Philip Renforth

Silicate Production and Availability for Mineral Carbonation

Atmospheric carbon dioxide sequestered as carbonates through the accelerated weathering of silicate minerals is proposed as a climate change mitigation technology with the potential to capture billions of tonnes of carbon per year. Although these materials can be mined expressly for carbonation, they are also produced by human activities (cement, iron and steel making, coal combustion, etc.). Despite their potential, there is poor global accounting of silicates produced in this way. This paper presents production estimates (by proxy) of various silicate materials including aggregate and mine waste, cement kiln dust, construction and demolition waste, iron and steel slag, and fuel ash. Approximately 7-17 billion tonnes are produced globally each year with an approximate annual sequestration potential of 190-332 million tonnes C. These estimates provide justification for additional research to accurately quantify the contemporary production of silicate minerals and to determine the location and carbon capture potential of historic material accumulations.

Contaminant mobility and carbon sequestration downstream of the Ajka (Hungary) red mud spill: The effects of gypsum dosing

A number of emergency pollution management measures were enacted after the accidental release of caustic bauxite processing residue that occurred in Ajka, western Hungary in October, 2010. These centred on acid and gypsum dosing to reduce pH and minimise mobility of oxyanion contaminants mobile at high pH. This study assessed the effectiveness of gypsum dosing on contaminant mobility and carbon sequestration through assessment of red mud and gypsum-affected fluvial sediments via elemental analysis and stable isotope analysis. There was a modest uptake of contaminants (notably As, Cr, and Mn) on secondary carbonate-dominated deposits in reaches subjected to gypsum dosing. C and O stable isotope ratios of carbonate precipitates formed as a result of gypsum dosing were used to quantify the importance of the neutralisation process in sequestering atmospheric carbon dioxide. This process was particularly pronounced at sites most affected by gypsum addition, where up to 36% of carbonate-C appears to be derived from atmospheric in-gassing of CO(2). The site is discussed as a large scale analogue for potential remedial approaches and carbon sequestration technologies that could be applied to red mud slurries and other hyperalkaline wastes. The results of this work have substantial implications for the aluminium production industry in which 3-4% of the direct CO(2) emissions may be offset by carbonate precipitation. Furthermore, carbonation by gypsum addition may be important for contaminant remediation, also providing a physical stabilisation strategy for the numerous historic stockpiles of red mud.

Investigating carbonate formation in urban soils as a method for capture and storage of atmospheric carbon

This paper investigates the potential for engineered urban soils to capture and store atmospheric carbon (C). Calcium (Ca) and magnesium (Mg) bearing waste silicate minerals within the soil environment can capture and store atmospheric C through the process of weathering and secondary carbonate mineral precipitation. Anthropogenic soils, known to contain substantial quantities of Ca and Mg-rich minerals derived from demolition activity (particularly cement and concrete), were systematically sampled at the surface across a 10 ha brownfield site, Science Central, located in the urban centre of Newcastle upon Tyne, U.K. Subsequent analysis yielded average carbonate contents of 21.8±4.7% wt CaCO(3). Isotopic analysis demonstrated δ(18)O values between -9.4‰ and -13.3‰ and δ(13)C values between -7.4‰ and -13.6‰ (relative to Pee Dee Belemnite), suggesting that up to 39.4±8.8% of the carbonate C has been captured from the atmosphere through hydroxylation of dissolved CO(2) in high pH solutions. The remaining carbonate C is derived from lithogenic sources. 37.4 kg of atmospheric CO(2) has already been captured and stored as carbonate per Mg of soil across the site, representing a carbon dioxide (CO(2)) removal rate of 12.5 kg CO(2) Mg(-1) yr(-1). There is the potential for capture and storage of a further 27.3 kg CO(2) Mg(-1) in residual reactive materials, which may be exploited through increased residence time (additional in situ weathering). Overall, the Science Central site has the potential to capture and store a total of 64,800 Mg CO(2) as carbonate minerals. This study illustrates the potential for managing urban soils as tools of C capture and storage, an important ecosystem service, and demonstrates the importance of studying C storage in engineering urban anthropogenic soils.

Behavior of Aluminum, Arsenic, and Vanadium during the Neutralization of Red Mud Leachate by HCl, Gypsum, or Seawater

Red mud leachate (pH 13) collected from Ajka, Hungary is neutralized to < pH 10 by HCl, gypsum, or seawater addition. During acid neutralization >99% Al is removed from solution during the formation of an amorphous boehmite-like precipitate and dawsonite. Minor amounts of As (24%) are also removed from solution via surface adsorption of As onto the Al oxyhydroxides. Gypsum addition to red mud leachate results in the precipitation of calcite, both in experiments and in field samples recovered from rivers treated with gypsum after the October 2010 red mud spill. Calcite precipitation results in 86% Al and 81% As removal from solution, and both are nonexchangeable with 0.1 mol L(-1) phosphate solution. Contrary to As associated with neoformed Al oxyhydroxides, EXAFS analysis of the calcite precipitates revealed only isolated arsenate tetrahedra with no evidence for surface adsorption or incorporation into the calcite structure, possibly as a result of very rapid As scavenging by the calcite precipitate. Seawater neutralization also resulted in carbonate precipitation, with >99% Al and 74% As removed from solution during the formation of a poorly ordered hydrotalcite phase and via surface adsorption to the neoformed precipitates, respectively. Half the bound As could be remobilized by phosphate addition, indicating that As was weakly bound, possibly in the hydrotalcite interlayer. Only 5-16% V was removed from solution during neutralization, demonstrating a lack of interaction with any of the neoformed precipitates. High V concentrations are therefore likely to be an intractable problem during the treatment of red mud leachates.

