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Leonardite

Leonardite is a naturally occurring, oxidized form of lignite coal characterized by its high content of humic acids, typically appearing as a soft, waxy, black or brown, shiny, vitreous mineraloid that is readily soluble in alkaline solutions.^[1]^[2] This mineraloid forms through the natural oxidation and weathering of lignite deposits, often found at shallow depths overlying more compact coal seams in regions such as North Dakota in the United States, Alberta and Saskatchewan in Canada, and parts of Thailand and other lignite-bearing areas.^[3]^[4] The term "leonardite" originally refers to a specific deposit discovered in the early 20th century near Leonard, North Dakota, but it is now commonly applied to similar oxidized lignites worldwide.^[3]^[5] Chemically, leonardite is rich in humic substances, with humic acid content ranging from approximately 39% to 85% depending on the deposit, alongside fulvic acids and mineral matter such as silica, clay, gypsum, and trace elements like iron, manganese, zinc, and potassium.^[6]^[7] Its pH varies from acidic (around 1.8–6.2), and it contains significant organic matter (19–61%), making it distinct from unoxidized lignite due to the presence of carboxyl groups and other functional groups that enhance its solubility and bioactivity.^[6]^[8] Leonardite is primarily valued for its applications as a soil conditioner and biostimulant in agriculture, where extracts of humic and fulvic acids improve nutrient uptake, enhance soil microbial activity, and reported to increase crop yields in various studies, including on tomatoes.^[9]^[10] It is also used in horticulture, reclamation of saline or depleted soils, and as a feed additive in aquaculture to support growth and water quality.^[1]^[11] Global resources are substantial; for example, speculative resources in Alberta alone exceed 2 million tonnes, supporting its commercial extraction and processing into fertilizers and amendments.^[1]

Definition and Properties

Physical Characteristics

Leonardite is a soft, waxy mineraloid characterized by a black or brown coloration and a shiny, vitreous appearance. This earthy substance often presents as a loose, porous mass that is easily crumbled due to its friable nature, a trait first noted in outcrop exposures where it contrasts with the more compact and harder underlying lignite.^[2] In terms of solubility, leonardite dissolves readily in alkaline solutions, such as sodium hydroxide, forming dark-brown solutions with minimal residue, while remaining insoluble in water and acids, where it can be reprecipitated at pH levels of 4 or below.^[2] The density of leonardite typically falls in the range of 1.1 to 1.5 g/cm³, reflecting its lightweight and absorbent structure compared to denser coal forms. Moisture content varies significantly by deposit, often ranging from 20% to 40%, which contributes to its swelling behavior when exposed to water—expanding to several times its original volume in some types.^[12]^[13]

Chemical Composition

Leonardite is primarily composed of humic substances, which form the core of its organic fraction and account for up to 90% of the material, including humic acids (typically 30-80%), fulvic acids, and humins.^[14]^[6] The overall organic matter content in leonardite ranges from 56% to 85%, distinguishing it as a concentrated source of these complex macromolecules derived from the oxidation of lignitic precursors.^[15]^[16] The elemental composition of leonardite reflects its oxidized nature, with carbon comprising 50-60%, oxygen 30-40%, hydrogen 4-6%, and nitrogen 1-2% on a dry basis, alongside sulfur at around 0.5-2%.^[4]^[17] This higher oxygen content compared to lignite results from extensive oxidation processes during its formation, enhancing its reactivity through increased oxygenated functional groups.^[2]^[18] Trace minerals are also present, including potassium (0.8-2.5%), iron (0.6-5%), phosphorus, calcium, magnesium, and zinc, which contribute to its agronomic value.^[15]^[6] At the molecular level, leonardite's humic substances feature a heterogeneous structure combining aromatic and aliphatic chains, enriched with functional groups such as carboxyl, phenolic hydroxyl, and carbonyl moieties.^[14]^[19] These groups confer acidic properties, with the material typically exhibiting a pH of 3.7-6.2, and enable ion exchange and chelation capabilities.^[6] The International Humic Substances Society (IHSS) utilizes leonardite-derived humic acid as a reference standard for modeling and research due to its representative composition.^[17]^[20]

