Constraining the Capacity of Global Croplands to CO2 Drawdown via Mineral Weathering.

Terrestrial enhanced weathering of alkaline silicate minerals is a promising climate change mitigation strategy with the potential to limit the global temperature rise. The formation and accumulation of pedogenic carbonate and bicarbonate in soils/subsoils and groundwater offers a large sink for C storage; the amount of soil inorganic carbon (SIC) presently held within soils has been estimated to be 720-950 Gt of C. These values can be augmented by the addition of a variety of calcium and magnesium silicates via enhanced weathering. While the concept of the application of finely milled silicate rocks for faster weathering rates is well established, there has been limited discussion on the role of local climate, natural SIC content (i.e., the SIC innately present in the soil), and soil pH (among other important agronomic factors) on silicate weathering when applied to croplands, especially in view that the aim is to establish terrestrial enhanced weathering as a carbon dioxide removal (CDR) strategy on a global scale. In this work, we emphasized the importance of soil pH and soil temperature on silicate weathering and looked to estimate an upper limit of (i.e., constrain) the global capacity until the year 2100 for enhanced rock weathering (ERW) to draw down CO2 in the form of accumulated pedogenic carbonate or soluble bicarbonate. We assessed the global spatial distribution of cropland soil pH, which serves as a proxy for local innate SIC; annual rate of pluvial (rainfall) precipitation; and soil temperature, and found that the potential CO2 drawdown difference between faster and slower weathering silicates is narrower in Asia, Africa, and South America, while the gap is larger for Europe, North America, and Oceania.

Mineral-Soil-Plant-Nutrient Synergisms of Enhanced Weathering for Agriculture: Short-Term Investigations Using Fast-Weathering Wollastonite Skarn.

Enhanced weathering is a proposed carbon dioxide removal (CDR) strategy to accelerate natural carbon sequestration in soils via the amendment of silicate rocks to agricultural soils. Among the suitable silicates (such as basalt and olivine), the fast-weathering mineral wollastonite (CaSiO3) stands out. Not only does the use of wollastonite lead to rapid pedogenic carbonate formation in soils, it can be readily detected for verification of carbon sequestration, but its weathering within weeks to months influences soil chemistry and plant growth within the same crop cycle of its application. This enables a variety of short-term experimental agronomic studies to be conducted to demonstrate in an accelerated manner what could take years to be observed with more abundant but slower weathering silicates. This study presents the results of three studies that were conducted to investigate three distinct aspects of wollastonite skarn weathering in soils in the context of both agricultural and horticultural plants. The first study investigated the effect of a wide range of wollastonite skarn dosages in soil (1.5-10 wt.%) on the growth of green beans. The second study provides insights on the role of silicon (Si) release during silicate weathering on plant growth (soybeans and lettuce). The third study investigated the effect of wollastonite skarn on the growth of spring rye when added to soil alongside a nitrogen-based coated fertilizer. The results of these three studies provide further evidence that amending soil with crushed silicate rocks leads to climate-smart farming, resulting in inorganic carbon sequestration, as well as better plant growth in agricultural (soybean and spring rye) and horticultural (green bean and lettuce) crops. They also demonstrate the value of working with wollastonite skarn as a fast-weathering silicate rock to accelerate our understanding of the mineral-soil-plant-nutrient synergism of enhanced weathering.

Ultrasound assisted cyanotoxin extraction for nematode inhibition in soil.

Root-knot nematodes are one of the plant damaging nematodes in agriculture causing a projected annual yield loss of ∼12 % (∼$160 billion) worldwide. Conventional solutions to control these plant-parasitic nematodes involve chemical nematicides. To reduce the use of harmful chemicals, microalgal extracts can be used as greener alternatives for nematode management. Microalgae produce valuable metabolites, including cyanotoxins which can aid in nematode suppression. In this study, two microalgae species, Trichormus variabilis and Nostoc punctiforme, were treated with ultrasound for intensified recovery of secondary metabolites. Ultrasound results in cell wall disruption of the microalgal species, thus resulting in enhanced release of secondary metabolites. Microalgal biomass was treated with an ultrasound probe at 50 % amplitude, 20 kHz frequency, using water as the extraction medium, for 5-30 min. The extraction efficiency was determined in terms of the total chlorophyll (Chl) content of the extract. Microscopic images of the treated cells were also investigated to gain insight into the effect of the ultrasonication time on the cell morphology. Our results suggest that ultrasonication resulted in the intensified release of secondary metabolites, as established through the total chlorophyll content of the ultrasonicated microalgal samples as well as the microscopic images of the ruptured cells. The best extraction for Trichormus variabilis was achieved with 15 min extraction time where the Total Chl content increased by 29 times (compared to the non-ultrasonicated sample), and for the Nostoc punctiforme, 30 min extraction time gave the highest metabolite recovery of 6.4 times higher than the non-ultrasonicated sample. Ultrasonicated algal extracts were then tested for their nematicidal potential against root-knot nematode, Meloidogyne hapla, in infested field soil samples. Experimental study was conducted using different concentrations of each microalga, Trichormus sp. and Nostoc sp., individually, as well as in combination. The nematode count for the treated soil was compared with that of the control (untreated soil). Ultrasonicated microalgal extracts showed 66% to 100% inhibition on root-knot nematodes in the soil samples tested.

