Valorization of cow manure via hydrothermal carbonization for phosphorus recovery and adsorbents for water treatment.

The increased quantities of manure being generated by livestock and their extensive agronomic use have raised concerns around run-off impacting soil and groundwater quality. Manure contains valuable nutrients (especially phosphorus) that are critical to agriculture, but when directly land-applied the run-off of such nutrients contributes to eutrophication of waterways. This study investigates the hydrothermal carbonization of cow manure at two industrially feasible process extremes: 190 °C, 1 h and 230 °C, 3 h, to concentrate and then recover phosphorus from the solid hydrochar via acid leaching and precipitation. Up to 98 wt% of phosphorus initially present in the hydrochar (88% in the raw manure) can be recovered, with the dominant crystalline species being hydroxyapatite. Acid leached hydrochars were subsequently pyrolyzed at 600 °C for 30 min, and then evaluated as adsorbent materials for water remediation by using methylene blue as a model adsorbate. Although pyrolyzed hydrochars have surface areas an order of magnitude higher (160-236 m2/g) than the non-pyrolyzed acid leached hydrochars (11-23 m2/g), their adsorption capacity is three times lower. Furthermore, while the higher carbonization temperature leads to greater recovery of phosphorus, it likewise leads to higher heavy metal concentrations in the precipitate (ranging from 0.1 to 100 mgmetal/gppt). As such, lower temperature carbonization followed by acid-extraction - without further solid processing - is a potential pathway to recover phosphorus and adsorbent materials.

Synergistic improvements in energy recovery and bio-oil quality through integrated thermochemical valorization of agro-industrial waste of varying moisture content.

Two thermochemical valorization schemes were investigated for co-upgrading dry and wet agricultural wastes through integrated hydrothermal carbonization (HTC) and pyrolysis. In the first pathway, dry and wet wastes were co-carbonized. The resulting hydrochar was pyrolyzed to yield an energy dense biochar (26-32 MJ/kg) high in fixed carbon (41-86 wt%) and low in volatile matter (6-12 wt%). The resulting bio-oil was lower in carboxylic acids and higher in phenols than predicted based on an additive scheme. In pathway two, wet waste (only) underwent HTC and the resulting hydrochar was mixed with dry waste and the mixture pyrolyzed. This pathway showed a lower biochar yield (32-67 wt%) and lower HHV values (24-31 MJ/kg) but higher fixed carbon content (65-84 wt%). The bio-oil contained more carboxylic acids than pathway 1 bio-oil. Pathway 1 biochars were more thermally reactive than pathway 2 biochars, reflecting a synergistic deoxygenation that occurs when incorporating dry waste in HTC prior to pyrolysis.

Improving nutrients ratio in class A biosolids through vivianite recovery: Insights from a wastewater resource recovery facility.

Class A biosolids from water resource recovery facilities (WRRFs) are increasingly used as sustainable alternatives to synthetic fertilizers. However, the high phosphorus to nitrogen ratio in biosolids leads to a potential accumulation of phosphorus after repeated land applications. Extracting vivianite, an FeP mineral, prior to the final dewatering step in the biosolids treatment can reduce the P content in the resulting class A biosolids and achieve a P:N ratio closer to the 1:2 of synthetic fertilizers. Using ICP-MS, IC, UV-Vis colorimetric methods, Mössbauer spectroscopy, and SEM-EDX, a full-scale characterization of vivianite at the Blue Plains Advanced Wastewater Treatment Plant (AWTTP) was surveyed throughout the biosolids treatment train. Results showed that the vivianite-bound phosphorus in primary sludge thickening, before pre-dewatering, after thermal hydrolysis, and after anaerobic digestion corresponded to 8 %, 52 %, 40 %, and 49 % of the total phosphorus in the treatment influent. Similarly, the vivianite-bound iron concentration also corresponded to 8 %, 52 %, 40 %, and 49 % of the total iron present (from FeCl3 dosing), because the molar ratio between total iron and total incoming phosphorus was 1.5:1, which is the same stoichiometry of vivianite. Based on current P:N levels in the Class A biosolids at Blue Plains, a vivianite recovery target of 40 % to ideally 70 % is required in locations with high vivianite content to reach a P:N ratio in the resulting class A biosolid that matches synthetic fertilizers of 1:1.3 to 1:2, respectively. A financial analysis on recycling iron from the recovered vivianite had estimated that 14-25 % of Blue Plain's annual FeCl3 demand can potentially be met. Additionally, model simulations with Visual Minteq were used to evaluate the pre-treatment options that maximize vivianite recovery at different solids treatment train locations.

