Assessment of Cellulose Nanofiber-Based Elastase Biosensors to Inflammatory Disease as a Function of Spacer Length and Fluorescence Response.

Inflammatory disease biomarker detection has become a high priority in point-of-care diagnostic research in relation to chronic wounds, with a variety of sensor-based designs becoming available. Herein, two primary aspects of biosensor design are examined: (1) assessment of a cellulose nanofiber (CNF) matrix derived from cotton ginning byproducts as a sensor transducer surface; and (2) assessment of the relation of spacer length and morphology between the CNF cellulose backbone and peptide fluorophore as a function of sensor activity for porcine pancreatic and human neutrophil elastases. X-ray crystallography, specific surface area, and pore size analyses confirmed the suitability of CNF as a matrix for wound care diagnostics. Based upon the normalized degree of substitution, a pegylated-linker connecting CNF transducer substrate to peptide fluorophore showed the greatest fluorescence response, compared to short- and long-chain alkylated linkers.

Uncovering surface area and micropores in almond shell biochars by rainwater wash.

Biochars have been considered for adsorption of contaminants in soil and water, as well as conditioning and improving soil quality. Pore surface area is an important property of biochar. Biochars were created from shells of two almond varieties with different ash content. The pyrolysis was performed at 650 and 800°C for 40-240min. Significant surface areas developed at the higher temperature and at pyrolysis times of 120min and longer. Washing the materials in synthetic rainwater removed ash and exposed additional surface area, particularly in small-diameter pores. When results from low-ash almond shell biochars were compared with high-ash almond shell biochars, it was found that the pore distribution was more uniform for the high-ash starting material and almost independent of pyrolysis time or washing. The result from the washing study is important as it suggested that adsorptive properties may change once biochars are exposed to rainwater.

Influence of post-treatment strategies on the properties of activated chars from broiler manure.

There are a myriad of carbonaceous precursors that can be used advantageously to produce activated carbons or chars, due to their low cost, availability and intrinsic properties. Because of the nature of the raw material, production of granular activated chars from broiler manure results in a significant ash fraction. This study was conducted to determine the influence of several pre- and post-treatment strategies in various physicochemical and adsorptive properties of the resulting activated chars. Pelletized samples of broiler litter and cake were pyrolyzed at 700 °C for 1h followed by a 45 min steam activation at 800 °C at different water flow rates from 1 to 5 mL min(-1). For each activation strategy, samples were either water-rinsed or acid-washed and rinsed or used as is (no acid wash/rinse). Activated char's physicochemical and adsorptive properties towards copper ions were selectively affected by both pre- and post-treatments. Percent ash reduction after either rinsing or acid washing ranged from 1.1 to 15.1% but washed activated chars were still alkaline with pH ranging from 8.4 to 9.1. Acid washing or water rinsing had no significant effect in the ability of the activated char to adsorb copper ions, however it significantly affected surface area, pH, ash content and carbon content. Instead, manure type (litter versus cake) and the activation water flow rate were determining factors in copper ion adsorption which ranged from 38 mg g(-1) to 104 mg g(-1) of activated char. Moreover, strong positive correlations were found between copper uptake and concentration of certain elements in the activated char such as phosphorous, sulfur, calcium and sodium. Rinsing could suffice as a post treatment strategy for ash reduction since no significant differences in the carbon properties were observed between rinsed and acid wash treatments.

Heavy metal and phenol adsorptive properties of biochars from pyrolyzed switchgrass and woody biomass in correlation with surface properties.

In this work, the surface structures of biochars, derived from three types of biomass, switchgrass (SG), hardwood (HW) and softwood (SW) through either fast pyrolysis (FP) in a fluidized-bed reactor (at 500 °C) or slow pyrolysis (at 500° and 700 °C), were studied in detail, and compared with that of the activated carbons obtained by steam activation of the slow pyrolyzed biochars (at 500 °C). The surface acidic functional groups were determined quantitatively by the Boehm Titration method. The adsorptive properties of heavy metals, Zn(2+) and Cu(2+) onto the biochars and the activated carbons were investigated by the adsorption isotherms and SEM images, and correlated with the surface properties. ATR-FTIR and GC techniques were used to analyze the adsorptive behavior of phenol onto the biochars and activated carbons, and the results demonstrated that phenol adsorption capability is directly proportional to the micropore surface area as well as the combined level of the accessible carboxylic and lactonic groups. The relative adsorption capacity with respect to the biomass precursor follows the order: SW > HW > SG.

Biochar: a synthesis of its agronomic impact beyond carbon sequestration.