Urban Farming with Enhanced Rock Weathering As a Prospective Climate Stabilization Wedge.

With no single carbon capture and sequestration solution able to limit the global temperature rise to 1.5-2.0 °C by 2100, additional climate stabilization measures are needed to complement current mitigation approaches. Urban farming presents an easy-to-adopt pathway toward carbon neutrality, unlocking extensive urban surface areas that can be leveraged to grow food while sequestering CO2. Urban farming involves extensive surface areas, such as roofs, balconies, and vertical spaces, allowing for soil presence and atmospheric carbon sequestration through air-to-soil contact. In this viewpoint we also advocate the incorporation of enhanced rock weathering (ERW) into urban farming, providing a further opportunity for this recognized negative emissions technology that is gaining momentum worldwide to gain greater utilization.

Monitoring Pedogenic Inorganic Carbon Accumulation Due to Weathering of Amended Silicate Minerals in Agricultural Soils.

The present study aims to demonstrate a systematic procedure for monitoring inorganic carbon induced by enhanced weathering of comminuted rocks in agricultural soils. To this end, the core soil samples taken at different depth (including 0-15 cm, 15-30 cm, and 30-60 cm profiles) are collected from an agriculture field, the topsoil of which has already been enriched with an alkaline earth metal silicate containing mineral (such as wollastonite). After transporting to the laboratory, the soil samples are air-dried and sieved. Then, the inorganic carbon content of the samples is determined by a volumetric method called calcimetry. The representative results presented herein showed five folded increments of inorganic carbon content in the soils amended with the Ca-silicate compared to control soils. This compositional change was accompanied by more than 1 unit of pH increase in the amended soils, implying high dissolution of the silicate. Mineralogical and morphological analyses, as well as elemental composition, further corroborate the increase in the inorganic carbon content of silicate-amended soils. The sampling and analysis methods presented in this study can be adopted by researchers and professionals looking to trace pedogenic inorganic carbon changes in soils and subsoils, including those amended with other suitable silicate rocks such as basalt and olivine. These methods can also be exploited as tools for verifying soil inorganic carbon sequestration by private and governmental entities to certify and award carbon credits.

Optimizing Inorganic Carbon Sequestration and Crop Yield With Wollastonite Soil Amendment in a Microplot Study.

Carbon dioxide (CO2) is a major greenhouse gas, and its concentration in the atmosphere is increasing continuously, hence there is an urgent need to reduce its level in the atmosphere. Soils offer a large natural sink to store CO2. This study focuses on sequestering CO2 in the agricultural soils as inorganic carbon, which can be accomplished by adding alkaline-earth silicates. Wollastonite is used in this study as a soil amendment, to sequester CO2 via the geochemical route of mineral carbonation. The first objective of the present study was to evaluate the effect of mixing a wide range of dosages of wollastonite, as a soil amendment, on the growth performance of two leguminous plants frequently used in agricultural sector: soybean and alfalfa. The plants were grown with different wollastonite dosages (3-20 kg·m-2 for soybean and 3-40 kg·m-2 for alfalfa), for a duration of 14 weeks in a microplot experiment in Ontario, Canada. The second objective was to find evidence of enhanced weathering of wollastonite in soil, in addition to the augmentation of inorganic carbon content in soil. For this, mineralogical assessment of the soils was performed using XRD and SEM-EDS analyses. Wollastonite increased the soybean yield by two-fold in the plot amended with 10 kg·m-2. At all dosages, wollastonite increased the alfalfa growth in terms of height and above-ground biomass dry weight, as well as root biomass. The rate of CO2 sequestration, at optimum wollastonite dosage, reached 0.08 kg CO2·m-2·month-1. XRD and SEM-EDS analyses indicated accumulation of calcite in wollastonite-amended soil and formation of other weathering products. The results obtained from this study help to understand the impact of wollastonite soil amendment on agronomy, and will aid in implementing such negative emissions technology by informing farmers and industry alike that the use of wollastonite contributes toward global climate change mitigation while supporting crop yield. The findings of this study add to the existing body of knowledge on enhanced weathering as an atmospheric CO2 removal technology, providing further evidence that wollastonite weathering in agricultural soils can lead to significant capacity for CO2 sequestration as inorganic carbon, while concurrently promoting plant growth.

