Review of per- and poly-fluoroalkyl treatment in combustion-based thermal waste systems in the United States.

Per- and poly-fluoroalkyl substances (PFAS) are a class of synthetic chemicals known for their widespread presence and environmental persistence. Carbon-fluorine (C-F) bonds are major components among PFAS and among the strongest organic bonds, thus destroying PFAS may present significant challenge. Thermal treatment such as incineration is an effective and approved method for destroying many halogenated organic chemicals. Here, we present the results of existing studies and testing at combustion-based thermal treatment facilities and summarize what is known regarding PFAS destruction and mineralization at such units. Available results suggest the temperature and residence times reached by some thermal treatment systems are generally favorable to the destruction of PFAS, but the possibility for PFAS or fluorinated organic byproducts to escape destruction and adequate mineralization and be released into the air cannot be ruled out. Few studies have been conducted at full-scale operating facilities, and none to date have attempted to characterize possible fluorinated organic products of incomplete combustion (PICs). Further, the ability of existing air pollution control (APC) systems, designed primarily for particulate and acid gas control, to reduce PFAS air emissions has not been determined. These data gaps remain primarily due to the previous lack of available methods to characterize PFAS destruction and PIC concentrations in facility air emissions. However, newly developed stack testing methods offer an improved understanding of the extent to which thermal waste treatment technologies successfully destroy and mineralize PFAS in these waste streams.

Per- and Polyfluoroalkyl Substances (PFAS) in Facemasks: Potential Source of Human Exposure to PFAS with Implications for Disposal to Landfills.

Facemasks are important tools for fighting against disease spread, including Covid-19 and its variants, and some may be treated with per- and polyfluoroalkyl substances (PFAS). Nine facemasks over a range of prices were analyzed for total fluorine and PFAS. The PFAS compositions of the masks were then used to estimate exposure and the mass of PFAS discharged to landfill leachate. Fluorine from PFAS accounted only for a small fraction of total fluorine. Homologous series of linear perfluoroalkyl carboxylates and the 6:2 fluorotelomer alcohol indicated a fluorotelomer origin. Inhalation was estimated to be the dominant exposure route (40%-50%), followed by incidental ingestion (15%-40%) and dermal (11%-20%). Exposure and risk estimates were higher for children than adults, and high physical activity substantially increased inhalation exposure. These preliminary findings indicate that wearing masks treated with high levels of PFAS for extended periods of time can be a notable source of exposure and have the potential to pose a health risk. Despite modeled annual disposal of ~29-91 billion masks, and an assuming 100% leaching of individual PFAS into landfill leachate, mask disposal would contribute only an additional 6% of annual PFAS mass loads and less than 11 kg of PFAS discharged to U.S. wastewater.

Assessing the Fate of Dissolved Organic Compounds in Landfill Leachate and Wastewater Treatment Systems.

Landfill leachate and municipal wastewater are major sources of chemical pollutants that contaminate our drinking water sources. Evaluating the dissolved organic chemical composition in wastewater treatment plants is therefore essential to understand how the discharge impacts the environment, wildlife, and human health. In this study, we utilized a nontargeted analysis method coupling liquid chromatography and tandem mass spectrometry (LC-MS/MS) to analyze chemical features at different points along two landfill leachate treatment plants (LLTPs) and two municipal wastewater treatment plants (WWTPs) in the Southeastern United States. Significant feature differences were observed for the WWTPs where activated sludge clarification was employed versus the LLTPs utilizing reverse osmosis. Specifically, even though both LLTPs had the largest number of features in their influent water, their effluent following reverse osmosis yielded a lower number of features than the WWTPs. Additionally, the clarification processes of each WWTP exhibited different efficiencies as chemical disinfection removed more features than UV disinfection. Feature identification was then made using the LC, MS, and MS/MS information. Analysis of the identified molecules showed that lipids were the most effectively removed from all plants, while alkaloid and organic nitrogen compounds were the most recalcitrant.

Evidence of thermophilic waste decomposition at a landfill exhibiting elevated temperature regions.