Green solvents to enhance hydrochar quality and clarify effects of secondary char.

Several limitations hinder the industrial-scale implementation of hydrothermal carbonization (HTC) of biomass, especially the quality of as-carbonized hydrochar. This work investigates solvent extraction of hydrochars to enhance their potential applications. Hydrochars were produced at several HTC temperatures (190, 220, 250 °C) from cellulose and extracted using combinations of green polar solvents (ethyl acetate, acetone, and methanol). Results show that the composition of the extractable fraction resembles that of the HTC liquor, rich in carboxylic acids and furan derivatives, while the non-extractable solid phase shows improved thermal profiles devoid of highly volatile compounds. Carbon microspheres (non-dissolvable secondary char) are unaffected by extraction. The organics adsorbed on the hydrochar surface comprise highly volatile species and solvent washing effectively removes them.

Addition of in situ clay catalysts at different process points in a cascaded hydrothermal carbonization-pyrolysis process for agro-industrial waste valorization.

Agro-industrial wastes can be thermochemically converted to sustainable fuels and upcycled carbon products. However, processing such feedstocks through pyrolysis or hydrothermal carbonization (HTC) alone yields fuels that require significant downstream upgrading. In this work, apple pomace was treated via a cascaded HTC-pyrolysis process using inexpensive and abundant clay catalysts, montmorillonite and attapulgite. Clays were added pre-HTC to raw biomass or to hydrochar pre-pyrolysis to examine the effect of addition as a function of process insertion point. Both clays produce similar bio-oils when they are added at the same process point. However, bio-oil was affected by the point in which clay was added to the process (before or after HTC). When clay was added pre-HTC, the bio-oil had an average hydrocarbon content twice that when clay was added to the hydrochar after HTC, prior to pyrolysis.

Uncovering the transition between hydrothermal carbonization and liquefaction via secondary char extraction: A case study using food waste.

Despite the ability to perform both processes in the same reactor, hydrothermal carbonization (HTC) and hydrothermal liquefaction (HTL) are considered two distinct processes differentiated by their reaction temperatures. As temperatures increase from the less severe HTC range into the HTL regime, the product distribution progressively favors an organic bio-oil phase relative to solid hydrochar. Solvents are commonly used to extract bio-oil from the solid residues produced during HTL, and to separate the amorphous secondary char from the coal-like primary char of HTC hydrochars. This suggests secondary char is a HTL biocrude precursor. Lipid-rich food waste was hydrothermally processed between 190 and 340 °C, spanning HTC to HTL conditions. Higher temperatures produce more gas, less liquid, and similar amounts of a progressively less oxygenated hydrochars, suggesting a gradual transition from HTC to HTL. However, analyses of ethanol-separated primary chars and secondary chars tell a different story. While the primary char is progressively more carbonized with temperature, the secondary char composition sharply changes at 250 °C. That is, lipid hydrolysis begins around 220 °C, but proceeds rather completely at 250 °C and above. A lower HTL temperature reduces the energy cost of the hydrothermal process, yet enables full lipid hydrolysis into long chain fatty acids while minimizing recondensation and repolymerization of fatty acids onto the primary char and their subsequent amidation. This maximizes the conversion of lipid-rich feedstocks into liquid fuel precursors with up to 70 % energy recovery.

Effect of solvent and feedstock selection on primary and secondary chars produced via hydrothermal carbonization of food wastes.

Hydrothermal carbonization is a thermochemical process that converts wet waste biomass into hydrochar, a renewable solid fuel that comprises a coal-like primary phase and an oily secondary phase. The varying oxidation rates of these phases may result in an inefficient energy recovery when combusting the hydrochar, as secondary char is more reactive. Brewer's spent grain, dairy cheese whey and food waste were hydrothermally carbonized at 250 °C. The hydrochars were extracted using six solvents to evaluate the hydrochar partitioning between primary and secondary char phases. Feedstock nature and solvent selection impact the amount and composition of these phases detected. For lipid-rich feedstocks, ethanol extracts up to 50 wt% secondary char enriched in liquid fuel precursors from a solid primary char with enhanced coal-like characteristics. For substrates rich in carbohydrates, proteins, and lignocellulose, less secondary char is produced. Acetone and dichloromethane remove the oily secondary char and maximize primary char yield.