Carbon dioxide efficiency of terrestrial enhanced weathering.

Terrestrial enhanced weathering, the spreading of ultramafic silicate rock flour to enhance natural weathering rates, has been suggested as part of a strategy to reduce global atmospheric CO2 levels. We budget potential CO2 sequestration against associated CO2 emissions to assess the net CO2 removal of terrestrial enhanced weathering. We combine global spatial data sets of potential source rocks, transport networks, and application areas with associated CO2 emissions in optimistic and pessimistic scenarios. The results show that the choice of source rocks and material comminution technique dominate the CO2 efficiency of enhanced weathering. CO2 emissions from transport amount to on average 0.5-3% of potentially sequestered CO2. The emissions of material mining and application are negligible. After accounting for all emissions, 0.5-1.0 t CO2 can be sequestered on average per tonne of rock, translating into a unit cost from 1.6 to 9.9 GJ per tonne CO2 sequestered by enhanced weathering. However, to control or reduce atmospheric CO2 concentrations substantially with enhanced weathering would require very large amounts of rock. Before enhanced weathering could be applied on large scales, more research is needed to assess weathering rates, potential side effects, social acceptability, and mechanisms of governance.

Passive sequestration of atmospheric CO2 through coupled plant-mineral reactions in urban soils.

Photosynthetic removal of CO(2) from the atmosphere is an important planetary carbon dioxide removal mechanism. Naturally, an amount equivalent to all atmospheric carbon passes through the coupled plant-soil system within 7 years. Plants cycle up to 40% of photosynthesized carbon through their roots, providing a flux of C at depth into the soil system. Root-exuded carboxylic acids have the potential to supply 4-5 micromoles C hr(-1)g(-1) fresh weight to the soil solution, and enhance silicate mineral weathering. Ultimately, the final product of these root-driven processes is CO(2), present in solution as bicarbonate. This combines with Ca liberated by corrosion associated with silicate mineral weathering to enter the soil-water system and to produce pedogenic calcium carbonate precipitates. Combining understanding of photosynthesis and plant root physiology with knowledge of mineral weathering provides an opportunity to design artificial soils or to plan land use in ways that maximize removal and sequestration of atmospheric CO(2) through artificially enhanced pedogenic carbonate precipitation. This process requires relatively low energy and infrastructure inputs. It offers a sustainable carbon dioxide removal mechanism analogous to the use of constructed wetlands for the passive remediation of contaminated waters, and is likely to achieve wide public acceptance.

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.,

Occupational Therapy Predischarge Home Visits: A Study from a Community Hospital

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.

Rapid Removal of Atmospheric CO2 by Urban Soils

The characteristics of 79 patients in a community hospital having an occupational therapy home visit during a period of one year were monitored. The processes of the home visit were examined and, in particular, the relationships of diagnosis and overall measures of levels of functioning – the Physical Self-Maintenance (PSM) and Instrumental Activities of Daily Living (IADL) scales – with the recommendations of the occupational therapists were analysed. The 79 patients had a mean age of 78.5 years; 27 (34.2%) were male and 58 (73.4%) lived alone. The mean time spent in the home by the occupational therapist was 49 minutes and the mean time for the whole visit including travelling time was 108.4 minutes. Only one patient (1.3%) was completely independent in all six PSM categories and no patient was completely independent in all eight IADL items. Seventy-two (91.6%) patients were eventually discharged to a non-institutional setting, mainly the patients own home. Current diagnosis, except for cerebrovascular disease, was not significantly related to higher overall dependency, recommended equipment or carer visit frequency. Higher overall dependency showed significant relationships with recommended carer frequency and time spent assessing the patient in the home, but not consistently with recommended equipment or home adaptations. When specific categories of equipment were considered, for example that for use in the kitchen, overall low dependency was significantly related to the recommendation for this type of equipment. The study confirms the need for assessments beyond those of diagnosis alone in rehabilitation. Overall measures of levels of functioning, although useful in measuring outcomes, are of less certain value for assessment. Specific subcategories of dependency scales are probably of more value than overall scores for occupational therapy assessment.

Biogeochemical processes and geotechnical applications: Progress, opportunities and challenges

The measured calcium carbonate content of soils to a depth of 100 mm at a large urban development site has increased over 18 months at a rate that corresponds to the sequestration of 85 t of CO2/ha (8.5 kg of CO2 m(-2)) annually. This is a consequence of rapid weathering of calcium silicate and hydroxide minerals derived from the demolition of concrete structures, which releases Ca that combines with CO2 ultimately derived from the atmosphere, precipitating as calcite. Stable isotope data confirm an atmospheric origin for carbonate carbon, and 14C dating indicates the predominance of modern carbon in the pedogenic calcite. Trial pits show that carbonation extends to depths of ≥1 m. Work at other sites shows that the occurrence of pedogenic carbonates is widespread in artificially created urban soils containing Ca and Mg silicate minerals. Appropriate management of fewer than 12000 ha of urban land to maximize calcite precipitation has the potential to remove 1 million t of CO2 from the atmosphere annually. The maximal global potential is estimated to be approximately 700-1200 Mt of CO2 per year (representing 2.0-3.7% of total emissions from fossil fuel combustion) based on current rates of production of industry-derived Ca- and Mg-bearing materials.