The negative emission potential of alkaline materials

The potential of biomass energy carbon capture and storage is unclear. Here the authors estimated the negative emissions potential from highly alkaline materials, by-products and wastes and showed that these materials have a CO2 storage potential of 2.5–7.5 billion tonnes per year by 2100

The Potential of Carbon Storage in the Ocean as Bicarbonate

Bicarbonate (HCO3-) and carbonate (CO32-) ions in the ocean are a fundamental component of the global carbon cycle. The oceans contain approximately 38,000 billion tonnes of C as HCO3- and CO32- (40x that in the atmosphere) with fluxes between different parts of this reservoir on the order of \u3c1 GtC per year (Figure 1). Eventually, most of anthropogenic CO2 emitted to the atmosphere will be incorporated into this sink as a consequence of mineral weathering. Intentionally storing additional CO2 as HCO3- in the ocean has been suggested since the mid-90s (e.g., ocean liming, accelerated weathering of limestone, enhanced weathering), but estimates on storage potential, environmental impact, and technical feasibility remain poorly constrained. Our recent work has used the output of recent modelling studies in an attempt to estimate the carbon storage potential of this reservoir, and it is apparent that trillions of tonnes of CO2 can be stored with marginal changes in ocean chemistry when the impact is distributed globally. The changes are more acute around the points of addition, and vary with each technology. All proposals for ocean bicarbonate storage require the extraction, comminution, transport, and dissolution of silicate or carbonate rocks. While the global decadal scale-up of such an operation to impact the climate is not unprecedented, it raises questions regarding environmental and social acceptability. Please click Additional Files below to see the full abstract

Assessing ocean alkalinity for carbon sequestration

Over the coming century humanity may need to find reservoirs to store several trillions of tons of carbon dioxide (CO2) emitted from fossil fuel combustion, which would otherwise cause dangerous climate change if it were left in the atmosphere. Carbon storage in the ocean as bicarbonate ions (by increasing ocean alkalinity) has received very little attention. Yet, recent work suggests sufficient capacity to sequester copious quantities of CO2. It may be possible to sequester hundreds of billions to trillions of tonnes of C without surpassing post-industrial average carbonate saturation states in the surface ocean. When globally distributed, the impact of elevated alkalinity is potentially small, and may help ameliorate the effects of ocean acidification. However, the local impact around addition sites may be more acute but is specific to the mineral and technology. The alkalinity of the ocean increases naturally because of rock weathering in which > 1.5 moles of carbon are removed from the atmosphere for every mole of magnesium or calcium dissolved from silicate minerals (e.g., wollastonite, olivine, anorthite), and 0.5 moles for carbonate minerals (e.g., calcite, dolomite). These processes are responsible for naturally sequestering 0.5 billion of CO2 tons per year. Alkalinity is reduced in the ocean through carbonate mineral precipitation, which is almost exclusively formed from biological activity. Most of the previous work on the biological response to changes in carbonate chemistry have focused on acidifying conditions. More research is required to understand carbonate precipitation at elevated alkalinity to constrain the longevity of carbon storage. A range of technologies have been proposed to increase ocean alkalinity (accelerated weathering of limestone, enhanced weathering, electrochemical promoted weathering, ocean liming), the cost of which may be comparable to alternative carbon sequestration proposals (e.g., $20 - 100 tCO2-1). There are still many unanswered technical, environmental, social, and ethical questions, but the scale of the carbon sequestration challenge warrants research to address these.</p

The potential environmental response to increasing ocean alkalinity for negative emissions

The negative emissions technology, artificial ocean alkalinization (AOA), aims to store atmospheric carbon dioxide (CO2) in the ocean by increasing total alkalinity (TA). Calcium carbonate saturation state (ΩCaCO3) and pH would also increase meaning that AOA could alleviate sensitive regions and ecosystems from ocean acidification. However, AOA could raise pH and ΩCaCO3 well above modern-day levels, and very little is known about the environmental and biological impact of this. After treating a red calcifying algae (Corallina spp.) to elevated TA seawater, carbonate production increased by 60% over a control. This has implication for carbon cycling in the past, but also constrains the environmental impact and efficiency of AOA. Carbonate production could reduce the efficiency of CO2 removal. Increasing TA, however, did not significantly influence Corallina spp. primary productivity, respiration, or photophysiology. These results show that AOA may not be intrinsically detrimental for Corallina spp. and that AOA has the potential to lessen the impacts of ocean acidification. However, the experiment tested a single species within a controlled environment to constrain a specific unknown, the rate change of calcification, and additional work is required to understand the impact of AOA on other organisms, whole ecosystems, and the global carbon cycle