Element/Compound	Typical Range (% dry basis)	Source
Carbon (C)	50-60	[web:9], [web:39]
Oxygen (O)	30-40	[web:9], [web:39]
Hydrogen (H)	4-6	[web:9], [web:17], [web:39]
Nitrogen (N)	1-2	[web:9], [web:17], [web:39]
Potassium (K₂O)	1-3	^[6]
Iron (Fe)	0.6-5	[web:91]

Origins and Geology

Formation Process

Leonardite develops as a result of the partial oxidation and weathering of near-surface lignite deposits, a process that transforms low-rank coal into a more oxidized, humic-enriched material over millions of years. This occurs primarily in coal beds where the overlying sediment layer is thin and porous, facilitating the ingress of atmospheric oxygen and moisture to drive the reaction.^[5] The underlying lignite itself forms from the accumulation of plant-derived peat in ancient swampy, wetland environments under humid, reducing conditions during the Paleocene epoch (66–56 million years ago).^[5] The core mechanism of leonardite formation involves both chemical and microbial oxidation processes that progressively alter the organic structure of the lignite. Exposure to aerobic conditions at the surface promotes the breakdown of carbon bonds, incorporating oxygen and enhancing the degree of humification, which converts the partially decomposed plant matter into complex humic substances.^[21] Microbial activity, particularly from bacteria capable of solubilizing low-rank coal, contributes to this transformation by facilitating the release and polymerization of humic-like compounds under oxidative stress.^[22] Chemical analyses confirm the extent of this oxidation, revealing an elevated oxygen content in leonardite—typically 28-29% by weight—compared to unoxidized lignite at 19-20%, alongside increased levels of humic acids that reflect advanced humification.^[23] These changes occur in settings where ongoing exposure to air and water sustains the aerobic, humid conditions necessary for sustained weathering without deeper burial that would lead to higher coal ranks. The resulting material exhibits greater solubility and reactivity due to the proliferation of carboxyl and phenolic functional groups formed during this prolonged geological process.

Global Occurrence

Leonardite is predominantly associated with Paleogene- and Neogene-age lignite deposits in sedimentary basins worldwide, where it forms as an oxidized, near-surface variant of lignite, often appearing as weathered rims or outcrops of lignite seams.^[5] These geological settings facilitate oxidation through exposure to air and moisture, resulting in varying degrees of humic acid content and quality depending on the extent of weathering and local environmental conditions.^[5] The most significant commercial deposits occur in North America, particularly in the Williston Basin of western North Dakota, USA, where leonardite is mined from the Paleocene Fort Union Formation across 24 counties, including Adams, Billings, and Bowman.^[5] These resources, identified through over 20,000 drill holes, underlie areas with thin overburden, enabling economic extraction, and have supported mining operations for over 50 years east of Williston, serving as a primary global source for humic substances.^[24] In Canada, substantial deposits are found in the Estevan area of southeastern Saskatchewan and the Battle River and Sheerness coalfields of Alberta, where the material is termed humalite; Alberta alone holds measured resources of approximately 118,000 tonnes and speculative resources exceeding 2 million tonnes (as of 1993), primarily in weathered subbituminous coals and carbonaceous shales.^[25] Beyond North America, notable occurrences include the Ptolemais basin in Western Macedonia, Greece, within lignite fields of the Neogene basin system, where leonardite benches are extracted alongside matrix lignite for humic acid production.^[26] In Turkey, deposits are distributed across multiple lignite-bearing regions, such as Bursa-Davutlar, Balıkesir-Balya, Adana-Tufanbeyli, Tekirdağ-Saray, and Konya-Beyşehir, with varying humic content suitable for agricultural applications.^[27] Australia's Victoria hosts high-quality leonardite-type materials in the Gippsland Basin's brown coal fields, particularly in southeastern areas like Bacchus Marsh, which have been studied for carbon geosequestration potential due to their organic-rich composition.^[28] Minor deposits or leonardite-like oxidized lignites are reported in New Zealand's lignite fields and Germany's brown coal regions, though these are less commercially developed compared to primary sites.^[29] Overall, North American resources alone are estimated in the millions of tons of mineable material, underscoring the continent's dominance in global supply.^[25]

