Kinetics of maize cob and bean straw pyrolysis and combustion.

Kinetic studies are important for the design and optimisation of thermochemical processes. This study involved analysis of the pyrolysis and combustion behaviour of the agricultural residues (bean straw and maize cob) by non-isothermal thermogravimetric analysis. Increasing the heating rate from 10 to 40 K min-1 during both combustion and pyrolysis increased the degradation rate of both feedstocks and the gaseous yields of H2O, CO and CO2. The activation energies determined by the Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose methods varied which reveals that the pyrolysis and combustion of these agricultural residues are complex processes involving multiple reactions. The average activation energy of maize cob and bean straw were 214.15 and 252.09 kJ mol-1 for pyrolysis and 202.26 and 165.64 kJ mol-1 for combustion, respectively. The order of reaction ranged between 9.0-10.3 and 6.3-13.3 for both feedstocks in combustion and inert environments, respectively. Modelled data is important to enable the optimisation of reactor design for pyrolysis and combustion for energy generation from agricultural residues.

Biochar benefits carbon off-setting in blue-green infrastructure soils - A lysimeter study.

Carbon sequestration with amendments in blue-green infrastructure soils could off-set anthropogenic greenhouse gas emissions to alleviate climate change. In this 3-year study, the effects of wheat straw and its biochar on carbon sequestration in an urban landscaping soil were investigated under realistic outdoor conditions using two large-scale lysimeters. Both amendments were carried out by incorporating pellets at 0-15 cm soil depth with an equivalent initial total carbon input of 2% of the dry soil weight. Soil carbon, carbon isotope ratios, dissolved carbon in leachates, CO2-C emissions, carbon fixed in above ground vegetation, soil water content, soil bulk electrical conductivity, and water infiltration rates, were then compared between the 2 lysimeters. After 3 years, we observed that, despite having a 17.2% lower vegetation growth, soil organic and inorganic carbon content was higher by 28.8% and 41.5%, respectively, in biochar as compared to wheat straw amended soil. Carbon isotope analysis confirmed the greater stability of the added carbon in the biochar amended soil. Water content was on average 23.2% and 13.0% in the straw pellet and biochar amended soil, respectively, whereas water infiltration rates were not significantly different between the two lysimeters. Overall, the incorporation of wheat straw biochar into soil could store an estimated 30 tonnes of carbon per hectare in city blue-green infrastructure spaces. Interviews involving institution stakeholders examined the feasibility of this biochar application. Stakeholders recognized the potential of biochar as an environment-friendly means for carbon offsetting, but were concerned about the practicality of biochar production and application into soil and increased maintenance work. Consequently, additional potential benefits of biochar for environmental management such as improving the quality of polluted run-off in stormwater treatment systems should be emphasized to make biochar an attractive proposition in sustainable urban development.

Removal of atmospheric CO2 by engineered soils in infrastructure projects.

The use of crushed basic igneous rock and crushed concrete for enhanced rock weathering and to facilitate pedogenic carbonate precipitation provides a promising method of carbon sequestration. However, many of the controls on precipitation and subsequent effects on soil properties remain poorly understood. In this study, engineered soil plots, with different ratios of concrete or dolerite combined with sand, have been used to investigate relationships between sequestered inorganic carbon and geotechnical properties, over a two-year period. Cone penetration tests with porewater pressure measurements (CPTu) were conducted to determine changes in tip resistance and pore pressure. C and O isotope analysis was carried out to confirm the pedogenic origin of carbonate minerals. TIC analysis shows greater precipitation of pedogenic carbonate in plots containing concrete than those with dolerite, with the highest sequestration values of plots containing each material being equivalent to 33.7 t C ha-1 yr-1 and 17.5 t C ha-1 yr-1, respectively, calculated from extrapolation of results derived from the TIC analysis. TIC content showed reduction or remained unchanged for the top 0.1 m of soil; at a depth of 0.2 m however, for dolerite plots, a pattern of seasonal accumulation and loss of TIC emerged. CPTu tip resistance measurements showed that the presence of carbonates had no observable effect on penetration resistance, and in the case of porewater pressure measurements, carbonate precipitation does not change the permeability of the substrate, and so does not affect drainage. The results of this study indicate that both the addition of dolerite and concrete serve to enhance CO2 removal in soils, that soil temperature appears to be a control on TIC precipitation, and that mineral carbonation in constructed soils does not lead to reduced drainage or an increased risk of flooding.

