Single-walled carbon nanotube transport in representative municipal solid waste landfill conditions.

Single-walled carbon nanotubes (SWNTs) are being used in many consumer products and devices. It is likely that as some of these products reach the end of their useful life, they will be discarded in municipal solid waste landfills. However, there has been little work evaluating the fate of nanomaterials in solid waste environments. The purpose of this study is to systematically evaluate the influence of organic matter type and concentration in landfill-relevant conditions on SWNT transport through a packed-bed of mixed municipal solid waste collectors. The influence of individual waste materials on SWNT deposition is also evaluated. Transport experiments were conducted through saturated waste-containing columns over a range of simulated leachate conditions representing both mature and young leachates. Results indicate that SWNT transport may be significant in mature waste environments, with mobility decreasing with decreasing humic acid concentration. SWNT mobility in the presence of acetic acid was inhibited, suggesting their mobility in young waste environments may be small. SWNTs also exhibited collector media-dependent transport, with greatest transport in glass and least in paper. These results represent the first study evaluating how leachate age and changes in waste composition influence potential SWNT mobility in landfills.

Hydrothermal carbonization of municipal waste streams.

Hydrothermal carbonization (HTC) is a novel thermal conversion process that can be used to convert municipal waste streams into sterilized, value-added hydrochar. HTC has been mostly applied and studied on a limited number of feedstocks, ranging from pure substances to slightly more complex biomass such as wood, with an emphasis on nanostructure generation. There has been little work exploring the carbonization of complex waste streams or of utilizing HTC as a sustainable waste management technique. The objectives of this study were to evaluate the environmental implications associated with the carbonization of representative municipal waste streams (including gas and liquid products), to evaluate the physical, chemical, and thermal properties of the produced hydrochar, and to determine carbonization energetics associated with each waste stream. Results from batch carbonization experiments indicate 49-75% of the initially present carbon is retained within the char, while 20-37% and 2-11% of the carbon is transferred to the liquid- and gas-phases, respectively. The composition of the produced hydrochar suggests both dehydration and decarboxylation occur during carbonization, resulting in structures with high aromaticities. Process energetics suggest feedstock carbonization is exothermic.

An assessment of bioreactor landfill costs and benefits.

Because effective operation of bioreactor landfills involves careful operation and construction of infrastructure beyond that necessary in traditional landfills, upfront capital and operating costs are greater than those associated with traditional landfills. Prior to investing in bioreactor landfills, landfill owners must be convinced that larger short-term expenses (e.g., liquid and/or air injection infrastructure) will be balanced by future economic benefits (e.g., extension of landfill life, reduced leachate treatment costs, etc.). The purpose of this paper is to describe an economic model developed to evaluate the impact of various operational (anaerobic, aerobic, or hybrid) and construction (retrofit and as-built) bioreactor landfill strategies on project economics. Model results indicate retrofit bioreactor landfills are more expensive than traditional landfills, while both the as-built and aerobic bioreactor landfills are less costly. Simulation results indicate the parameters that influence bioreactor economics most significantly are airspace recovery, gas recovery and subsequent use to generate electricity, and savings resulting from reduced leachate treatment costs.

Quantifying the sensitivity of feedstock properties and process conditions on hydrochar yield, carbon content, and energy content.

Hydrothermal carbonization (HTC) is a wet, low temperature thermal conversion process that continues to gain attention for the generation of hydrochar. The importance of specific process conditions and feedstock properties on hydrochar characteristics is not well understood. To evaluate this, linear and non-linear models were developed to describe hydrochar characteristics based on data collected from HTC-related literature. A Sobol analysis was subsequently conducted to identify parameters that most influence hydrochar characteristics. Results from this analysis indicate that for each investigated hydrochar property, the model fit and predictive capability associated with the random forest models is superior to both the linear and regression tree models. Based on results from the Sobol analysis, the feedstock properties and process conditions most influential on hydrochar yield, carbon content, and energy content were identified. In addition, a variational process parameter sensitivity analysis was conducted to determine how feedstock property importance changes with process conditions.