History and Discovery

Initial Identification

Leonardite was first identified in the early 20th century among lignite outcrops in western North Dakota by geologists conducting surveys of the region's coal resources. These outcrops, part of the Fort Union Formation, revealed a soft, oxidized material associated with lignite beds, occurring at shallow depths and distinguished by its earthy texture and brown color. Early observations noted its presence in counties such as Bowman and Slope, where it formed through natural weathering processes affecting the lignite deposits.^[30] The material was named leonardite in honor of Arthur G. Leonard, the first director of the North Dakota Geological Survey, who served from 1903 to 1932 and played a pivotal role in documenting North Dakota's mineral resources. Leonard, a professor of geology at the University of North Dakota, led extensive field investigations into the state's lignite formations during the 1910s and 1920s, highlighting the unique oxidized characteristics of this substance that set it apart from unweathered lignite. His work emphasized its potential as a distinct resource, leading to the adoption of the term in recognition of his contributions.^[31] In geological surveys from the late 1910s through the 1920s, leonardite was formally described as a distinct mineraloid. It is characterized by elevated oxygen content (around 28-29%) and high humic acid levels (30-80%), which impart greater solubility compared to standard lignite.^[2]^[31] These properties were noted in early scientific characterizations that established leonardite as a valuable oxidized variant of lignite, paving the way for further study. Leonard co-authored the 1925 North Dakota Geological Survey Bulletin 4, "The Lignite Deposits of North Dakota," which provided detailed descriptions of lignite resources in the state.^[24]

Commercial Development

Commercial mining of leonardite in North Dakota began in the mid-20th century, initially focused on extracting humic acids for industrial applications.^[2] By the 1960s, operations had commercialized, with early production targeting agricultural uses before shifting to oil rig drilling mud additives.^[32] This expansion was driven by the material's high humic content, making it a viable resource from lignitic outcrops in the Williston Basin.^[33] A pivotal development occurred in 1947 when leonardite was introduced as a domestic alternative to imported quebracho tannins for stabilizing drilling fluids, addressing wartime supply shortages.^[34] Demand surged in the 1970s and 1980s alongside growth in the fertilizer sector, as agricultural applications for soil enhancement gained traction amid increasing farm productivity needs.^[32] In the 2020s, emphasis has shifted toward sustainable sourcing practices, integrating leonardite into climate-resilient farming strategies to mitigate soil degradation from environmental changes.^[35] Major producers operate primarily in the United States, such as Leonardite Products in North Dakota, and Canada, where historical extraction occurred in Alberta until 1983.^[36]^[31] The global market, valued at over $1.2 billion for leonardite-derived humic products, relies heavily on exports of humic substances for agriculture and remediation.^[37] Annual production exceeds 1 million tonnes worldwide, though challenges persist, including depletion of high-quality deposits and variability in humic acid content across sources.^[38]^[39] In sensitive regions like Alberta's basins, mining requires environmental assessments to ensure compliance with reclamation standards.^[31]

Extraction and Processing

Mining Methods

Leonardite deposits, typically located near the surface, are extracted primarily through surface mining techniques, including open-pit and strip mining methods, especially in lignite-rich regions like North Dakota. These approaches are favored due to the material's shallow depth, often no more than 20 feet, allowing for efficient removal of overburden and selective excavation in sections of 2 to 3 acres.^[40]^[41] Mechanical excavation is the standard practice, utilizing equipment such as professional excavators, front-end loaders, and in larger lignite-associated operations, draglines or scrapers to loosen and remove the soft, earthy material. Front-end loaders handle the removal of interbedded clay layers, while dump trucks transport the excavated leonardite to nearby processing sites, typically within a few miles. The friable nature of leonardite enables low-cost operations, as it requires minimal blasting or heavy-duty rock-breaking equipment compared to harder minerals.^[40] Post-extraction, the material, which contains 40-50% moisture, undergoes initial sun-drying in stockpiles followed by mechanical drying using natural gas heaters at temperatures up to 145°F and crushing in hammer mills to reduce particle size and remove impurities. This processing yields a dry, humic-rich product representing approximately 50-60% of the mined volume after moisture removal, with no chemical additives introduced during mining stages.^[40] Environmental considerations are integral to operations, with reclamation efforts involving the separate stockpiling and replacement of topsoil, subsoil, and overburden for backfilling pits to restore pre-mining contours. Revegetation follows, using native or approved seed mixes to promote land productivity and stability, in compliance with state regulations under the North Dakota Public Service Commission. Sites undergo regular inspections to ensure adherence.^[42]^[43] Key challenges include dust control in the semi-arid climate of North Dakota, addressed through water suppression and vegetative covers during active mining, and water management to minimize usage for haul roads and processing while preventing erosion. These measures help mitigate impacts on air quality and local hydrology in water-scarce areas.^[44]