Characterising the biophysical, economic and social impacts of soil carbon sequestration as a greenhouse gas removal technology.

To limit warming to well below 2°C, most scenario projections rely on greenhouse gas removal technologies (GGRTs); one such GGRT uses soil carbon sequestration (SCS) in agricultural land. In addition to their role in mitigating climate change, SCS practices play a role in delivering agroecosystem resilience, climate change adaptability and food security. Environmental heterogeneity and differences in agricultural practices challenge the practical implementation of SCS, and our analysis addresses the associated knowledge gap. Previous assessments have focused on global potentials, but there is a need among policymakers to operationalise SCS. Here, we assess a range of practices already proposed to deliver SCS, and distil these into a subset of specific measures. We provide a multidisciplinary summary of the barriers and potential incentives towards practical implementation of these measures. First, we identify specific practices with potential for both a positive impact on SCS at farm level and an uptake rate compatible with global impact. These focus on: (a) optimising crop primary productivity (e.g. nutrient optimisation, pH management, irrigation); (b) reducing soil disturbance and managing soil physical properties (e.g. improved rotations, minimum till); (c) minimising deliberate removal of C or lateral transport via erosion processes (e.g. support measures, bare fallow reduction); (d) addition of C produced outside the system (e.g. organic manure amendments, biochar addition); (e) provision of additional C inputs within the cropping system (e.g. agroforestry, cover cropping). We then consider economic and non-cost barriers and incentives for land managers implementing these measures, along with the potential externalised impacts of implementation. This offers a framework and reference point for holistic assessment of the impacts of SCS. Finally, we summarise and discuss the ability of extant scientific approaches to quantify the technical potential and externalities of SCS measures, and the barriers and incentives to their implementation in global agricultural systems.

Passive CO2 removal in urban soils: Evidence from brownfield sites.

Management of urban brownfield land can contribute to significant removal of atmospheric CO2 through the development of soil carbonate minerals. However, the potential magnitude and stability of this carbon sink is poorly quantified as previous studies address a limited range of conditions and short durations. Furthermore, the suitability of carbonate-sequestering soils for construction has not been investigated. To address these issues we measured total inorganic carbon, permeability and ground strength in the top 20 cm of soil at 20 brownfield sites in northern England, between 2015 and 2017. Across all sites accumulation occurred at a rate of 1-16 t C ha-1 yr-1, as calcite (CaCO3), corresponding to removal of approximately 4-59 t CO2 ha-1 yr-1, with the highest rate in the first 15 years after demolition. C and O stable isotope analysis of calcite confirms the atmospheric origin of the measured inorganic carbon. Statistical modelling found that pH and the content of fine materials (combined silt and clay content) were the best predictors of the total inorganic carbon content of the samples. Measurement of permeability shows that sites with carbonated soils possess a similar risk of run-off or flooding to sandy soils. Soil strength, measured as in-situ bearing capacity, increased with carbonation. These results demonstrate that the management of urban brownfield land to retain fine material derived from concrete crushing on site following demolition will promote calcite precipitation in soils, and so offers an additional CO2 removal mechanism, with no detrimental effect on drainage and possible improvements in strength. Given the large area of brownfield land that is available for development, the contribution of this process to CO2 removal by urban soils needs to be recognised in CO2 mitigation policies.

Evaluation of raw material extraction, processivng, construction and disposal of cement and concrete products: datasets and calculations.

To evaluate the material flows associated with construction and demolition in different countries it is necessary to have a consistent set of data. However, data collected by regulators and governments differ and this study used concrete as a case in point. Concrete is a significant man-made material in construction whose use reflects socio-economic variation between countries. Flows of natural components, cement and aggregates, are investigated from extraction to final disposal following demolition (Tangtinthai et al., 2019). The housing sector dominates the use of concrete in urbanized areas and greatly reflects socio-economic and resource extraction issues. To compare concrete stock, use and policies of contrasting countries the data from Thailand and Great Britain (GB) are considered, but as reported they differ for each country. We present here the results of the calculations required to generate an internally consistent database for Great Britain and for Thailand that enables an informed materials flow analysis to be undertaken on materials consumed and generated during construction and demolition of concrete structures. The research methodology and calculations for national cement and concrete production (including clinker, cement kiln dust, gypsum, and aggregates) and the resulting datasets help to make projections that shape policy requirements for Thailand and other emerging economies as reported in (Tangtinthai et al., 2019).

Role of policy in managing mined resources for construction in Europe and emerging economies.