The impact of temperature and gas-phase oxygen on kinetics of in situ ammonia removal in bioreactor landfill leachate.

Microcosm experiments aimed at defining a rate equation that describes how different environmental conditions (i.e., gas-phase oxygen concentrations, temperature and ammonia concentration) may impact in situ ammonia removal were conducted. Results indicate that ammonia removal can readily occur at various gas-phase oxygen levels (between 0.7% and 100%) and over a range of temperatures (22, 35 and 45 degrees C). Slowest rates occurred with lower gas-phase oxygen concentrations. All rate data, except at 45 degrees C and 5% oxygen, fit well (r2=0.75) to a multiplicative Monod equation with terms describing the impact of oxygen, pH, temperature and ammonia concentration. All ammonia half-saturation values are relatively high when compared to those generally found in wastewater treatment, suggesting that the rate may be affected by the mass transfer of oxygen and/or ammonia. Additionally, as the temperature increases, the ammonia half-saturation value also increases. The multiplicative Monod model developed can be used to aid in designing and operating field-scale studies.

Hydrothermal carbonization of food waste for nutrient recovery and reuse.

Food waste represents a rather large and currently underutilized source of potentially available and reusable nutrients. Laboratory-scale experiments evaluating the hydrothermal carbonization of food wastes collected from restaurants were conducted to understand how changes in feedstock composition and carbonization process conditions influence primary and secondary nutrient fate. Results from this work indicate that at all evaluated reaction times and temperatures, the majority of nitrogen, calcium, and magnesium remain integrated within the solid-phase, while the majority of potassium and sodium reside in the liquid-phase. The fate of phosphorus is dependent on reaction times and temperatures, with solid-phase integration increasing with higher reaction temperature and longer time. A series of leaching experiments to determine potential solid-phase nutrient availability were also conducted and indicate that, at least in the short term, nitrogen release from the solids is small, while almost all of the phosphorus present in the solids produced from carbonizing at 225 and 250°C is released. At a reaction temperature of 275°C, smaller fractions of the solid-phase total phosphorus are released as reaction times increase, likely due to increased solids incorporation. Using these data, it is estimated that up to 0.96% and 2.30% of nitrogen and phosphorus-based fertilizers, respectively, in the US can be replaced by the nutrients integrated within hydrochar and liquid-phases generated from the carbonization of currently landfilled food wastes.

In situ ammonia removal in bioreactor landfill leachate.

Although bioreactor landfills have many advantages associated with them, challenges remain, including the persistence of NH(3)-N in the leachate. Because NH(3)-N is both persistent and toxic, it will likely influence when the landfill is biologically stable and when post-closure monitoring may end. An in situ nitrogen removal technique would be advantageous. Recent studies have shown the efficacy of such processes; however, they are lacking the data required to enable adequate implementation at field-scale bioreactor landfills. Research was conducted to evaluate the kinetics of in situ ammonia removal in both acclimated and unacclimated wastes to aid in developing guidance for field-scale implementation. Results demonstrate that in situ nitrification is feasible in an aerated solid waste environment and that the potential for simultaneous nitrification and denitrification (even under low biodegradable C:N conditions) in field-scale bioreactor landfills is significant due to the presence of both aerobic and anoxic areas. All rate data fit well to Monod kinetics, with specific rates of removal of 0.196 and 0.117 mgN/day-g dry waste and half-saturation constants of 59.6 and 147 mgN/L for acclimated and unacclimated wastes, respectively. Although specific rates of ammonia removal in the unacclimated waste are lower than in the acclimated waste, a relatively quick start-up of ammonia removal was observed in the unacclimated waste. Using the removal rate expressions developed will allow for estimation of the treatment times and volumes necessary to remove NH(3)-N from recirculated landfill leachate.

