Lynda H. Wartelle

Immobilization of heavy metal ions (CuII, CdII, NiII, and PbII) by broiler litter-derived biochars in water and soil.

Chars, a form of environmental black carbon resulting from incomplete burning of biomass, can immobilize organic contaminants by both surface adsorption and partitioning mechanisms. The predominance of each sorption mechanism depends upon the proportion of organic to carbonized fractions comprising the sorbent. Information is currently lacking in the effectiveness of char amendment for heavy metal immobilization in contaminated (e.g., urban and arms range) soils where several metal contaminants coexist. The present study employed sorbents of a common biomass origin (broiler litter manure) that underwent various degrees of carbonization (chars formed by pyrolysis at 350 and 700 degrees C and steam-activated analogues) for heavy metal (Cd(II), Cu(II), Ni(II), and Pb(II)) immobilization in water and soil. ATR-FTIR, (1)H NMR, and Boehm titration results suggested that higher pyrolysis temperature and activation lead to the disappearance (e.g., aliphatic -CH(2) and -CH(3)) and the formation (e.g., C-O) of certain surface functional groups, portions of which are leachable. Both in water and in soil, pH increase by the addition of basic char enhanced the immobilization of heavy metals. Heavy metal immobilization resulted in nonstoichiometric release of protons, that is, several orders of magnitude greater total metal concentration immobilized than protons released. The results suggest that with higher carbonized fractions and loading of chars, heavy metal immobilization by cation exchange becomes increasingly outweighed by other controlling factors such as the coordination by pi electrons (C=C) of carbon and precipitation.

Influence of Pyrolysis Temperature on Biochar Property and Function as a Heavy Metal Sorbent in Soil

While a large-scale soil amendment of biochars continues to receive interest for enhancing crop yields and to remediate contaminated sites, systematic study is lacking in how biochar properties translate into purported functions such as heavy metal sequestration. In this study, cottonseed hulls were pyrolyzed at five temperatures (200, 350, 500, 650, and 800 °C) and characterized for the yield, moisture, ash, volatile matter, and fixed carbon contents, elemental composition (CHNSO), BET surface area, pH, pHpzc, and by ATR-FTIR. The characterization results were compared with the literature values for additional source materials: grass, wood, pine needle, and broiler litter-derived biochars with and without post-treatments. At respective pyrolysis temperatures, cottonseed hull chars had ash content in between grass and wood chars, and significantly lower BET surface area in comparison to other plant source materials considered. The N:C ratio reached a maximum between 300 and 400 °C for all biomass sources considered, while the following trend in N:C ratio was maintained at each pyrolysis temperature: wood≪cottonseed hull≈grass≈pine needle≪broiler litter. To examine how biochar properties translate into its function as a heavy metal (NiII, CuII, PbII, and CdII) sorbent, a soil amendment study was conducted for acidic sandy loam Norfolk soil previously shown to have low heavy metal retention capacity. The results suggest that the properties attributable to the surface functional groups of biochars (volatile matter and oxygen contents and pHpzc) control the heavy metal sequestration ability in Norfolk soil, and biochar selection for soil amendment must be made case-by-case based on the biochar characteristics, soil property, and the target function.

Contaminant immobilization and nutrient release by biochar soil amendment: Roles of natural organic matter

Contamination of soil interstitial waters by labile heavy metals such as Cu(II), Cd(II), and Ni(II) is of worldwide concern. Carbonaceous materials such as char and activated carbon have received considerable attention in recent years as soil amendment for both sequestering heavy metal contaminants and releasing essential nutrients like sulfur. Information is currently lacking in how aging impacts the integrity of biochars as soil amendment for both agricultural and environmental remediation purposes. Major contributors to biochar aging in soils are: sorption of environmental constituents, especially natural organic matter (NOM), and oxidation. To investigate the impact of NOM and organic fractions of chars, we employed broiler litter-derived chars and steam-activated carbons that underwent varying degrees of carbonization, in the presence and absence of NOM having known carboxyl contents. For aging by oxidation, we employed phosphoric acid activated carbons that underwent varying degrees of oxidation during activation. The results suggest that the organic fractions of biochars, and NOM having high carboxyl contents can mobilize Cu(II) retained by alkaline soil. Base treatment of broiler litter-derived char formed at low pyrolysis temperature (350 degrees C) improved the immobilization of all heavy metals investigated, and the extent of immobilization was similar to, or slightly greater than pecan shell-derived phosphoric acid activated carbons. Portions of total sulfur were released in soluble form in soil amended with broiler litter-derived carbons, but not pecan shell-derived phosphoric acid activated carbons.