Humic Substance Extraction

The primary method for extracting humic substances from leonardite involves alkaline extraction, which solubilizes humic acids due to the material's high humic content, up to 85% on a dry, ash-free basis.^[45] This process targets the isolation of humic acids, with potential for producing derivatives like potassium humate when using potassium-based alkalis. The extraction begins with pulverizing the raw leonardite ore to increase surface area, followed by mixing it with an alkaline solution such as 0.5 M sodium hydroxide (NaOH) or potassium hydroxide (KOH) at a typical solid-to-liquid ratio of 1:10.^[46]^[47] The mixture is agitated for several hours under conditions that maintain a pH of approximately 12-13 to ensure solubilization of humic acids, though operational pH ranges from 7 to 12 are reported in some protocols.^[47] The slurry is then filtered or centrifuged to separate the soluble humate fraction from insoluble residues like humin. The filtrate is acidified with hydrochloric acid (HCl) to a pH of 1-2, causing humic acids to precipitate as a solid.^[48]^[49] The precipitate is collected, washed with deionized water to remove salts, and dried, yielding typically 20-80% recovery of humic acids based on the original humic content.^[45]^[48] When KOH is employed instead of NaOH, the process directly yields potassium humate, a water-soluble form suitable for liquid fertilizer formulations.^[47] Byproducts include fulvic acids, obtained through further fractionation of the post-precipitation supernatant via resin adsorption (e.g., XAD-8) or dialysis, as fulvic acids remain soluble at acidic pH.^[48] This alkaline procedure aligns with the standard method established by the International Humic Substances Society (IHSS) for preparing reference leonardite humic acid samples, ensuring consistency for research and commercial applications. Similar methods are used globally, with adaptations for local deposits.^[48] Alternative methods include solvent extraction using organic solvents like dimethylformamide (DMF) or acidified ethanol, which can achieve targeted isolation but typically result in lower yields (under 50%) compared to alkaline approaches and are less commonly adopted due to cost and environmental concerns.^[50] Emerging eco-friendly variations, such as bioleaching with microbial consortia or ultrasound-assisted alkaline extraction, offer potential for reduced chemical use by enzymatically degrading the matrix or enhancing solubilization, though these remain experimental with yields below 60% as of 2024.^[51]^[52]

Applications and Uses

Agricultural and Soil Applications

Leonardite serves as a valuable soil amendment in agriculture, primarily applied at rates of 100-500 kg/ha to improve soil structure, enhance water retention capacity, and increase nutrient availability for crops.^[53] This application introduces humic substances that bind soil particles, reducing erosion and improving aeration in degraded soils. By elevating soil organic matter, leonardite promotes better root development and stimulates microbial activity, which in turn supports nutrient cycling and carbon sequestration, contributing to long-term soil fertility.^[54] The amendment enhances plant nutrient uptake, particularly for micronutrients like iron and macronutrients such as potassium, by chelating them into more bioavailable forms that plants can readily absorb.^[55] This is especially beneficial in nutrient-poor or alkaline conditions, where leonardite helps counteract fixation of elements in the soil. Studies have demonstrated yield increases of 10-20% in crops including tomatoes, cotton, and grapevines when leonardite is incorporated, attributing these gains to improved soil health and plant vigor.^[56] It proves particularly effective in calcareous and sandy soils, where it mitigates issues like poor water-holding capacity and low organic content.^[54] Commercial products derived from leonardite, such as HUMAX—a concentrated liquid humic acid extract—are utilized for both soil incorporation and foliar applications to boost crop productivity.^[57] These formulations deliver humic substances directly to plant tissues or roots, enhancing stress tolerance and nutrient efficiency. Recent research from the 2020s highlights leonardite's role in climate change adaptation, showing that sulfur-enriched variants improve drought resistance in maize by maintaining yield under water-limited conditions in calcareous soils.^[55] Such applications underscore its potential for sustainable farming amid increasing environmental pressures.^[35]