Investigating the role of feedstock properties and process conditions on products formed during the hydrothermal carbonization of organics using regression techniques.

The purpose of this study is to develop regression models that describe the role of process conditions and feedstock chemical properties on carbonization product characteristics. Experimental data were collected and compiled from literature-reported carbonization studies and subsequently analyzed using two statistical approaches: multiple linear regression and regression trees. Results from these analyses indicate that both the multiple linear regression and regression tree models fit the product characteristics data well. The regression tree models provide valuable insight into parameter relationships. Relative weight analyses indicate that process conditions are more influential to the solid yields and liquid and gas-phase carbon contents, while feedstock properties are more influential on the hydrochar carbon content, energy content, and the normalized carbon content of the solid.

Assessing the environmental impact of energy production from hydrochar generated via hydrothermal carbonization of food wastes.

Although there are numerous studies suggesting hydrothermal carbonization is an environmentally advantageous process for transformation of wastes to value-added products, a systems level evaluation of the environmental impacts associated with hydrothermal carbonization and subsequent hydrochar combustion has not been conducted. The specific objectives of this work are to use a life cycle assessment approach to evaluate the environmental impacts associated with the HTC of food wastes and the subsequent combustion of the generated solid product (hydrochar) for energy production, and to understand how parameters and/or components associated with food waste carbonization and subsequent hydrochar combustion influence system environmental impact. Results from this analysis indicate that HTC process water emissions and hydrochar combustion most significantly influence system environmental impact, with a net negative GWP impact resulting for all evaluated substituted energy-sources except biomass. These results illustrate the importance of electricity production from hydrochar particularly when it is used to offset coal-based energy sources. HTC process water emissions result in a net impact to the environment, indicating a need for developing appropriate management strategies. Results from this analysis also highlight a need for additional exploration of liquid and gas-phase composition, a better understanding of how changes in carbonization conditions (e.g., reaction time and temperature) influence metal and nutrient fate, and the exploration of liquid-phase treatment.

Influence of feedstock chemical composition on product formation and characteristics derived from the hydrothermal carbonization of mixed feedstocks.

As the exploration of the carbonization of mixed feedstocks continues, there is a distinct need to understand how feedstock chemical composition and structural complexity influence the composition of generated products. Laboratory experiments were conducted to evaluate the carbonization of pure compounds, mixtures of the pure compounds, and complex feedstocks comprised of the pure compounds (e.g., paper, wood). Results indicate that feedstock properties do influence carbonization product properties. Carbonization product characteristics were predicted using results from the carbonization of the pure compounds and indicate that recovered solids energy contents are more accurately predicted than solid yields and the carbon mass in each phase, while predictions associated with solids surface functional groups are more difficult to predict using this linear approach. To more accurately predict carbonization products, it may be necessary to account for feedstock structure and/or additional feedstock properties.

Using liquid waste streams as the moisture source during the hydrothermal carbonization of municipal solid wastes.

Hydrothermal carbonization (HTC) is a thermal conversion process that can be an environmentally beneficial approach for the conversion of municipal solid wastes to value-added products. The influence of using activated sludge and landfill leachate as initial moisture sources during the carbonization of paper, food waste and yard waste over time at 250°C was evaluated. Results from batch experiments indicate that the use of activated sludge and landfill leachate are acceptable alternative supplemental liquid sources, ultimately imparting minimal impact on carbonization product characteristics and yields. Regression results indicate that the initial carbon content of the feedstock is more influential than any of the characteristics of the initial liquid source and is statistically significant when describing the relationship associated with all evaluated carbonization products. Initial liquid-phase characteristics are only statistically significant when describing the solids energy content and the mass of carbon in the gas-phase. The use of these alternative liquid sources has the potential to greatly increase the sustainability of the carbonization process. A life cycle assessment is required to quantify the benefits associated with using these alternative liquid sources.

Influence of process water quality on hydrothermal carbonization of cellulose.