Micro-structured copper and nickel metal foams for wastewater disinfection: proof-of-concept and scale-up.

It is necessary to disinfect treated wastewater prior to discharge to reduce exposure risks to humans and the environment. The currently practiced wastewater disinfection technologies are challenged by toxic by-products, chemicals and energy demand, a range of effectiveness limitations, among other concerns. An effective, eco-friendly, and energy-efficient alternative disinfection technique is desirable to modernize and enhance wastewater treatment operations. Copper and nickel micro-structured metal foams, and a conventional copper mesh, were evaluated as disinfecting surfaces for treating secondary-treated wastewater contaminated with coliform bacteria. The micro-structured copper foam was adopted for scale-up study, due to its stable and satisfactory bactericidal performance obtained over a wide range of bacterial concentrations and metal-to-liquid ratios. Three scales of experiments, using two types of reactor designs, were performed using municipal wastewater to determine the optimal scale-up factors: small lab-scale batch reactor, intermediate lab-scale batch reactor, and pilot-scale continuous tubular reactor experiments. The performance was evaluated with the aim of minimizing metal material requirement with respect to bactericidal efficiency and leaching risks at all scales. Copper foam, at or above optimal conditions, consistently inactivated over 95 % of total coliforms, fecal coliforms and E.coli in wastewater at various scales, and leachate copper concentrations were determined to be below Canadian guideline values for outfall. This study successfully implemented the "structure" strategy of process intensification, and opens up the possibility to apply micro-structured copper foam in a range of other water disinfection systems, from pre-treatment to point-of-use, and should thus become a topic of further research.

Co-Benefits of Wollastonite Weathering in Agriculture: CO2 Sequestration and Promoted Plant Growth.

To lock atmospheric CO2 at anthropogenic timescale, fast weathering silicates can be applied to soil to speed up natural CO2 sequestration via enhanced weathering. Agricultural lands offer large area for silicate application, but expected weathering rates as a function of soil and crop type, and potential impacts on the crops, are not well known. This study investigated the role of plants on enhanced weathering of wollastonite (CaSiO3) in soils. Using rooftop pot experiments with leguminous beans (Phaseolus vulgaris L.) and nonleguminous corn (Zea mays L.), CO2 sequestration was inferred from total inorganic carbon (TIC) accumulation in the soil and thermogravimetric analysis, and mineral weathering rate was inferred from alkalinity of soil porewater. Soil amendment with wollastonite promoted enhanced plant growth: beans showed a 177% greater dry biomass weight and corn showed a 59% greater plant height and a 90% greater dry biomass weight. Wollastonite-amended soil cultivated with beans showed a higher TIC accumulation of 0.606 ± 0.086%, as compared to that with corn (0.124 ± 0.053%). This demonstrates that using wollastonite as a soil amendment, along with legume cultivation, not only buffers the soil against acidification (due to microbial nitrogen fixation) but also sequesters carbon dioxide (12.04 kg of CO2/tonne soil/month, 9 times higher than the soil without wollastonite amendment).

Extraction and applications of cyanotoxins and other cyanobacterial secondary metabolites.

The rapid proliferation of cyanobacteria in bodies of water has caused cyanobacterial blooms, which have become an increasing cause of concern, largely due to the presence of toxic secondary metabolites (or cyanotoxins). Cyanotoxins are the toxins produced by cyanobacteria that may be harmful to surrounding wildlife. They include hepatotoxins, neurotoxins and dermatotoxins, and are classified based on the organs they affect. There are also non-toxic secondary metabolites that include chelators and UV-absorbing compounds. This paper summarizes the optimal techniques for secondary metabolite extraction and the possible useful products that can be obtained from cyanobacteria, with additional focus given to products derived from secondary metabolites. It becomes evident that the potential for their use as biocides, chelators, biofuels, biofertilizers, pharmaceuticals, food and feed, and cosmetics has not yet been comprehensively studied or extensively implemented.

