Distribution of Per- and Polyfluoroalkyl Substances (PFASs) in a Waste-to-Energy Plant─Tracking PFASs in Internal Residual Streams.

Per- and polyfluoroalkyl substances (PFASs) constitute a diverse group of man-made chemicals characterized by their water- and oil-repellent properties and persistency. Given their widespread use in consumer products, PFASs will inevitably be present in waste streams sent to Waste-to-Energy (WtE) plants. We have previously observed a subset of PFASs in residual streams (ashes, treated process water, and flue gas) from a WtE plant. However, the transport and distribution of PFASs inside the WtE plant have remained unaddressed. This study is part of a comprehensive investigation to create a synoptic overview of the distribution of PFASs in WtE residues. PFASs were found in all sample types except for boiler ash. The total levels of 18 individual PFASs (Σ18PFASs) in untreated flue gas ranged from 5.2 to 9.5 ng m-3, decreasing with 35% ± 10% after wet flue gas treatment. Σ18PFASs in the condensate ranged from 46 to 50 ng L-1, of which perfluorohexanoic acid (PFHxA) made up 90% on a ng L-1 basis. PFHxA was also dominant in filter ash, where Σ18PFASs ranged from 0.28 to 0.79 ng g-1. This study shows that flue gas treatment can capture some PFASs and transfer them into WtE residues.

Emission of Per- and Polyfluoroalkyl Substances from a Waste-to-Energy Plant─Occurrence in Ashes, Treated Process Water, and First Observation in Flue Gas.

Per- and polyfluoroalkyl substances (PFASs) are a large group of compounds commonly used as industrial chemicals and constituents of consumer products, e.g., as surfactants and surface protectors. When products containing PFASs reach their end of life, some end up in waste streams sent to waste-to-energy (WtE) plants. However, the fate of PFASs in WtE processes is largely unknown, as is their potential to enter the environment via ash, gypsum, treated process water, and flue gas. This study forms part of a comprehensive investigation of the occurrence and distribution of PFASs in WtE residues. Sampling was performed during incineration of two different waste mixes: normal municipal solid waste incineration (MSWI) and incineration of a waste mix with 5-8 wt % sewage sludge added to the MSWI (referred to as Sludge:MSWI). PFASs were identified in all examined residues, with short-chain (C4-C7) perfluorocarboxylic acids being the most abundant. Total levels of extractable PFASs were higher during Sludge:MSWI than during MSWI, with the total annual release estimated to be 47 and 13 g, respectively. Furthermore, PFASs were detected in flue gas for the first time (4.0-5.6 ng m-3). Our results demonstrate that some PFASs are not fully degraded by the high temperatures during WtE conversion and can be emitted from the plant via ash, gypsum, treated process water, and flue gas.

Influence of hydrothermal carbonization conditions on the porosity, functionality, and sorption properties of microalgae hydrochars.

Green microalgae is a possible feedstock for the production of biofuels, chemicals, food/feed, and medical products. Large-scale microalgae production requires large quantities of water and nutrients, directing the attention to wastewater as a cultivation medium. Wastewater-cultivated microalgae could via wet thermochemical conversion be valorised into products for e.g., water treatment. In this study, hydrothermal carbonization was used to process microalgae polycultures grown in municipal wastewater. The objective was to perform a systematic examination of how carbonization temperature, residence time, and initial pH affected solid yield, composition, and properties. Carbonization temperature, time and initial pH all had statistically significant effects on hydrochar properties, with temperature having the most pronounced effect; the surface area increased from 8.5 to 43.6 m2 g-1 as temperature was increased from 180 to 260 °C. However, hydrochars produced at low temperature and initially neutral pH generally had the highest capacity for methylene blue adsorption. DRIFTS analysis of the hydrochar revealed that the pH conditions changed the functional group composition, implying that adsorption was electrostatic interactions driven. This study concludes that un-activated hydrochars from wastewater grown microalgae produced at relatively low hydrothermal carbonization temperatures adsorb methylene blue, despite having low surface area.

Evaluation of the Transformation and Leaching Behavior of Two Polyfluoroalkyl Phosphate Diesters in a Field Lysimeter Study.