Hydrothermal carbonization (HTC) is a thermal conversion process that has been shown to be environmentally and energetically advantageous for the conversion of wet feedstocks. Supplemental moisture, usually in the form of pure water, is added during carbonization to achieve feedstock submersion. To improve process sustainability, it is important to consider alternative supplemental moisture sources. Liquid waste streams may be ideal alternative liquid source candidates. Experiments were conducted to systematically evaluate how changes in pH, ionic strength, and organic carbon content of the initial process water influences cellulose carbonization. Results from the experiments conducted evaluating the influence of process water quality on carbonization indicate that changes in initial water quality do influence time-dependent carbonization product composition and yields. These results also suggest that using municipal and industrial wastewaters, with the exception of streams with high CaCl2 concentrations, may impart little influence on final carbonization products/yields.

Influence of reaction time and temperature on product formation and characteristics associated with the hydrothermal carbonization of cellulose.

Studies have demonstrated that hydrothermal carbonization of biomass and waste streams results in the formation of beneficial materials/resources with minimal greenhouse gas production. Data necessary to understand how critical process conditions influence carbonization mechanisms, product formation, and associated environmental implications are currently lacking. The purpose of this work is to hydrothermally carbonize cellulose at different temperatures and to systematically sample over a 96-h period to determine how changes in reaction temperature influence product evolution. Understanding cellulose carbonization will provide insight to carbonization of cellulosic biomass and waste materials. Results from batch experiments indicate that the majority of cellulose conversion occurs between the first 0.5-4h, and faster conversion occurs at higher temperatures. Data collected over time suggest cellulose solubilization occurs prior to conversion. The composition of solids recovered after 96h is similar at all temperatures, consisting primarily of sp(2) carbons (furanic and aromatic groups) and alkyl groups.

Hydrothermal carbonization of food waste and associated packaging materials for energy source generation.

Hydrothermal carbonization (HTC) is a thermal conversion technique that converts food wastes and associated packaging materials to a valuable, energy-rich resource. Food waste collected from local restaurants was carbonized over time at different temperatures (225, 250 and 275°C) and solids concentrations to determine how process conditions influence carbonization product properties and composition. Experiments were also conducted to determine the influence of packaging material on food waste carbonization. Results indicate the majority of initial carbon remains integrated within the solid-phase at the solids concentrations and reaction temperatures evaluated. Initial solids concentration influences carbon distribution because of increased compound solubilization, while changes in reaction temperature imparted little change on carbon distribution. The presence of packaging materials significantly influences the energy content of the recovered solids. As the proportion of packaging materials increase, the energy content of recovered solids decreases because of the low energetic retention associated with the packaging materials. HTC results in net positive energy balances at all conditions, except at a 5% (dry wt.) solids concentration. Carbonization of food waste and associated packaging materials also results in net positive balances, but energy needs for solids post-processing are significant. Advantages associated with carbonization are not fully realized when only evaluating process energetics. A more detailed life cycle assessment is needed for a more complete comparison of processes.

The effects of alkalinity and acidity of process water and hydrochar washing on the adsorption of atrazine on hydrothermally produced hydrochar.

Hydrothermal carbonization of simulated food waste was performed at 250 °C for 20 h using deionized water (DI) and 0.01 N solutions of HCl, NaCl, and NaOH. The hydrochars produced were washed with acetone and the adsorptive capacity of the washed and unwashed hydrochars for atrazine were characterized. Using a generalized linear model, it was shown that the adsorptive capacity of the washed hydrochar was significantly higher than that of the unwashed hydrochars. The HCl processed unwashed hydrochar has a slightly higher adsorptive capacity compared to the DI processed hydrochar while both the NaOH processed washed and unwashed hydrochars were slightly lower than the corresponding DI processed hydrochars. (13)C solid-state NMR results showed no discernible differences in surface functional groups among the washed hydrochars and among the unwashed hydrochars. A clear decrease in alkyl groups and an increase in aromatic/olefinic-C groups were observed after acetone washing. (1)H liquid-phase NMR showed carbon alkyl chains were present in the acetone wash. Interaction energies calculated using dispersion corrected density functional theory show that atrazine is more strongly adsorbed to surfaces without weakly associated alkyl groups.