Biochar has been heralded as an amendment to revitalize degraded soils, improve soil carbon sequestration, increase agronomic productivity, and enter into future carbon trading markets. However, scientific and economic technicalties may limit the ability of biochar to consistently deliver on these expectations. Past research has demonstrated that biochar is part of the black carbon continuum with variable properties due to the net result of production (e.g., feedstock and pyrolysis conditions) and postproduction factors (storage or activation). Therefore, biochar is not a single entity but rather spans a wide range of black carbon forms. Biochar is black carbon, but not all black carbon is biochar. Agronomic benefits arising from biochar additions to degraded soils have been emphasized, but negligible and negative agronomic effects have also been reported. Fifty percent of the reviewed studies reported yield increases after black carbon or biochar additions, with the remainder of the studies reporting alarming decreases to no significant differences. Hardwood biochar (black carbon) produced by traditional methods (kilns or soil pits) possessed the most consistent yield increases when added to soils. The universality of this conclusion requires further evaluation due to the highly skewed feedstock preferences within existing studies. With global population expanding while the amount of arable land remains limited, restoring soil quality to nonproductive soils could be key to meeting future global food production, food security, and energy supplies; biochar may play a role in this endeavor. Biochar economics are often marginally viable and are tightly tied to the assumed duration of agronomic benefits. Further research is needed to determine the conditions under which biochar can provide economic and agronomic benefits and to elucidate the fundamental mechanisms responsible for these benefits.

Influence of biochar on nitrogen fractions in a coastal plain soil.

Interest in the use of biochar from pyrolysis of biomass to sequester C and improve soil productivity has increased; however, variability in physical and chemical characteristics raises concerns about effects on soil processes. Of particular concern is the effect of biochar on soil N dynamics. The effect of biochar on N dynamics was evaluated in a Norfolk loamy sand with and without NHNO. High-temperature (HT) (≥500°C) and low-temperature (LT) (≤400°C) biochars from peanut hull ( L.), pecan shell ( Wangenh. K. Koch), poultry litter (), and switchgrass ( L.) and a fast pyrolysis hardwood biochar (450-600°C) were evaluated. Changes in inorganic, mineralizable, resistant, and recalcitrant N fractions were determined after a 127-d incubation that included four leaching events. After 127 d, little evidence of increased inorganic N retention was found for any biochar treatments. The mineralizable N fraction did not increase, indicating that biochar addition did not stimulate microbial biomass. Decreases in the resistant N fraction were associated with the high pH and high ash biochars. Unidentified losses of N were observed with HT pecan shell, HT peanut hull, and HT and LT poultry litter biochars that had high pH and ash contents. Volatilization of N as NH in the presence of these biochars was confirmed in a separate short-term laboratory experiment. The observed responses to different biochars illustrate the need to characterize biochar quality and match it to soil type and land use.

Chicken manure biochar as liming and nutrient source for acid Appalachian soil.

Acid weathered soils often require lime and fertilizer application to overcome nutrient deficiencies and metal toxicity to increase soil productivity. Slow-pyrolysis chicken manure biochars, produced at 350 and 700°C with and without subsequent steam activation, were evaluated in an incubation study as soil amendments for a representative acid and highly weathered soil from Appalachia. Biochars were mixed at 5, 10, 20, and 40 g kg into a Gilpin soil (fine-loamy, mixed, active, mesic Typic Hapludult) and incubated in a climate-controlled chamber for 8 wk, along with a nonamended control and soil amended with agronomic dolomitic lime (AgLime). At the end of the incubation, soil pH, nutrient availability (by Mehlich-3 and ammonium bicarbonate diethylene triamine pentaacetic acid [AB-DTPA] extractions), and soil leachate composition were evaluated. Biochar effect on soil pH was process- and rate-dependent. Biochar increased soil pH from 4.8 to 6.6 at the high application rate (40 g kg), but was less effective than AgLime. Biochar produced at 350°C without activation had the least effect on soil pH. Biochar increased soil Mehlich-3 extractable micro- and macronutrients. On the basis of unit element applied, increase in pyrolysis temperature and biochar activation decreased availability of K, P, and S compared to nonactivated biochar produced at 350°C. Activated biochars reduced AB-DTPA extractable Al and Cd more than AgLime. Biochar did not increase NO in leachate, but increased dissolved organic carbon, total N and P, PO, SO, and K at high application rate (40 g kg). Risks of elevated levels of dissolved P may limit chicken manure biochar application rate. Applied at low rates, these biochars provide added nutritional value with low adverse impact on leachate composition.

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 biochar's 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.

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.

Influence of soil properties on heavy metal sequestration by biochar amendment: 2. Copper desorption isotherms.