Production of biochar from crop residues and its application for anaerobic digestion.

Anaerobic digestion (AD) is a viable and cost-effective method for converting organic waste into usable renewable energy. The efficiency of organic waste digestion, nonetheless, is limited due to inhibition and instability. Accordingly, biochar is an effective method for improving the efficiency of AD by adsorbing inhibitors, promoting biogas generation and methane concentration, maintaining process stability, colonizing microorganisms selectively, and mitigating the inhibition of volatile fatty acids and ammonia. This paper reviews the features of crop waste-derived biochar and its application in AD systems. Four critical roles of biochar in AD systems were identified: maintaining pH stability, promoting hydrolysis, enhancing the direct interspecies electron transfer pathway, and supporting microbial development. This work also highlights that the interaction between biochar dose, amount of organic component in the substrate, and inoculum-to-substrate ratio should be the focus of future research before deploying commercial applications.

Characterization and adsorption applications of composite biochars of clay minerals and biomass.

Composite mineral-biochars of a homogeneous biomass (cellulose) and heterogeneous biomass (oak leaves) were fabricated with either 5 wt% or 10 wt% minerals (montmorillonite (MMT), kaolinite, and sand) and then pyrolyzed at 600 °C for 60 min. Characterizations including proximate analysis, ultimate analysis, surface area and porosity, morphology, and surface chemistry confirmed that minerals were present on the surface of biochar, and MMT/kaolinite-biochar composites showed a strengthening in the chars' aromatic structures, as well as increases in oxygen-containing surface functional groups. Methylene blue adsorption isotherms indicated that the MMT/kaolinite-biochars had higher adsorption capacities than pure biomass or biomass-sand biochars (110 mgMB/gchar and 24 mgMB/gchar for MMT-cellulose char and cellulose char, respectively). A multilinear model relating adsorption capacity and adsorbent properties was developed to measure the relative contribution of biochar properties to adsorption behavior. The model indicates that pore volume and hydrogen bonding were the dominant properties in controlling the adsorption of methylene blue onto the biochars. Findings from this work indicate that composite biochars prepared from biomass and inexpensive clay minerals are a promising adsorbent for remediating organic contaminants from water.

Metal leaching from antimicrobial cloth face masks intended to slow the spread of COVID-19.

Global health organizations recommend the use of cloth face coverings to slow the spread of COVID-19. Seemingly overnight, companies whose primary business is in no way related to healthcare or personal protective equipment-from mattresses manufacturers to big box stores-transitioned into the "mask business." Many companies advertise antimicrobial masks containing silver, copper, or other antimicrobials. Often, the techniques used to load such antimicrobials onto mask fibers are undisclosed, and the potential for metal leaching from these masks is yet unknown. We exposed nine so-called "antimicrobial" face masks (and one 100% cotton control mask) to deionized water, laundry detergent, and artificial saliva to quantify the leachable silver and copper that may occur during mask washing and wearing. Leaching varied widely across manufacturer, metal, and leaching solution, but in some cases was as high as 100% of the metals contained in the as-received mask after 1 h of exposure.

Valorization of cherry pits: Great Lakes agro-industrial waste to mediate Great Lakes water quality.

To meet human food and fiber needs in an environmentally and economically sustainable way, we must improve the efficiency of waste, water, and nutrient use by converting vast quantities of agricultural and food waste to renewable bioproducts. This work converts waste cherry pits, an abundant food waste in the Great Lakes region, to biochars and activated biochars via slow pyrolysis. Biochars produced have surface areas between 206 and 274 m2/g and increased bioavailability of Fe, K, Mg, Mn, and P. The biochars can be implemented as soil amendments to reduce nutrient run-off and serve as a valuable carbon sink (biochars contain 74-79% carbon), potentially mitigating harmful algal blooms in the Great Lakes. CO2-activated biochars have surface areas of up to 629 m2/g and exhibit selective metal adsorption for the removal of metals from simulated contaminated drinking water, an environmental problem plaguing this region. Through sustainable waste-to-byproduct valorization we convert this waste food biomass into biochar for use as a soil amendment and into activated biochars to remove metals from drinking water, thus alleviating economic issues associated with cherry pit waste handling and reducing the environmental impact of the cherry processing industry.

The Relationship between US Adults' Misconceptions about COVID-19 Vaccines and Vaccination Preferences.