Rapid urbanisation, with associated housing and infrastructure demands, leads to increased mining and use of non-renewable mineral raw materials needed for the construction industry including concrete and cement. In an emerging economy, like Thailand, which is part of Association of Southeast Asian Nations (ASEAN), current environmental management policies are insufficient to reduce raw material requirements or waste from demolition by generating inputs to construction through reuse or recycling. As part of the European Union (EU), Great Britain has successfully implemented integrated policies and achieved high rates of recycled aggregates in construction (29%) and a 70% reuse and recycling target for construction and demolition (C&D) waste. In this paper, Material Flow Analysis (MFA) of cement/concrete materials is combined with an interpretation of related policies to provide a deeper understanding how to achieve more sustainable management of natural resources. A comparative MFA for the construction industry in Great Britain and Thailand (representing an ASEAN country) has been developed that quantifies raw material inputs, buildings and infrastructure outputs, so that the practices in the two countries can be contrasted. We report domestic cement production and import/export data, and calculate the raw materials needed for cement and its calcination process for concrete production. Considering the most relevant policies and taxation in Great Britain, we identify possible ways forward for Thailand by introducing new policies and taxation that will have positive effects on raw material extraction, processing, construction and disposal practices and disposal behaviors. Following the MFA and policy analysis, we believe that similar benefits apply to other emerging economies.

Testing the ability of plants to access potassium from framework silicate minerals.

The availability of K, essential for plant growth, from syenite (a silicate rock in which potassium feldspar is the dominant mineral; >90wt%), and phlogopite mica has been demonstrated using carefully designed plant growth pot experiments in which the only added source of K was the mineral of interest, with no loss of nutrients through drainage. Using pure quartz sand as a soil, both growth (increase in diameter) of leek plants and K-content of the plant material showed a dose-dependent positive response to the application (114-43000mgK/pot) of milled syenite with increases in plant diameter of 0.5-0.7mm/week, increasing with application rate. Phlogopite mica (114-6000mgK/pot) supported the highest observed increase in diameter (approx. 1mm/week) and plant K-content, both similar to that observed for a positive control (KCl). These experiments demonstrate that plants can obtain K for growth from milled syenite, in which feldspar is the dominant K-bearing mineral, and confirm previous observations that micas can be an effective source of K.

Black Carbon Contribution to Organic Carbon Stocks in Urban Soil.

Soil holds 75% of the total organic carbon (TOC) stock in terrestrial ecosystems. This comprises ecosystem-derived organic carbon (OC) and black carbon (BC), a recalcitrant product of the incomplete combustion of fossil fuels and biomass. Urban topsoils are often enriched in BC from historical emissions of soot and have high TOC concentrations, but the contribution of BC to TOC throughout the urban soil profile, at a regional scale is unknown. We sampled 55 urban soil profiles across the North East of England, a region with a history of coal burning and heavy industry. Through combined elemental and thermogravimetic analyses, we found very large total soil OC stocks (31-65 kg m(-2) to 1 m), exceeding typical values reported for UK woodland soils. BC contributed 28-39% of the TOC stocks, up to 23 kg C m(-2) to 1 m, and was affected by soil texture. The proportional contribution of the BC-rich fraction to TOC increased with soil depth, and was enriched in topsoil under trees when compared to grassland. Our findings establish the importance of urban ecosystems in storing large amounts of OC in soils and that these soils also capture a large proportion of BC particulates emitted within urban areas.

Rapid Removal of Atmospheric CO2 by Urban Soils.

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.

Historical and technical developments of potassium resources.

The mining of soluble potassium salts (potash) is essential for manufacturing fertilizers required to ensure continuous production of crops and hence global food security. As of 2014, potash is mined predominantly in the northern hemisphere, where large deposits occur. Production tonnage and prices do not take into account the needs of the farmers of the poorest countries. Consequently, soils of some regions of the southern hemisphere are currently being depleted of potassium due to the expansion and intensification of agriculture coupled with the lack of affordable potash. Moving away from mined salts towards locally available resources of potassium, such as K-bearing silicates, could be one option to improve this situation. Overall, the global potash production system and its sustainability warrant discussion. In this contribution we examine the history of potash production and discuss the different sources and technologies used throughout the centuries. In particular, we highlight the political and economic conditions that favored the development of one specific technology over another. We identified a pattern of needs driving innovation. We show that as needs evolved throughout history, alternatives to soluble salts have been used to obtain K-fertilizers. Those alternatives may meet the incoming needs of our century, providing the regulatory and advisory practices that prevailed in the 20th century are revised.