There have been several reports of landfills exhibiting temperatures as high as 80 to 100 °C. This observation has motivated researchers to understand the causes of the elevated temperatures and to develop predictive models of landfill temperature. The objective of this research was to characterize the methanogenic activity of microbial communities that were derived from landfill samples excavated from a section of a landfill exhibiting gas well temperatures above 55 °C. Specific objectives were to: (1) determine the upper temperature limit for methane production; (2) evaluate the kinetics of methane generation when landfill-derived microcosms are incubated above and below their excavation temperature and derive a temperature inhibition function; and (3) evaluate microbial community shifts in response to temperature perturbations. Landfill microcosms were derived from 57 excavated landfill samples and incubated within ±2.5 °C of their excavation temperature between 42.5 °C and 87.5 °C. Results showed an optimum temperature for methane generation of ~57 °C and a 95% reduction in methane yield at ~72 °C. When select cultures were perturbed between 5 °C below and 15 °C above their in-situ temperature, both the rate and maximum methane production decreased as incubation temperature increased. Microbial community characterization using 16S rRNA amplicon sequencing suggests that thermophilic methanogenic activity can be attributed to methanogens of the genus Methanothermobacter. This study demonstrated that from a microbiological standpoint, landfills may maintain active methanogenic processes while experiencing temperatures in the thermophilic regime (<72 °C).

Tropical peatland carbon storage linked to global latitudinal trends in peat recalcitrance.

Peatlands represent large terrestrial carbon banks. Given that most peat accumulates in boreal regions, where low temperatures and water saturation preserve organic matter, the existence of peat in (sub)tropical regions remains enigmatic. Here we examined peat and plant chemistry across a latitudinal transect from the Arctic to the tropics. Near-surface low-latitude peat has lower carbohydrate and greater aromatic content than near-surface high-latitude peat, creating a reduced oxidation state and resulting recalcitrance. This recalcitrance allows peat to persist in the (sub)tropics despite warm temperatures. Because we observed similar declines in carbohydrate content with depth in high-latitude peat, our data explain recent field-scale deep peat warming experiments in which catotelm (deeper) peat remained stable despite temperature increases up to 9 °C. We suggest that high-latitude deep peat reservoirs may be stabilized in the face of climate change by their ultimately lower carbohydrate and higher aromatic composition, similar to tropical peats.

Chemical composition and methane potential of commercial food wastes.

There is increasing interest in anaerobic digestion in the U.S. However, there is little information on the characterization of commercial food waste sources as well as the effect of waste particle size on methane yield. The objective of this research was to characterize four commercial food waste sources: (1) university dining hall waste, (2) waste resulting from prepared foods and leftover produce at a grocery store, (3) food waste from a hotel and convention center, and (4) food preparation waste from a restaurant. Each sample was tested in triplicate 8L batch anaerobic digesters after shredding and after shredding plus grinding. Average methane yields for the university dining, grocery store, hotel, and restaurant wastes were 363, 427, 492, and 403mL/dry g, respectively. Starch exhibited the most complete consumption and particle size did not significantly affect methane yields for any of the tested substrates. Lipids represented 59-70% of the methane potential of the fresh substrates.

Comparison of Field Measurements to Methane Emissions Models at a New Landfill.

Estimates of methane emissions from landfills rely primarily on models due to both technical and economic limitations. While models are easy to implement, there is uncertainty due to the use of parameters that are difficult to validate. The objective of this research was to compare modeled emissions using several greenhouse gas (GHG) emissions reporting protocols including: (1) Intergovernmental Panel on Climate Change (IPCC); (2) U.S. Environmental Protection Agency Greenhouse Gas Reporting Program (EPA GHGRP); (3) California Air Resources Board (CARB); and (4) Solid Waste Industry for Climate Solutions (SWICS), with measured emissions data collected over three calendar years from a young landfill with no gas collection system. By working with whole landfill measurements of fugitive methane emissions and methane oxidation, the collection efficiency could be set to zero, thus eliminating one source of parameter uncertainty. The models consistently overestimated annual methane emissions by a factor ranging from 4-31. Varying input parameters over reasonable ranges reduced this range to 1.3-8. Waste age at the studied landfill was less than four years and the results suggest the need for measurements at additional landfills to evaluate the accuracy of the tested models to young landfills.

Decomposition and carbon storage of selected paper products in laboratory-scale landfills.

The objective of this study was to measure the anaerobic biodegradation of different types of paper products in laboratory-scale landfill reactors. The study included (a) measurement of the loss of cellulose, hemicellulose, organic carbon, and (b) measurement of the methane yields for each paper product. The test materials included two samples each of newsprint (NP), copy paper (CP), and magazine paper (MG), and one sample of diaper (DP). The methane yields, carbon storage factors and the extent of cellulose and hemicellulose decomposition all consistently show that papers made from mechanical pulps (e.g., NPs) are less degradable than those made from chemical pulps where essentially all lignin was chemically removed (e.g., CPs). The diaper, which is not only made from chemical pulp but also contains some gel and plastic, exhibited limited biodegradability. The extent of biogenic carbon conversion varied from 21 to 96% among papers, which contrasts with the uniform assumption of 50% by the Intergovernmental Panel on Climate Change (IPCC) for all degradable materials discarded in landfills. Biochemical methane potential tests also showed that the solids to liquid ratio used in the test can influence the results.