Contaminant desorption constrains the long-term effectiveness of remediation technologies, and is strongly influenced by dynamic non-equilibrium states of environmental and biological media. Information is currently lacking in the influence of biochar and activated carbon amendments on desorption of heavy metal contaminants from soil components. In this study, copper sorption-desorption isotherms were obtained for 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. Acidic pecan shell-derived activated carbon and basic broiler litter biochar were employed in desorption experiments designed to address both leaching by rainfall and toxicity characteristics. For desorption in synthetic rain water, broiler litter biochar amendment diminished sorption-desorption hysteresis. In acetate buffer (pH 4.9), significant copper leaching was observed, unless acidic activated carbon (pH(pzc)=3.07) was present. Trends observed in soluble phosphorus and zinc concentrations for sorption and desorption equilibria suggested acid dissolution of particulate phases that can result in a concurrent release of copper and other sorbed elements. In contrast, sulfur and potassium became depleted as a result of supernatant replacements only when amended carbon (broiler litter biochar) or soil (San Joaquin) contained appreciable amounts. A positive correlation was observed between the equilibrium aluminum concentration and initial copper concentration in soils amended with acidic activated carbon but not basic biochar, suggesting the importance of cation exchange mechanism, while dissolution of aluminum oxides cannot be ruled out.

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.

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.

Feasibility of mercury removal from simulated flue gas by activated chars made from poultry manures.

Increased emphasis on reduction of mercury emissions from coal fired electric power plants has resulted in environmental regulations that may in the future require application of activated carbons as mercury sorbents for mercury removal. At the same time, the quantity of poultry manure generated each year is large and technologies that take advantage of the material should be explored. The purpose of the work was to obtain preliminary data to investigate if activated chars made from different poultry manures could adsorb mercury from simulated flue gas. In laboratory experiments, activated chars made from chicken cake and litter removed mercury from the gas as well as a commercial alternative. It was also found that acid-washing these chars after activation may improve pore structure but does not influence the mercury removal efficiency. Activated chars were also made from turkey cake and litter. These raw materials produced activated chars with similar pore structure as those made from chicken manure, but they did not adsorb mercury as well. Acid-washing the turkey manure-based chars improved their performance, but this step would add to the cost of production. Preliminary evaluations suggest that unwashed activated chars may cost as little as $0.95/kg to produce.

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.

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.

Activated carbons from flax shive and cotton gin waste as environmental adsorbents for the chlorinated hydrocarbon trichloroethylene.

Agricultural by-products represent a considerable quantity of harvested commodity crops. The use of by-products as precursors for the production of widely used adsorbents, such as activated carbons, may impart a value-added component of the overall biomass harvested. Our objective in this paper is to show that flax shive and cotton gin waste can serve as a precursor for activated carbon that can be used for adsorption of trichloroethylene (TCE) from both the liquid and gas phases. Testing was conducted on carbon activated with phosphoric acid or steam. The results show that activated carbon made from flax shive performed better than select commercial activated carbons, especially at higher TCE concentrations. The activation method employed had little effect on TCE adsorption in gas or vapor phase studies but liquid phase studies suggested that steam activation is slightly better than phosphoric acid activation. As expected, the capacity for the activated carbons depended on the fluid phase equilibrium concentration. At a fluid concentration of 2 mg of TCE/L of fluid, the capacity of the steam activated carbon made from flax shive was similar at 64 and 80 mg TCE/g of carbon for the vapor and liquid phases, respectively. Preliminary cost estimates suggest that the production costs of such carbons are $1.50 to $8.90 per kg, depending on activation method and precursor material; steam activation was significantly less expensive than phosphoric acid activation.

Anion and cation leaching or desorption from activated carbons from municipal sludge and poultry manure as affected by pH.

The conversion of municipal sludge and poultry manure to activated carbon results in a significant ash fraction that contains several different anions and cations. The objectives of this study were to determine whether the select ions are released or leached from virgin carbon into the sorption medium at different pH values. Activated carbon was placed in solutions of pH 1, 5, or 7, and the leaching of six cations (cadmium, chromium, copper, nickel, lead, and zinc) and two anions (arsenate and selenate) was recorded. Considerable quantities of zinc and copper were removed at pH 1 from all carbon sources. However, the amounts leached at pH 5 and 7 were small or undetectable. Our results indicate that leaching or desorption from carbons made from municipal sludge or poultry manure is pH-dependent and occurs readily under highly acidic conditions but minimally under pH conditions typically seen in contaminated water or wastewater.

Granular activated carbons from broiler manure: physical, chemical and adsorptive properties.

Broiler manure produced at large concentrated facilities poses risks to the quality of water and public health. This study utilizes broiler litter and cake as source materials for granular activated carbon production and optimizes conditions for their production. Pelletized manure samples were pyrolyzed at 700 degrees C for 1 h followed by activation in an inert atmosphere under steam at different water flow rates, for a period ranging from 15 to 75 min. Carbon physical and adsorptive properties were dependent on activation time and quantity of steam used as activant, yields varied from 18% to 28%, surface area varied from 253 to 548 m2/g and copper ion adsorption varied from 0.13 to 1.92 mmol Cu2+/g carbon. Best overall performing carbons were steam activated for 45 min at 3 ml/min. Comparative studies with commercial carbons revealed the broiler cake-based carbon as having the highest copper ion efficiency.