Ground gas monitoring: implications for hydraulic fracturing and CO2 storage.

Understanding the exchange of carbon dioxide (CO2) and methane (CH4) between the geosphere and atmosphere is essential for the management of anthropogenic emissions. Human activities such as carbon capture and storage and hydraulic fracturing ("fracking") affect the natural system and pose risks to future global warming and to human health and safety if not engineered to a high standard. In this paper an innovative approach of expressing ground gas compositions is presented, using data derived from regulatory monitoring of boreholes in the unsaturated zone at infrequent intervals (typically 3 months) with data from a high frequency monitoring instrument deployed over periods of weeks. Similar highly variable trends are observed for time scales ranging from decades to hourly for boreholes located close to sanitary landfill sites. Additionally, high frequency monitoring data confirm the effect of meteorological controls on ground gas emissions; the maximum observed CH4 and CO2 concentrations in a borehole monitored over two weeks were 40.1% v/v and 8.5% v/v respectively, but for 70% of the monitoring period only air was present. There is a clear weakness in current point monitoring strategies that may miss emission events and this needs to be considered along with obtaining baseline data prior to starting any engineering activity.

Microbial degradation of crude oil hydrocarbons on organoclay minerals.

The role of organoclays in hydrocarbon removal during biodegradation was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. The clays used for this study were Na-montmorillonite and saponite. These two clays were treated with didecyldimethylammonium bromide to produce organoclays which were used in this study. The study indicated that clays with high cation exchange capacity (CEC) such as Na-montmorillonite produced an organomontmorillonite that was inhibitory to biodegradation of the crude oil hydrocarbons. Extensive hydrophobic interaction between the organic phase of the organoclay and the crude oil hydrocarbons is suggested to render the hydrocarbons unavailable for biodegradation. However, untreated Na-montmorillonite was stimulatory to biodegradation of the hydrocarbons and is believed to have done so because of its high surface area for the accumulation of microbes and nutrients making it easy for the microbes to access the nutrients. This study indicates that unlike unmodified montmorillonites, organomontmorillonite may not serve any useful purpose in the bioremediation of crude oil spill sites where hydrocarbon removal by biodegradation is desired within a rapid time period.

Effect of interlayer cations of montmorillonite on the biodegradation and adsorption of crude oil polycyclic aromatic compounds.

Cation exchange capacity, surface acidity and specific surface area are surface properties of clay minerals that make them act as catalysts or supports in most biogeochemical processes hence making them play important roles in environmental control. However, the role of homoionic clay minerals during the biodegradation of polycyclic aromatic compounds is not well reported. In this study, the effect of interlayer cations of montmorillonites in the removal of some crude oil polycyclic aromatic compounds during biodegradation was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. The homoionic montmorillonites were prepared via cation exchange reactions by treating the unmodified montmorillonite with the relevant metallic chloride. The study indicated that potassium-montmorillonite and zinc-montmorillonite did not enhance the biodegradation of the polycyclic aromatic hydrocarbons whereas calcium-montmorillonite, and ferric-montmorillonite enhanced their biodegradation significantly. Adsorption of polycyclic aromatic hydrocarbons was significant during biodegradation with potassium- and zinc-montmorillonite where there was about 45% removal of the polycyclic aromatic compounds by adsorption in the experimental microcosm containing 5:1 ratio (w/w) of clay to oil.

Biodegradation and adsorption of C1- and C2-phenanthrenes and C1- and C2-dibenzothiophenes in the presence of clay minerals: effect on forensic diagnostic ratios.

The impact of modified montmorillonites on adsorption and biodegradation of crude oil C1-phenanthrenes, C1-dibenzothiophenes, C2-phenanthrenes and C2-dibenzothiophenes was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. Consequently, the effect on C1-dibenzothiophenes/C1-phenanthrenes, C2-dibenzothiophenes/C2-phenanthrenes, 2+3-methyldibenzothiophene/4-methyldibenzothiophene and 1-methyldibenzothiophene/4-methyldibenzothiophene ratios commonly used as diagnostic ratios for oil forensic studies was evaluated. The clay mineral samples were treated to produce acid activated montmorillonite, organomontmorillonite and homoionic montmorillonite which were used in this study. The different clay minerals (modified and unmodified) showed varied degrees of biodegradation and adsorption of the C1-phenanthrenes, C1-dibenzothiophenes, C2-phenanthrenes and C2-dibenzothiophenes. The study indicated that as opposed to biodegradation, adsorption has no effect on the diagnostic ratios. Among the diagnostic ratios reviewed, only C2-dibenzothiophenes/C2-phenanthrenes ratio was neither affected by adsorption nor biodegradation making this ratio very useful in forensic studies of oil spills and oil-oil correlation.