Enhanced metal adsorption by soybean hulls modified with citric acid

Abstract A method was developed to enhance metal ion adsorption of soybean hulls for wastewater treatment using copper ion (Cu2+) as a typical metal ion. Hulls, extracted with 0.1 N NaOH, were modified with different citric acid (CA) concentrations (0.1-1.2 M) at 120°C for 90 min. CA-modified hulls had adsorption capacities for Cu2+ from 0.68 to 2.44 mmoles/g, which was much higher than for unmodified hulls (0.39 mmoles/g). The total negative charge for these hulls also increased with increasing CA concentration and was about twice the copper ion adsorption capacity at all CA concentrations. The need for NaOH (base) extraction (BE) before CA modification was examined. CA-modified, non-extracted (NE) and CA-modified, BE hulls were compared for adsorption kinetics and adsorption capacity. Base extraction resulted in modified hulls with faster adsorption kinetics and slightly lower adsorption capacity for copper ion than NE hulls. For BE, CA-modified hulls, increasing the temperature from 25°C to 60°C appeared to have no effect on the rate of copper ion removal from solution. CA modification of soybean hulls greatly enhanced metal ion removal and resulted in a product with possible commercial potential for metal ion remediation.

Acid-activated carbons from almond shells: physical, chemical and adsorptive properties and estimated cost of production.

Abstract A series of phosphoric-acid activated carbons were made from almond shells using six different activation or activation/oxidation methods. The carbons were compared to each other and to two commercial carbons in an effort to ascertain the relative value of the carbons in terms of yield, surface area, attrition, surface functional groups, organic uptake, metal uptake, as well as estimated cost of production. Of the six methods investigated, the method that produced the best overall performing almond shell carbon and least expensive carbon in terms of production cost was the “Air-Activation” method. This method involved the simultaneous activation and oxidation of almond shells under an air atmosphere.

Influence of soil properties on heavy metal sequestration by biochar amendment: 1. Copper sorption isotherms and the release of cations.

The amendment of carbonaceous materials such as biochars and activated carbons is a promising in situ remediation strategy for both organic and inorganic contaminants in soils and sediments. Mechanistic understandings in sorption of heavy metals on amended soil are necessary for appropriate selection and application of carbonaceous materials for heavy metal sequestration in specific soil types. In this study, copper sorption isotherms were obtained for soils having distinct characteristics: clay-rich, alkaline San Joaquin soil with significant heavy metal sorption capacity, and eroded, acidic Norfolk sandy loam soil having low capacity to retain copper. The amendment of acidic pecan shell-derived activated carbon and basic broiler litter biochar lead to a greater enhancement of copper sorption in Norfolk soil than in San Joaquin soil. In Norfolk soil, the amendment of acidic activated carbon enhanced copper sorption primarily via cation exchange mechanism, i.e., release of proton, calcium, and aluminum, while acid dissolution of aluminum cannot be ruled out. For San Joaquin soil, enhanced copper retention by biochar amendment likely resulted from the following additional mechanisms: electrostatic interactions between copper and negatively charged soil and biochar surfaces, sorption on mineral (ash) components, complexation of copper by surface functional groups and delocalized π electrons of carbonaceous materials, and precipitation. Influence of biochar on the release of additional elements (e.g., Al, Ca) must be carefully considered when used as a soil amendment to sequester heavy metals.

Retention of Heavy Metals by Carboxyl Functional Groups of Biochars in Small Arms Range Soil

Long-term effectiveness of biochar for heavy metal stabilization depends upon biochars sorptive property and recalcitrance in soil. To understand the role of carboxyl functional groups on heavy metal stabilization, cottonseed hull biochar and flax shive steam-activated biochar having a low O/C ratio (0.04-0.06) and high fixed carbon content (~80% dry weight basis) were oxidized using concentrated H(2)SO(4)/HNO(3) and 30% HNO(3). Oxidized and unoxidized biochars were characterized for O/C ratio, total acidity, pH, moisture, ash, volatile matter, and fixed carbon contents, Brunauer-Emmett-Teller surface area, and attenuated total reflectance Fourier transform infrared spectral features. Characterized biochars were amended (2%, 5%, 10%, and 20% in grams of biochar per gram of soil) on a sandy, slightly acidic (pH 6.27) heavy metal contaminated small arms range soil fraction (<250 μm) having low total organic carbon (0.518%) and low cation exchange capacity (0.95 cmol(c) kg(-1)). Oxidized biochars rich in carboxyl functional groups exhibited significantly greater Pb, Cu, and Zn stabilization ability compared to unoxidized biochars, especially in pH 4.9 acetate buffer (standard solution for the toxicity characteristic leaching procedure). Oppositely, only oxidized biochars caused desorption of Sb, indicating a counteracting impact of carboxyl functional groups on the solubility of anions and cations. The results suggested that appropriate selection of biochar oxidant will produce recalcitrant biochars rich in carboxyl functional groups for a long-term heavy metal stabilization strategy in contaminated soils.