While mass vaccination has blunted the pandemic in the United States, pockets of vaccine hesitancy remain. Through a nationally representative survey of 1027 adult Americans conducted in February 2021, this study examined individual misconceptions about COVID-19 vaccine safety; the demographic factors associated with these misconceptions; and the relationship between misconceptions and willingness to vaccinate. Misconceptions about vaccine safety were widespread. A sizeable minority (40%) believed that vaccine side effects are commonly severe or somewhat severe; 85% significantly underestimated the size and scale of the clinical trials; and a sizeable share believed either that the vaccines contain live coronavirus (10%) or were unsure (38%), a proxy for fears that vaccination itself may cause infection. These misconceptions were particularly acute among Republicans, Blacks, individuals with lower levels of educational attainment, and unvaccinated individuals. Perceived side effect severity and underestimating the size of the clinical trials were both significantly associated with vaccine hesitancy.

Integrated thermochemical conversion process for valorizing mixed agricultural and dairy waste to nutrient-enriched biochars and biofuels.

Hydrothermal carbonization (HTC) and pyrolysis are two promising thermochemical conversion strategies to valorize agricultural wastes, yet neither process can be implemented alone to sustainably upgrade both wet and dry feedstocks. HTC is ideal for wet feedstocks, such as manure, but its solid hydrochars suffer from low surface area and stability. Pyrolysis is well suited to dry agricultural residues, but pyrolysis biochars have low nutrient contents and bio-oils are often highly oxygenated. We propose an integrated process that co-pyrolyzes a nutrient-rich cow manure hydrochar with raw agricultural residues, which effectively reduces the environmental impact of these wastes while producing value-added bioproducts. Biochars produced from the proposed process are more suitable for soil amendments due to their enhancement in bioavailable nutrients and surface area than the manure hydrochars and raw biomass. Co-pyrolysis of blends enriched with cow manure yield oils higher in alkanes and alkenes with fewer oxygenated compounds.

Heterogeneous biochars from agriculture residues and coal fly ash for the removal of heavy metals from coking wastewater.

While we have started down the path towards a global transition to a green economy, as with most things we began with the "low-hanging fruit," such that increasingly difficult material and chemical conversions remain. Coking is one such example; it is unlikely that steel production will transition away from using coking coal anytime in the near future, such that coking wastewater remains a global environmental challenge. However, we can develop greener methods and materials to treat such waste. The present work demonstrates how wheat straw, an abundant agricultural residue, can be co-pyrolyzed and co-activated with coal fly ash to produce a high surface area biochar. Coal fly ash has previously been shown to promote devolatilization and deoxygenation of pyrolyzed biofuels. This work shows how coal fly ash increases microporosity as well as aromaticity of the surface functional groups, while decreasing carbonyl but preserving or only slightly decreasing ketones and carboxylic acids. CO2-activation of 5 and 10 wt% fly ash with wheat straw blends yields heterogeneous biochars with adsorption capacities upwards of 170 mgmetal gchar -1, with 5 wt% blends showing higher capacity and adsorption uptake rates than the 0 or 10 wt% blends. The adsorption of the four heavy metals ions (Ni2+, Co2+, Zn2+, and Mn2+) was chemical in nature, with cobalt preferentially adsorbing to the char surface. The overall adsorption rate is limited by an initial rapid uptake to fill available surface adsorption sites.

Ligands and media impact interactions between engineered nanomaterials and clay minerals.

The exponential growth in technologies incorporating engineered nanomaterials (ENMs) requires plans to handle waste ENM disposal and accidental environmental release throughout the material life cycle. These scenarios motivate efforts to quantify and model ENM interactions with diverse background particles and solubilized chemical species in a variety of environmental systems. In this study, quantum dot (QD) nanoparticles and clay minerals were mixed in a range of water chemistries in order to develop simple assays to predict aggregation trends. CdSe QDs were used as a model ENM functionalized with either negatively charged or zwitterionic small molecule ligand coatings, while clays were chosen as an environmentally relevant sorbent given their potential as an economical water treatment technology and ubiquitous presence in nature. In our unbuffered experimental systems, clay type impacted pH, which resulted in a change in zwitterionic ligand speciation that favored aggregation with kaolinite more than with montmorillonite. With kaolinite, the zwitterionic ligand-coated QD exhibited greater than ten times the relative attachment efficiency for QD-clay heteroaggregation compared to the negatively charged ligand coated QD. Under some conditions, particle oxidative dissolution and dynamic sorption of ions and QDs to surfaces complicated the interpretation of the removal kinetics. This work demonstrates that QDs stabilized by small molecule ligands and electrostatic surface charges are highly sensitive to changes in water chemistry in complex media. Natural environments enable rapid dynamic physicochemical changes that will influence the fate and mobility of ENMs, as seen by the differential adsorption of water-soluble QDs to our clay media.

