and trees. Concurrently, the production and uptake of the greenhouse gases carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) change: due to the accelerated decomposition of peat in the presence of oxygen, drained peatlands are generally considered to lose peat carbon (C). We measured CO2 exchange with the eddy covariance (EC) method above a drained nutrient-poor peatland forest in southern Finland for 16 months in 2004–2005. The site, classified as a dwarf-shrub pine bog, had been ditched about 35 years earlier. CH4 and N2O fluxes were measured at 2–5-week intervals with the chamber technique. Drainage had resulted in a relatively little change in the water table level, being on average 40 cm below the ground in 2005. The annual net ecosystem exchange was −870 ± 100 g CO2 m−2 yr−1 in the calendar year 2005, indicating net CO2 uptake from the atmosphere. The site was a small sink of CH4 (−0.12 g CH4 m−2 yr−1) and a small source of N2O (0.10 g N2O m−2 yr−1). Photosynthesis was detected throughout the year when the air temperature exceeded −3 °C. As the annual accumulation of C in the above and below ground tree biomass (175 ± 35 g C m−2) was significantly lower than the accumulation observed by the flux measurement (240 ± 30 g C m−2), about 65 g C m−2 yr−1 was likely to have accumulated as organic matter into the peat soil. This is a higher average accumulation rate than previously reported for natural northern peatlands, and the first time C accumulation has been shown by EC measurements to occur in a forestry-drained peatland. Our results suggest that forestry-drainage may significantly increase the CO2 uptake rate of nutrient-poor peatland ecosystems.


2009 ◽  
Vol 6 (4) ◽  
pp. 6579-6599
Author(s):  
S. V. Smith ◽  
J.-P. Gattuso

Abstract. Geochemical theory describes long term cycling of atmospheric CO2 between the atmosphere and rocks at the Earth surface in terms of rock weathering and precipitation of sedimentary minerals. Chemical weathering of silicate rocks takes up atmospheric CO2, releases cations and HCO3− to water, and precipitates SiO2, while CaCO3 precipitation consumes Ca2+ and HCO3− and releases one mole of CO2 to the atmosphere for each mole of CaCO3 precipitated. At steady state, according to this theory, the CO2 uptake and release should equal one another. In contradiction to this theory, carbonate precipitation in the present surface ocean releases only about 0.6 mol of CO2 per mole of carbonate precipitated. This is a result of the buffer effect described by Ψ, the molar ratio of net CO2 gas evasion to net CaCO3 precipitation from seawater in pCO2 equilibrium with the atmosphere. This asymmetry in CO2 flux between weathering and precipitation would quickly exhaust atmospheric CO2, posing a conundrum in the classical weathering and precipitation cycle. While often treated as a constant, Ψ actually varies as a function of salinity, pCO2, and temperature. Introduction of organic C reactions into the weathering-precipitation couplet largely reconciles the relationship. ψ in the North Pacific Ocean central gyre rises from 0.6 to 0.9, as a consequence of organic matter oxidation in the water column. ψ records the combined effect of CaCO3 and organic reactions and storage of dissolved inorganic carbon in the ocean, as well as CO2 gas exchange between the ocean and atmosphere. Further, in the absence of CaCO3 reactions, Ψ would rise to 1.0. Similarly, increasing atmospheric pCO2 over time, which leads to ocean acidification, alters the relationship between organic and inorganic C reactions and carbon storage in the ocean. Thus, the carbon reactions and ψ can cause large variations in oceanic carbon storage with little exchange with the atmosphere.