Biodegradation of crude oil saturated fraction supported on clays.

The role of clay minerals in crude oil saturated hydrocarbon removal during biodegradation was investigated in aqueous clay/saturated hydrocarbon microcosm experiments with a hydrocarbon degrading microorganism community. The clay minerals used for this study were montmorillonite, palygorskite, saponite and kaolinite. The clay mineral samples were treated with hydrochloric acid and didecyldimethylammonium bromide to produce acid activated- and organoclays respectively which were used in this study. The production of organoclay was restricted to only montmorillonite and saponite because of their relative high CEC. The study indicated that acid activated clays, organoclays and unmodified kaolinite, were inhibitory to biodegradation of the hydrocarbon saturates. Unmodified saponite was neutral to biodegradation of the hydrocarbon saturates. However, unmodified palygorskite and montmorillonite were stimulatory to biodegradation of the hydrocarbon saturated fraction and appears to do so as a result of the clays' ability to provide high surface area for the accumulation of microbes and nutrients such that the nutrients were within the 'vicinity' of the microbes. Adsorption of the saturated hydrocarbons was not significant during biodegradation.

Effect of modified montmorillonites on the biodegradation and adsorption of biomarkers such as hopanes, steranes and diasteranes.

The effect of modified montmorillonites on the biodegradation and adsorption of selected steranes, diasteranes and hopanes was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. The unmodified montmorillonite was treated with didecyldimethylammonium bromide, hydrochloric acid and the relevant metallic chloride to produce organomontmorillonite, acid activated montmorillonite and homoionic montmorillonite respectively which were used in this study. The study indicated that organomontmorillonite, acid activated montmorillonite and potassium montmorillonite did not support the biodegradation of the selected steranes, diasteranes and hopanes as alteration of the biomarkers via biodegradation varied from a paltry 2-6 %. The adsorption of the selected biomarkers on acid activated montmorillonite and organomontmorillonite was also poor. However, adsorption of the biomarkers on potassium montmorillonite was relatively high. Sodium montmorillonite and unmodified montmorillonite appear to stimulate the biodegradation of the selected biomarkers moderately (30-35 %) with adsorption occurring at low level. Calcium montmorillonite and ferric montmorillonite effected significant biodegradation (51-60 %) of the selected biomarkers.

Compositional changes of crude oil SARA fractions due to biodegradation and adsorption on colloidal support such as clays using Iatroscan.

The compositional changes of saturates, aromatics, resins and asphaltenes (SARA) fractions in aqueous clay/oil microcosm experiments with a hydrocarbon-degrading microorganism community were analysed using Iatroscan. The clay mineral samples used in this study were organomontmorillonite, acid-activated montmorillonite and K, Ca, Zn and Cr montmorillonites produced by modifying the original montmorillonite sample. The evaluation and quantification of biodegradation and adsorption were carried out using a combination of the Iatroscan and gravimetric analysis. The SARA compositions in the presence of organomontmorillonite and acid-activated montmorillonite after incubation follow the same pattern in which the aromatic fraction is higher than the other fractions unlike in the presence of unmodified, K, Ca and Zn montmorillonites, where the saturates fraction is higher than the other fractions. Changes in SARA fractions due to biodegradation seemed to occur most in the presence of unmodified and calcium montmorillonites; hence, the removal of SARA fractions due to biodegradation was significant and enhanced in the presence of these two clay samples. However, biodegradation in the presence of organomontmorillonite and acid-activated and Cr montmorillonites was hindered. The study indicated that Cr montmorillonite adsorbed resins most, whereas Zn and K montmorillonites adsorbed aromatics most after incubation.

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.

Persistence of soil organic matter as an ecosystem property.

Globally, soil organic matter (SOM) contains more than three times as much carbon as either the atmosphere or terrestrial vegetation. Yet it remains largely unknown why some SOM persists for millennia whereas other SOM decomposes readily--and this limits our ability to predict how soils will respond to climate change. Recent analytical and experimental advances have demonstrated that molecular structure alone does not control SOM stability: in fact, environmental and biological controls predominate. Here we propose ways to include this understanding in a new generation of experiments and soil carbon models, thereby improving predictions of the SOM response to global warming.