Mineral carbonation in soils : engineering the soil carbon sink

Rapid anthropogenic climate change is one of the greatest challenges that human civilisation will face in the 21st century. A 25-180 % increase in atmospheric carbon dioxide content since the early 1800’s and a predicted increase of 2-3% each year will lead to a 2-6°C rise in tropospheric temperatures. The consequences of increased atmospheric temperatures are profound and would put unsustainable strain on human infrastructure, which was conservatively estimated in the Stern Review (2006) to cost approximately 20% of GDP. Given the political, technical, economic and social barriers preventing the transition to a low carbon economy, there is an unequivocal need to research ‘geoengineering’ technologies that can bridge the gap between carbon emission reduction targets and actual emissions. Soil mineral carbonation is one such technology. The atmosphere is one of the smallest carbon pools at the Earth’s Surface (depending on how each pool is demarcated). Soils turn over the quantity of carbon in the atmosphere in under a decade and collectively form one of the largest carbon pools (3-4 times the quantity of carbon in the atmosphere). Land use change since the agricultural revolution has released 256 GtC (40 % of anthropogenic emissions). Research investigating the potential for carbon accumulation in soils is primarily focused on restoring organic carbon concentration to pre-agricultural values through modification of farming practices. The research presented in this thesis is the first that explores the potential of increasing the inorganic carbon pool as an emissions mitigation technology. Inorganic carbon accumulation is promoted by introducing divalent cation rich (predominantly calcium and magnesium) silicate and hydroxide minerals into the soil, which weather and supersaturate the soil solution with respect to carbonate minerals (predominantly calcite, aragonite, magnesite and dolomite). The carbon in the resultant precipitate is derived from the atmosphere. This is analogous to mineral carbonation technologies which induce carbonate precipitation from silicate weathering in industrial scale reactors at elevated temperatures and pressures. However, carbonation in soil exploits natural weathering processes to the same effect with minimal energy and infrastructure input. The research presented in this thesis broadly investigates soil mineral carbonation by contributing work towards the fundamental issues associated with application of soil mineral carbonation technology. Research activity described herein covers a range of laboratory batch weathering experiments, field work, geochemical modelling, plant growth trials, soil microcosm experiments and literature reviews. While eclectic, all work packages contribute to the same goal of describing the efficacy, effectiveness and potential impacts of soil mineral carbonation. The efficacy of mineral carbonation technology is primarily limited by the availability of appropriate silicate bearing material. A literature search suggests that approximately 15-16 Gt a- 1 of silicate rich ‘waste’ materials are produced as a consequence of human activity. This has a carbon capture potential between 190 and 332 MtC a-1, which is equivalent to other emissions mitigation strategies. Quarrying silicate specifically for carbonation is a suggested strategy that may be able to store on the order of 102 GtC a-1 (based on two sites in the US). Therefore, mineral carbonation may form part of global mitigation strategies collectively equivalent to 14 GtC a-1 to stabilise the CO2 concentration of the atmosphere at 500 parts per million by volume. Considering that the potential capacity of soil mineral carbonation is sufficient to act as a substantial emissions mitigation strategy it was appropriate to investigate issues associated with the application of such a technology. In the first instance, sites known to contain silicates were investigated. These include soils developed on natural silicates (on the Whin Sill in Northumberland), construction and demolition waste (at a brownfield site and waste transfer stations) and slag (at a former steelworks). Interpretation of fieldwork results suggests that inorganic carbon accumulation is rapid (up to 38 gC kg-1(soil) a-1), and is orders of magnitude xxv greater than organic carbon accumulation in natural soils. The average concentration of inorganic carbon (20-30 Kg m-3) is equivalent to organic carbon in natural soils. The unusually light carbon and oxygen isotope ratios of the carbonate (-3.1 ‰ and -27.5 ‰ for δ13C and -3.9 ‰ and -20.9 ‰ for δ18O) were used to determine that up to 55% of the carbon was derived from the atmosphere. The rate of carbon capture, which is the same as the precipitation rate of carbonate, is a function of solution chemistry. The more supersaturated a solution is with respect to a carbonate mineral, the more rapid the precipitation rate. Saturation of a solution is a function of divalent cation and carbonate anion concentration. Therefore, the supply of each of these components was investigated in laboratory experiments. Batch weathering experiments were used to investigate the supply of calcium from artificial silicates (hydrated cement gel). Up to 70-80 % of the calcium contained in the mineral was removed, which is consistent with efficiencies reported for conventional mineral carbonation. The log rate of weathering was between -10.66 and -6.86 mol Ca cm-2 sec-1, which is several orders of magnitude greater than that usually reported for natural silicates. Microcosm experiments were conducted to investigate the rate of supply of carbonate from the organic carbon mineralisation in high pH solutions. The research clearly demonstrates that high pH solutions inhibit the breakdown of organic carbon as a function of nutrient supply. Where organic carbon was successfully mineralised the log rates (-3.4 mmol g-1(field moist soil) sec-1) were equivalent to that found in previous studies. While the influx of dissolved carbonate mineral components into the soil solution is the primary controlling step in the rate of carbon accumulation, there is a complex relationship between soil physical properties and geochemistry. This was highlighted in a numerical model that was constructed for this thesis, which suggests that soil pore volume and particle size distribution are important variables. An additional numerical model was constructed to investigate the transportation of silicate material to the application site. This model suggests that an economics of soil mineral carbonation is a function of transport costs, the value of the silicate material and the price of carbon. Field observations, growth trials, microcosm experiments and previous research suggest a complex interaction between biology, weathering and carbonate precipitation. Additional work is required to investigate carbonate precipitation mediated by plant and microorganism activity and the degree to which soil mixed with silicates impact on ecosystem functioning. This research has demonstrated that mineral carbonation in soils could form a substantial emissions mitigation strategy, but additional work is required in a number of areas to which this thesis provides a suitable foundation.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