Energies ◽  
2019 ◽  
Vol 12 (15) ◽  
pp. 2903 ◽  
Author(s):  
Sung-Hoon Kang ◽  
Yang-Hee Kwon ◽  
Juhyuk Moon

In the cement industry, utilization of a sustainable binder that has a lower energy consumption and carbon dioxide (CO2) emission than Portland cement is becoming increasingly important. Air lime is a binder that hardens by absorbing CO2 from the atmosphere, and its raw material, hydrated lime, is manufactured at a lower temperature (around 900 °C) than cement (around 1450 °C). In this study, the amount and rate of CO2 uptake by air lime-based materials are quantitatively evaluated under ambient curing conditions of 20 °C, 60% relative humidity, and 0.04% CO2 concentration. In addition, the effects of the water-to-binder ratio (w/b) and silica fume addition on the material properties of the air lime mortar, such as strength, weight change, carbonation depth, and pore structure, are investigated. Unlike hydraulic materials, such as Portland cement, the air lime mortar did not set and harden under a sealed curing condition, however, once exposed to dry air, the mortar began to harden by absorbing CO2. During the first week, most of the internal water evaporated, thus, the mortar weight was greatly reduced. After that, however, both the weight and the compressive strength consistently increased for at least 180 days due to the carbonation reaction. Based on the 91-day properties, replacing 10% of hydrated lime with silica fume improved the compressive and flexural strengths by 27% and 13% respectively, whereas increasing the w/b from 0.4 to 0.6 decreased both strengths by 29% due to the increased volume of the capillary pores. The addition of silica fume and the change in the w/b had no significant impact on the amount of CO2 uptake, but these two factors were effective in accelerating the CO2 uptake rate before 28 days. Lastly, the air lime-based material was evaluated to be capable of recovering half of the emitted CO2 during the manufacture of hydrated lime within 3 months.


2014 ◽  
Vol 11 (3) ◽  
pp. 735-747 ◽  
Author(s):  
T. L. Smallman ◽  
M. Williams ◽  
J. B. Moncrieff

Abstract. The coupled numerical weather model WRF-SPA (Weather Research and Forecasting model and Soil-Plant-Atmosphere model) has been used to investigate a 3 yr time series of observed atmospheric CO2 concentrations from a tall tower in Scotland, UK. Ecosystem-specific tracers of net CO2 uptake and net CO2 release were used to investigate the contributions to the tower signal of key land covers within its footprint, and how contributions varied at seasonal and interannual timescales. In addition, WRF-SPA simulated atmospheric CO2 concentrations were compared with two coarse global inversion models, CarbonTrackerEurope and the National Oceanic and Atmospheric Administration's CarbonTracker (CTE-CT). WRF-SPA realistically modelled both seasonal (except post harvest) and daily cycles seen in observed atmospheric CO2 at the tall tower (R2 = 0.67, rmse = 3.5 ppm, bias = 0.58 ppm). Atmospheric CO2 concentrations from the tall tower were well simulated by CTE-CT, but the inverse model showed a poorer representation of diurnal variation and simulated a larger bias from observations (up to 1.9 ppm) at seasonal timescales, compared to the forward modelling of WRF-SPA. However, we have highlighted a consistent post-harvest increase in the seasonal bias between WRF-SPA and observations. Ecosystem-specific tracers of CO2 exchange indicate that the increased bias is potentially due to the representation of agricultural processes within SPA and/or biases in land cover maps. The ecosystem-specific tracers also indicate that the majority of seasonal variation in CO2 uptake for Scotland's dominant ecosystems (forests, cropland and managed grassland) is detectable in observations within the footprint of the tall tower; however, the amount of variation explained varies between years. The between years variation in detectability of Scotland's ecosystems is potentially due to seasonal and interannual variation in the simulated prevailing wind direction. This result highlights the importance of accurately representing atmospheric transport used within atmospheric inversion models used to estimate terrestrial source/sink distribution and magnitude.


2013 ◽  
Vol 4 (2) ◽  
pp. 869-873
Author(s):  
M. Heimann

Abstract. Becker et al. (2013) argue that an afforestation of 0.73 109 ha with Jatropha curcas plants would generate an additional terrestrial carbon sink of 4.3 PgC yr−1, enough to stabilise the atmospheric mixing ratio of carbon dioxide (CO2) at current levels. However, this is not consistent with the dynamics of the global carbon cycle. Using a well established global carbon cycle model, the effect of adding such a hypothetical sink leads to a reduction of atmospheric CO2 levels in the year 2030 by 25 ppm compared to a reference scenario. However, the stabilisation of the atmospheric CO2 concentration requires a much larger additional sink or corresponding reduction of anthropogenic emissions.