Demonstrating the suitability of canola residue biomass to biofuel conversion via pyrolysis through reaction kinetics, thermodynamics and evolved gas analyses.

The identification of biomasses for pyrolytic conversion to biofuels depends on many factors, including: moisture content, elemental and volatile matter composition, thermo-kinetic parameters, and evolved gases. The present work illustrates how canola residue may be a suitable biofuel feedstock for low-temperature (<450 °C) slow pyrolysis with energetically favorable conversions of up to 70 wt% of volatile matter. Beyond this point, thermo-kinetic parameters and activation energies, which increase from 154.3 to 400 kJ/mol from 65 to 80% conversion, suggest that the energy required to initiate conversion is thermodynamically unfavorable. This is likely due to its higher elemental carbon content than similar residues, leading to enhanced carbonization rather than devolatilization at higher temperatures. Evolved gas analysis supports limiting pyrolysis temperature; ethanol and methane conversions are maximized below 500 °C with ∼6% water content. Carbon dioxide is the dominant evolved gas beyond this temperature.

Vapor pressures and thermodynamics of oxygen-containing polycyclic aromatic hydrocarbons measured using Knudsen effusion.

Polycyclic aromatic hydrocarbons (PAHs) and their oxygenated derivatives (OPAHs) are ubiquitous environmental pollutants resulting from the incomplete combustion of coal and fossil fuels. Their vapor pressures are key thermodynamic data essential for modeling fate and transport within the environment. The present study involved nine PAHs containing oxygen heteroatoms, including aldehyde, carboxyl, and nitro groups, specifically 2-nitrofluorene, 9-fluorenecarboxylic acid, 2-fluorenecarboxaldehyde, 2-anthracenecarboxylic acid, 9-anthracenecarboxylic acid, 9-anthraldehyde, 1-nitropyrene, 1-pyrenecarboxaldehyde, and 1-bromo-2-naphthoic acid. The vapor pressures of these compounds, with molecular weights ranging from 194 to 251 g/mol, were measured using the isothermal Knudsen effusion technique in the temperature range of 329 to 421 K. The corresponding enthalpies of sublimation, calculated via the Clausius-Clapeyron equation, are compared to parent, nonoxygenated PAH compound data to determine the effect of the addition of these oxygen-containing heteroatoms. As expected, the addition of -CHO, -COOH, and -NO(2) groups onto these PAHs increases the enthalpy of sublimation and decreases the vapor pressure as compared to the parent PAH; the position of substitution also plays a significant role in determining the vapor pressure of these OPAHs.

Hydrothermal carbonization of Opuntia ficus-indica cladodes: Role of process parameters on hydrochar properties.

Opuntia ficus-indica cladodes are a potential source of solid biofuel from marginal, dry land. Experiments assessed the effects of temperature (180-250°C), reaction time (0.5-3h) and biomass to water ratio (B/W; 0.07-0.30) on chars produced via hydrothermal carbonization. Multivariate linear regression demonstrated that the three process parameters are critically important to hydrochar solid yield, while B/W drives energy yield. Heating value increased together with temperature and reaction time and was maximized at intermediate B/W (0.14-0.20). Microscopy shows evidence of secondary char formed at higher temperatures and B/W ratios. X-ray diffraction, thermogravimetric data, microscopy and inductively coupled plasma mass spectrometry suggest that calcium oxalate in the raw biomass remains in the hydrochar; at higher temperatures, the mineral decomposes into CO2 and may catalyze char/tar decomposition.

Improved prediction of higher heating value of biomass using an artificial neural network model based on proximate analysis.

As biomass becomes more integrated into our energy feedstocks, the ability to predict its combustion enthalpies from routine data such as carbon, ash, and moisture content enables rapid decisions about utilization. The present work constructs a novel artificial neural network model with a 3-3-1 tangent sigmoid architecture to predict biomasses' higher heating values from only their proximate analyses, requiring minimal specificity as compared to models based on elemental composition. The model presented has a considerably higher correlation coefficient (0.963) and lower root mean square (0.375), mean absolute (0.328), and mean bias errors (0.010) than other models presented in the literature which, at least when applied to the present data set, tend to under-predict the combustion enthalpy.