Steam- or carbon dioxide-activated carbons from almond shells: physical, chemical and adsorptive properties and estimated cost of production.

A series of steam- or carbon dioxide (CO2)-activated, granular activated carbons (GACs) were made from almond shells using six different activation or activation/oxidation conditions for each series. Unoxidized/oxidized pairs of GACs were compared among treatments and to two commercial GACs in order to determine the relative value of the carbons. Comparative terms included yield, surface area, attrition, surface charge, copper ion (Cu2+) uptake, adsorption of a mixture of six polar and non-polar organic compounds and an estimated cost of carbon production. Of the six conditions investigated for steam activation, two treatments consisting of a 1 h pyrolysis at either 700°C or 800°C, followed by a 2 h activation at 800°C with the introduction of water at a rate of 7.0 ml/min were the best overall performing unoxidized/oxidized pairs in terms of copper ion or organics adsorption, respectively. Of the six conditions investigated for carbon dioxide activation, a treatment consisting of a 1 h pyrolysis at 700°C, followed by a 2 h activation at 800°C using a 75% CO2/25% N2 gas mixture was the best overall performing unoxidized/oxidized pair. Our estimated costs of production indicate that steam-activated, unoxidized and oxidized carbons appear to be the most economical GACs to manufacture and also the most economical for removal of copper ions and organic compounds.

Sorption of deisopropylatrazine on broiler litter biochars.

Biochars have received increasing attention in recent years because of a large-scale soil amendment to improve soil fertility, immobilize contaminants, and to serve as a recalcitrant carbon stock. Information is currently lacking in factors controlling the sorption capacity of manure-derived biochars. In this study, sorption isotherms for deisopropylatrazine, a stable metabolite of the widely applied herbicide atrazine, were obtained in acidic aqueous media (pH 5.5) for broiler litter-derived biochars formed by pyrolysis at 350 and 700 °C with and without steam activation at 800 °C. An increase in the Freundlich distribution coefficient (KF) and isotherm nonlinearity (nF) was observed with pyrolysis temperature and steam-activation, suggesting that the surface area and aromaticity (degree of carbonization) are the factors controlling the sorption capacity of chars at low surface coverage. At high surface coverage, the isotherms became increasingly linear, suggesting sorption on noncarbonized fraction of biochars. In binary-solute experiments, the sorption of deisopropylatrazine was significantly diminished by Cu(II), further suggesting the predominance of the surface adsorption mechanism at low surface coverage of biochars.

Lead retention by broiler litter biochars in small arms range soil: impact of pyrolysis temperature.

Phosphorus-rich manure biochar has a potential for stabilizing Pb and other heavy metal contaminants, as well as serving as a sterile fertilizer. In this study, broiler litter biochars produced at 350 and 650 °C were employed to understand how biochars elemental composition (P, K, Ca, Mg, Na, Cu, Pb, Sb, and Zn) affects the extent of heavy metal stabilization. Soil incubation experiments were conducted using a sandy, slightly acidic (pH 6.11) Pb-contaminated (19906 mg kg(-1) total Pb primarily as PbCO(3)) small arms range (SAR) soil fraction (<250 μm) amended with 2-20 wt % biochar. The Pb stabilization in pH 4.9 acetate buffer reached maximum at lower (2-10 wt %) biochar amendment rate, and 350 °C biochar containing more soluble P was better able to stabilize Pb than the 650 °C biochar. The 350 °C biochar consistently released greater amounts of P, K, Mg, Na, and Ca than 650 °C biochar in both unbuffered (pH 4.5 sulfuric acid) and buffered (pH 4.9 acetate) systems, despite 1.9-4.5-fold greater total content of the 650 °C biochar. Biochars, however, did not influence the total extractable Pb over three consecutive equilibration periods consisting of (1) 1 week in pH 4.5 sulfuric acid (simulated leaching by rainfall), (2) 1 week in pH 4.9 acetate buffer (standard solution for toxicity characteristic leaching procedure), and (3) 1 h in pH 1.5 glycine at 37 °C (in vitro bioaccessibility procedure). Overall, lower pyrolysis temperature was favorable for stabilizing Pb (major risk driver of SAR soils) and releasing P, K, Ca, and other plant nutrients in a sandy acidic soil.