1992 ◽  
Vol 40 (5) ◽  
pp. 407 ◽  
Author(s):  
JA Taylor ◽  
J Lloyd

The biosphere plays an important role in determining the sources, sinks, levels and rates of change of atmospheric CO2 concentrations. Significant uncertainties remain in estimates of the fluxes of CO2 from biomass burning and deforestation, and uptake and storage of CO2 by the biosphere arising from increased atmospheric CO2 concentrations. Calculation of probable rates of carbon sequestration for the major ecosystem complexes and global 3-D tracer transport model runs indicate the possibility that a significant net CO2 uptake (> 1 Pg C yr-1), a CO2 'fertilisation effect', may be occurring in tropical rainforests, effectively accounting for much of the 'missing sink'. This sink may currently balance much of the CO2 added to the atmosphere from deforestation and biomass burning. Interestingly, CO2 released from biomass burning may itself be playing an important role in enhanced carbon storage by tropical rainforests. This has important implications for predicting future CO2 concentrations. If tropical rainforest destruction continues then much of the CO2 stored as a result of the CO2 'fertilisation effect' will be rereleased to the atmosphere and much of the 'missing sink' will disappear. These effects have not been considered in the IPCC (Intergovernmental Panel on Climate Change) projections of future atmospheric CO2 concentrations. Predictions which take account of the combined effects of deforestation, the return of carbon previously stored through the CO2 'fertilisation effect' and the loss of a large proportion of the 'missing sink' as a result of deforestation, would result in much higher predicted concentrations and rates of increase of atmospheric CO2 and, as a consequence, accelerated rates of climate change.


1977 ◽  
Vol 4 (4) ◽  
pp. 467 ◽  
Author(s):  
M Bodson ◽  
RW King ◽  
LT Evans ◽  
G Bernier

Flowering can be induced in the long-day plant Sinapis alba in 8-h photoperiods provided that the irradiance is close to that at which leaf photosynthesis is light-saturated (e.g. 96 J m-2 s-1). Three such 8-h cycles result in 10% flowering and six are required for full flowering, whereas only one long-day cycle of 16-20 h duration at a much lower irradiance (25 J m-2 s-1) is required for full flowering. High irradiance during the single long day promotes flowering when given for the first 8 h of a 16-h photoperiod, but is inhibitory over the last 8 h. Photosynthetic CO2 uptake is crucial for this response to high irradiance, as both its inhibitory and promotive effects on flowering are reversed by the removal of atmospheric CO2 during the period of high irradiance. Compared with plants kept in short days (8-h photoperiod), export of 14C-labelled assimilates from the leaf during a 24-h period was only 50-60% greater in plants exposed to a long day (20-h photoperiod), because plants in short days compensated to a degree for their shorter photosynthetic period by mobilizing leaf reserves during darkness. However, flowering can occur with no evident enhancement of supply of assimilate to the shoot apex, for example following dis- placement of the short day or on removal of atmospheric CO2 during the last 12 h of exposure to a 20-h long day. Also, the flowering response to radiant flux density during the second half of a long day shows an optimum between 15 and 70 J m-2 s-1, with reduced flowering both above and below this irradiance. Thus, although there is no absolute requirement for long days to induce flowering in S. alba, light reactions cther than photosynthesis probably contribute to photoperiodic induction in this species.


2005 ◽  
Vol 35 (3) ◽  
pp. 730-740 ◽  
Author(s):  
Nereu Augusto Streck

The amount of carbon dioxide (CO2) of the Earth´s atmosphere is increasing, which has the potential of increasing greenhouse effect and air temperature in the future. Plants respond to environment CO2 and temperature. Therefore, climate change may affect agriculture. The purpose of this paper was to review the literature about the impact of a possible increase in atmospheric CO2 concentration and temperature on crop growth, development, and yield. Increasing CO2 concentration increases crop yield once the substrate for photosynthesis and the gradient of CO2 concentration between atmosphere and leaf increase. C3 plants will benefit more than C4 plants at elevated CO2. However, if global warming will take place, an increase in temperature may offset the benefits of increasing CO2 on crop yield.


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