Single-walled carbon nanotube behavior in representative mature leachate.

Escalating production and subsequent incorporation of engineered nanomaterials in consumer products increases the likelihood of nanomaterials being discarded in landfills. Although direct measurement of particle disposal has not yet occurred, life cycle assessments suggest that over 50% of nanomaterials produced will eventually reside in landfills. Laboratory-scale experiments were conducted to evaluate how organics (humic acid: 20-800 mg/L), ionic strength (100-400 mM NaCl), and pH (6-8) typical of mature leachates influence carbon nanotube surface charge, relative stability, and mobility through representative solid waste environments. Results from the batch experiments suggest that the presence of high molecular weight organics, such as humic acid, acts to stabilize carbon nanotubes present in leachate, even at high ionic strengths (>100 mM NaCl). These results also suggest that in mature landfill leachate, as long as humic acid is present, ionic strength (when represented as NaCl) will be a dominant factor influencing nanomaterial stability. Column experiment results indicate the carbon nanotubes may be mobile through solid waste, suggesting particle placement within landfills needs to be examined more closely.

Thermal conversion of municipal solid waste via hydrothermal carbonization: comparison of carbonization products to products from current waste management techniques.

Hydrothermal carbonization (HTC) is a novel thermal conversion process that may be a viable means for managing solid waste streams while minimizing greenhouse gas production and producing residual material with intrinsic value. HTC is a wet, relatively low temperature (180-350 °C) thermal conversion process that has been shown to convert biomass to a carbonaceous residue referred to as hydrochar. Results from batch experiments indicate HTC of representative waste materials is feasible, and results in the majority of carbon (45-75% of the initially present carbon) remaining within the hydrochar. Gas production during the batch experiments suggests that longer reaction periods may be desirable to maximize the production of energy-favorable products. If using the hydrochar for applications in which the carbon will remain stored, results suggest that the gaseous products from HTC result in fewer g CO(2)-equivalent emissions than the gases associated with landfilling, composting, and incineration. When considering the use of hydrochar as a solid fuel, more energy can be derived from the hydrochar than from the gases resulting from waste degradation during landfilling and anaerobic digestion, and from incineration of food waste. Carbon emissions resulting from the use of the hydrochar as a fuel source are smaller than those associated with incineration, suggesting HTC may serve as an environmentally beneficial alternative to incineration. The type and extent of environmental benefits derived from HTC will be dependent on hydrochar use/the purpose for HTC (e.g., energy generation or carbon storage).

Removal of bisphenol A and 17α-ethinyl estradiol from landfill leachate using single-walled carbon nanotubes.