The dissolution of olivine added to soil: Implications for enhanced weathering

Chemical weathering of silicate minerals consumes atmospheric CO2 and is a fundamental component of geochemical cycles and of the climate system on long timescales. Artificial acceleration of such weathering (“enhanced weathering”) has recently been proposed as a method of mitigating anthropogenic climate change, by adding fine-grained silicate materials to continental surfaces. The efficacy of such intervention in the carbon cycle strongly depends on the mineral dissolution rates that occur, but these rates remain uncertain. Dissolution rates determined from catchment scale investigations are generally several orders of magnitude slower than those predicted from kinetic information derived from laboratory studies. Here we present results from laboratory flow-through dissolution experiments which seek to bridge this observational discrepancy by using columns of soil returned to the laboratory from a field site. We constrain the dissolution rate of olivine added to the top of one of these columns, while maintaining much of the complexity inherent in the soil environment. Continual addition of water to the top of the soil columns, and analysis of elemental composition of waters exiting at the base was conducted for a period of five months, and the solid and leachable composition of the soils was also assessed before and after the experiments. Chemical results indicate clear release of Mg2+ from the dissolution of olivine and, by comparison with a control case, allow the rate of olivine dissolution to be estimated between 10−16.4 and 10−15.5 moles(Mg) cm−2 s−1. Measurements also allow secondary mineral formation in the soil to be assessed, and suggest that no significant secondary uptake of Mg2+ has occurred. The olivine dissolution rates are intermediate between those of pure laboratory and field studies and provide a useful constraint on weathering processes in natural environments, such as during soil profile deepening or the addition of mineral dust or volcanic ash to soils surfaces. The dissolution rates also provide critical information for the assessment of enhanced weathering including the expected surface-area and energy requirements

The Dissolution of Olivine Added to Soil at 4°C: Implications for Enhanced Weathering in Cold Regions

Crushed olivine was added to a soil core to mimic enhanced weathering, and water was continually dripped through for ~6 months. Our experiments were conducted at 4°C, and are compared to previously run identical experiments at 19°C. Olivine dissolution rates in both experiments start out similar, likely due to fines and sharp crystal corners. However, after >100 days of reaction, the dissolution rate at 4°C was two orders of magnitude lower than at 19°C. The accumulation of heavy metals, such as Ni and Cd, was low in both experiments, but soil retention of these elements was proportionally higher at higher temperatures, likely due to enhanced sorption and formation of clays. Overall, this study suggests that olivine dissolution rates in experiments that mimic natural settings are orders of magnitude slower than in normal laboratory experiments, and that enhanced weathering may be a considerably less efficient method of carbon dioxide removal at low climatic temperatures. Both of these conclusions have implications for the application of enhanced weathering as a CO2 removal method