Two-way Valorization of Blast Furnace Slag: Synthesis of Precipitated Calcium Carbonate and Zeolitic Heavy Metal Adsorbent.

The aim of this work is to present a zero-waste process for storing CO2 in a stable and benign mineral form while producing zeolitic minerals with sufficient heavy metal adsorption capacity. To this end, blast furnace slag, a residue from iron-making, is utilized as the starting material. Calcium is selectively extracted from the slag by leaching with acetic acid (2 M CH3COOH) as the extraction agent. The filtered leachate is subsequently physico-chemically purified and then carbonated to form precipitated calcium carbonate (PCC) of high purity (<2 wt% non-calcium impurities, according to ICP-MS analysis). Sodium hydroxide is added to neutralize the regenerated acetate. The morphological properties of the resulting calcitic PCC are tuned for its potential application as a filler in papermaking. In parallel, the residual solids from the extraction stage are subjected to hydrothermal conversion in a caustic solution (2 M NaOH) that leads to the predominant formation of a particular zeolitic mineral phase (detected by XRD), namely analcime (NaAlSi2O6∙H2O). Based on its ability to adsorb Ni2+, as reported from batch adsorption experiments and ICP-OES analysis, this product can potentially be used in wastewater treatment or for environmental remediation applications.

Tolerance of Chemoorganotrophic Bioleaching Microorganisms to Heavy Metal and Alkaline Stresses.

The bioleaching potential of the bacterium Bacillus mucilaginosus and the fungus Aspergillus niger towards industrial residues was investigated by assessing their response towards various heavy metals (including arsenic, cadmium, cobalt, chromium, nickel, lead, and zinc) and elevated pH. The plate diffusion method was performed for each metal to determine the toxicity effect. Liquid batch cultures were set up for more quantitative evaluation as well as for studying the influence of basicity. Growth curves were prepared using bacterial/fungal growth counting techniques such as plate counting, optical density measurement, and dry biomass determination. Cadmium, nickel, and arsenite had a negative influence on the growth of B. mucilaginosus, whereas A. niger was sensitive to cadmium and arsenate. However, it was shown that growth recovered when microorganisms cultured in the presence of these metals were inoculated onto metal-free medium. Based on the findings of the bacteriostatic/fungistatic effect of the metals and the adaptability of the microorganisms to fairly elevated pH values, it is concluded that both strains have potential applicability for further research concerning bioleaching of alkaline waste materials.

Impacts of nickel nanoparticles on mineral carbonation.

This work presents experimental results regarding the use of pure nickel nanoparticles (NiNP) as a mineral carbonation additive. The aim was to confirm if the catalytic effect of NiNP, which has been reported to increase the dissolution of CO2 and the dissociation of carbonic acid in water, is capable of accelerating mineral carbonation processes. The impacts of NiNP on the CO2 mineralization by four alkaline materials (pure CaO and MgO, and AOD and CC steelmaking slags), on the product mineralogy, on the particle size distribution, and on the morphology of resulting materials were investigated. NiNP-containing solution was found to reach more acidic pH values upon CO2 bubbling, confirming a higher quantity of bicarbonate ions. This effect resulted in acceleration of mineral carbonation in the first fifteen minutes of reaction time when NiNP was present. After this initial stage, however, no benefit of NiNP addition was seen, resulting in very similar carbonation extents after one hour of reaction time. It was also found that increasing solids content decreased the benefit of NiNP, even in the early stages. These results suggest that NiNP has little contribution to mineral carbonation processes when the dissolution of alkaline earth metals is rate limiting.

Atom-efficient route for converting incineration ashes into heavy metal sorbents.

Bottom ashes produced from municipal solid-waste incineration are suitable for sorbent synthesis because of their inherent composition, high alkalinity, metastable mineralogy, and residual heat. This work shows that bottom ashes can be atom-efficiently converted into valuable sorbents without the need for costly and hazardous chemicals. The ashes were hydrothermally treated in rotary autoclaves at autogenic pH conditions to promote the conversion of precursor mineral phases into zeolites and layered silicate hydrates. Two main mineral phases were formed: katoite and sodium aluminum phosphate silicate hydrate. These mineral alterations are accompanied by a tenfold increase in specific surface area and a twofold reduction in average particle size. Performance evaluation of the new sorbents for Cd(2+), Zn(2+), and Pb(2+) adsorption at pH5 indicates sorption capacities of 0.06, 0.08, and 0.22 mmol g(-1), respectively, which are similar to those of natural adsorbents and synthetic materials obtained from more demanding synthesis conditions.