In this study, the adsorption of bisphenol A (BPA) and 17α-ethinyl estradiol (EE2) from landfill leachate onto single-walled carbon nanotubes (SWCNTs) was investigated. Different leachate solutions were prepared by altering the pH, ionic strength, and dissolved organic carbon (DOC) in the solutions to mimic the varying water conditions that occur in leachate during the various stages of waste decomposition. The youngest and oldest leachate solutions contained varying DOC and background chemistry and were represented by leachate Type A (pH = 5.0; DOC = 2500 mg/L; conductivity = 12,500 µS/cm; [Ca(2+)] = 1200 mg/L; [Mg(2+)] = 470 mg/L) and Type E (pH = 7.5; DOC = 250 mg/L; conductivity = 3250 µS/cm; [Ca(2+)] = 60 mg/L; [Mg(2+)] = 180 mg/L). These solutions were subsequently combined in different ratios to produce intermediate solutions, labeled B-D, to replicate time-dependent changes in leachate composition. Overall, a larger fraction of EE2 was removed as compared to BPA, consistent with its higher log K(OW) value. The total removal of BPA and EE2 decreased in older leachate solutions, with the adsorptive capacity of SWCNTs decreasing in the order of leachate Type A > Type B > Type C > Type D > Type E. An increase in the pH from 3.5 to 11 decreased the adsorption of BPA by 22% in young leachate and by 10% in old leachate. The changes in pH did not affect the adsorption of EE2 in the young leachate, but did reduce adsorption by 32% in the old leachate. Adjusting the ionic strength using Na(+) did not significantly impact adsorption, while increasing the concentration of Ca(2+) resulted in a 12% increase in the adsorption of BPA and a 19% increase in the adsorption of EE2. DOC was revealed to be the most influential parameter in this study. In the presence of hydrophilic DOC, represented by glucose in this study, adsorption of the endocrine disrupting compounds (EDCs) onto the SWCNTs was not affected. In the absence of SWCNTs, hydrophobic DOC (i.e., humic acid) adsorbed 15-20% of BPA and EE2. However, when the humic acid and SWCNTs were both present, the overall adsorptive capacity of the SWCNTs was reduced. Hydrophobic (π-π electron donor-acceptor) interactions between the EDCs and the constituents in the leachate, as well as interactions between the SWCNTs and the EDCs, are proposed as potential adsorption mechanisms for BPA and EE2 onto SWCNTs.

Iron-mediated trichloroethene reduction within nonaqueous phase liquid.

Aqueous slurries or suspensions containing reactive iron nanoparticles are increasingly suggested as a potential means for remediating chlorinated solvent nonaqueous phase liquid (NAPL) source zones. Aqueous-based treatment approaches, however, may be limited by contaminant dissolution from the NAPL and the subsequent contaminant transport to the reactive nanoparticles. Reactions occurring within (or at the interface) of the NAPL may alleviate these potential limitations, but this approach has received scant attention due to concerns associated with the reactivity of iron within nonaqueous phases. Results presented herein suggest that iron nanoparticles are reactive with TCE-NAPL and exhibit dechlorination rates proportional to the concentration of (soluble) water present within the NAPL. Reactivity was assessed over a 12-day period for five water contents ranging from 0.31 M to 4.3M, with n-butanol used to enhance water solubility in the NAPL. Rates of dechlorination were generally slower than those reported for aqueous-phase dechlorination, but were not observed to slow over the course of the 12-day period. The lack of observed deactivation may indicate the potential that highly efficient (with respect to utilization of available electrons) dechlorination reactions can be engineered to occur within nonaqueous liquids. These results suggest a need for subsequent investigations which focus on understanding the mechanisms of the reactions occurring within NAPL, as well as those assessing the utility of controlling both the iron and water content within a NAPL source zone.

Sustainable disposal of municipal solid waste: post bioreactor landfill polishing.

Sustainable disposal of municipal solid waste (MSW) requires assurance that contaminant release will be minimized or prevented within a reasonable time frame before the landfill is abandoned so that the risk of contamination release is not passed to future generations. This could be accomplished through waste acceptance criteria such as those established by the European Union (EU) that prohibit land disposal of untreated organic matter. In the EU, mechanical, biological and/or thermal pretreatment of MSW is therefore necessary prior to landfilling which is complicated and costly. In other parts of the world, treatment within highly engineered landfills is under development, known as bioreactor landfills. However, the completed bioreactor landfill still contains material, largely nonbiodegradable carbon and ammonia that may be released to the environment over the long-term. This paper provides a conceptual analysis of an approach to ensure landfill sustainability by the rapid removal of these remaining materials, leachate treatment and recirculation combined with aeration. The analysis in this paper includes a preliminary experimental evaluation using real mature leachate and waste samples, a modeling effort using a simplified mass balance approach and input parameters from real typical bioreactor cases, and a cost estimate for the suggested treatment method.