Industrial and Remediation Uses

Leonardite serves as a key additive in the oil and gas industry, particularly in drilling fluids, where its humic acid content helps stabilize mud systems by controlling viscosity and acting as a dispersant.^[5] These properties replace traditional tannins, enabling effective rheology management in both water-based and oil-based muds during exploration.^[58] Organophilic variants of leonardite exhibit high thermal stability, maintaining functionality up to elevated temperatures encountered in deep wells, which supports its use in high-pressure, high-temperature environments.^[59] This application has grown in the 2020s due to increasing eco-regulations favoring biodegradable, low-toxicity alternatives in sustainable drilling practices.^[58] In environmental remediation, leonardite binds heavy metals such as cadmium, zinc, lead, and uranium in contaminated soils, reducing their bioavailability and mobility through complexation with humic substances. When mixed with compost, it decreases plant uptake of these metals, facilitating safer phytoremediation by stabilizing pollutants in the root zone.^[19] Studies show bioavailability reductions of 30-50% for cadmium in amended sites, enhancing soil restoration without extensive excavation.^[60] Additionally, leonardite-based humic extracts enable soil washing techniques that extract heavy metals like copper, zinc, and chromium into aqueous solutions for removal, offering an efficient ex-situ cleanup method.^[61] Beyond drilling and remediation, leonardite functions as a stabilizer for ion-exchange resins in water treatment processes, where its organic acids prevent resin fouling and extend operational life by mitigating organic buildup. In ceramics manufacturing, leonardite acts as a natural binder in formulations, such as those combined with basalt powders for porous membranes, improving structural integrity during sintering without synthetic additives.^[62] As an animal feed supplement, leonardite enhances nutrient absorption and lipid metabolism in livestock, with additions to broiler diets increasing high-density lipoprotein levels and reducing triglycerides, thereby supporting overall health and growth efficiency. It is also used as a feed additive in aquaculture to promote growth and improve water quality.^[63]^[11]

References

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[58]
Humax® | JH Biotech Inc.
Humax is a concentrated liquid humic acid from Leonardite, a naturally occurring substance that can be used as a soil or foliar application.
[59]
Dynamic thermal aging of water-based drilling fluids with different ...
To use lignite and leonardite as drilling mud additives is absolutely necessary for their humic/fulvic acid content to be released as part of the process. Thus, ...
[60]
US4778608A - High temperature drilling mud composition
... leonardite, that is particularly useful in a water-based drilling mud and exhibits unexpected stability and rheological functionality at the high ...
[61]
Phytoremediation strategies for mitigating environmental toxicants
Oct 15, 2024 · They also reported that both cow manure and leonardite reduced Cd concentrations by 3.3-fold and 1.6-fold, respectively, suggesting that a ...<|separator|>
[62]
Soil washing with solutions of humic substances from manure ...
Humic Substances (HS) from Leonardite and two different composts were used as biosurfactants to wash heavy metals (Cu, Pb, Zn, Cd, Cr) from a soil.
[63]
Fabrication of Ag nanoparticles coated leonardite basalt ceramic ...
This study aimed to fabricate a novel, low-cost, and environmental-friendly ceramic membrane based on basalt and leonardite powders via press and sintering ...
[64]
Evaluation of leonardite as a feed additive on lipid metabolism and ...
The increased serum HDL and decreased total triglycerides suggest that leonardite is a promising feed additive to improve lipid metabolism. The higher serum Mg ...Missing: animal supplement