Chemical changes during anaerobic decomposition of hardwood, softwood, and old newsprint under mesophilic and thermophilic conditions.

The anaerobic decomposition of plant biomass is an important aspect of global organic carbon cycling. While the anaerobic metabolism of cellulose and hemicelluloses to methane and carbon dioxide are well-understood, evidence for the initial stages of lignin decomposition is fragmentary. The objective of this study was to look for evidence of chemical transformations of lignin in woody tissues [hardwood (HW), softwood (SW), and old newsprint (ONP)] after anaerobic decomposition using Klason and acid-soluble lignin, CuO oxidation, and 2D NMR. Tests were conducted under mesophilic and thermophilic conditions, and lignin associations with structural carbohydrates are retained. For HW and ONP, the carbon losses could be attributed to cellulose and hemicelluloses, while carbon loss in SW was attributable to an uncharacterized fraction (e.g., extractives etc.). The 2D NMR and chemical degradation methods revealed slight reductions in ß-O-4 linkages for HW and ONP, with no depolymerization of lignin in any substrate.

Measurement of carbon storage in landfills from the biogenic carbon content of excavated waste samples.

Landfills are an anaerobic ecosystem and represent the major disposal alternative for municipal solid waste (MSW) in the U.S. While some fraction of the biogenic carbon, primarily cellulose (Cel) and hemicellulose (H), is converted to carbon dioxide and methane, lignin (L) is essentially recalcitrant. The biogenic carbon that is not mineralized is stored within the landfill. This carbon storage represents a significant component of a landfill carbon balance. The fraction of biogenic carbon that is not reactive in the landfill environment and therefore stored was derived for samples of excavated waste by measurement of the total organic carbon, its biogenic fraction, and the remaining methane potential. The average biogenic carbon content of the excavated samples was 64.6±18.0% (average±standard deviation), while the average carbon storage factor was 0.09±0.06g biogenic-C stored per g dry sample or 0.66±0.16g biogenic-C stored per g biogenic C.

Wood biodegradation in laboratory-scale landfills.

The objective of this research was to characterize the anaerobic biodegradability of major wood products in municipal waste by measuring methane yields, decay rates, the extent of carbohydrate decomposition, carbon storage, and leachate toxicity. Tests were conducted in triplicate 8 L reactors operated to obtain maximum yields. Measured methane yields for red oak, eucalyptus, spruce, radiata pine, plywood (PW), oriented strand board (OSB) from hardwood (HW) and softwood (SW), particleboard (PB) and medium-density fiberboard (MDF) were 32.5, 0, 7.5, 0.5, 6.3, 84.5, 0, 5.6, and 4.6 mL CH(4) dry g(-1), respectively. The red oak, a HW, exhibited greater decomposition than either SW (spruce and radiata), a trend that was also measured for the OSB-HW relative to OSB-SW. However, the eucalyptus (HW) exhibited toxicity. Thus, wood species have unique methane yields that should be considered in the development of national inventories of methane production and carbon storage. The current assumption of uniform biodegradability is not appropriate. The ammonia release from urea formaldehyde as present in PB and MDF could contribute to ammonia in landfill leachate. Using the extent of carbon conversion measured in this research, 0-19.9%, predicted methane production from a wood mixture using the Intergovernmental Panel for Climate Change waste model is only 7.9% of that predicted using the 50% carbon conversion default.

Estimation of waste component-specific landfill decay rates using laboratory-scale decomposition data.

The current methane generation model used by the U.S. EPA (Landfill Gas Emissions Model) treats municipal solid waste (MSW) as a homogeneous waste with one decay rate. However, component-specific decay rates are required to evaluate the effects of changes in waste composition on methane generation. Laboratory-scale rate constants, k(lab), for the major biodegradable MSW components were used to derive field-scale decay rates (k(field)) for each waste component using the assumption that the average of the field-scale decay rates for each waste component, weighted by its composition, is equal to the bulk MSW decay rate. For an assumed bulk MSW decay rate of 0.04 yr(-1), k(field) was estimated to be 0.298, 0.171, 0.015, 0.144, 0.033, 0.02, 0.122, and 0.029 yr(-1), for grass, leaves, branches, food waste, newsprint, corrugated containers, coated paper, and office paper, respectively. The effect of landfill waste diversion programs on methane production was explored to illustrate the use of component-specific decay rates. One hundred percent diversion of yard waste and food waste reduced the year 20 methane production rate by 45%. When a landfill gas collection schedule was introduced, collectable methane was most influenced by food waste diversion at years 10 and 20 and paper diversion at year 40.