In this study, 6:2 and 8:2 polyfluoroalkyl phosphate diester (diPAP) were individually investigated in lysimeters under near-natural conditions. Leachate was sampled for 2 years, as was the soil after the experiment. In the leachate of the diPAP-spiked soils, perfluorocarboxylic acids (PFCAs) of different chain lengths were detected [23.2% (6:2 diPAP variant) and 20.8% (8:2 diPAP variant) of the initially applied molar amount]. After 2 years, the soils still contained 36-37% 6:2 diPAP and 41-45% 8:2 diPAP, respectively, in addition to smaller amounts of PFCAs (1.5 and 10.6%, respectively). Amounts of PFCAs found in the grass were low (<0.1% in both variants). The recovery rate of both 6:2 diPAP and 8:2 diPAP did not reach 100% (63.9 and 83.2%, respectively). The transformation of immobile diPAPs into persistent mobile PFCAs and their transport into the groundwater shows a pathway for human exposure to hazardous PFCAs through drinking water and irrigation of crops.

Degradation and Plant Transfer Rates of Seven Fluorotelomer Precursors to Perfluoroalkyl Acids and F-53B in a Soil-Plant System with Maize (Zea mays L.).

Fluorotelomer precursors in soil constitute a reservoir for perfluoroalkyl acids (PFAAs) in the environment. In the present study, precursor degradation and transfer rates of seven fluorotelomer precursors and F-53B (chlorinated polyfluoroalkyl ether sulfonates) were investigated in pot experiments with maize plants (Zea mays L.). The degradation of fluorotelomer precursors to perfluoroalkyl carboxylic acids (PFCAs) and their uptake spectra corresponded to those of fluorotelomer alcohol (FTOH) in terms of the number of perfluorinated carbon atoms. Short-chain PFCAs were translocated into the shoots (in descending order perfluoropentanoic, perfluorobutanoic, and perfluorohexanoic acid), whereas long-chain PFCAs mainly remained in the soil. In particular, fluorotelomer phosphate diesters (diPAPs) were retained in the soil and showed the highest degradation potential including evidence of α-oxidative processes. F-53B did not degrade to PFAAs and its constituents were mainly detected in the roots with minor uptake into the shoots. The results demonstrate the important role of precursors as an entry pathway for PFCAs into the food chain.

Leaching and Transformation of Perfluoroalkyl Acids and Polyfluoroalkyl Phosphate Diesters in Unsaturated Soil Column Studies.

Per- and polyfluoroalkyl substances (PFAS) are environmentally ubiquitous, anthropogenic substances with adverse effects on organisms, which shows the need to study their environmental fate and leaching behavior. In the present soil columns study, the leaching behavior and fate of nontransformable and transformable (precursors) were investigated. Ten nontransformable PFAS in two different soils, two precursors and two field soils, which were already contaminated with a mixture of PFAS, and two uncontaminated controls, were set up for a time span of 2 years. At the end of the study, the molecular balance could not be closed for nontransformable PFAS. This effect was positively correlated to the fluorinated carbon chain length. The precursors, which were both polyfluoroalkyl phosphate diesters (diPAP), had different transformation products and transformation rates, with a higher rate for 6:2 diPAP than 8:2 diPAP. After 2 years, amounts of diPAP were still found in the soil with no significant vertical movement, showing high adsorption to soils. Transformation products were estimated to be simultaneously formed. They were predominantly found in the percolation water; the amounts left in soil were negligible. Up to half of the initial precursor amounts could not be balanced and were considered missing amounts. The results of contaminated field soil experiments showed the challenge to estimate PFAS leaching without knowing all occurring precursors and complex transformation dynamics. For this purpose, it was shown that a broad examination of contaminated soil with different analytical methods can help with qualitative estimations of leaching risks. For a better quantitative estimation, analytical determination of more PFAS and a quantification of the missing amounts are needed. Environ Toxicol Chem 2022;41:2065-2077. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Occurrence of per- and polyfluoroalkyl substances and unidentified organofluorine in leachate from waste-to-energy stockpile - A case study.

Per- and polyfluoroalkyl substances (PFASs) are a diverse group of chemicals used in consumer products, which will inevitably end up in waste streams. Landfills are widely recognized secondary point sources of PFASs, but other types of waste management sites have received less attention. Therefore, in a case study presented here we investigated releases of PFASs from temporarily stored waste by determining quantities of 34 PFASs in leachate from a Waste-to-Energy stockpile (45 000 ± 2000 tonnes) during five months in 2019. We also measured extractable organofluorine (EOF) to account for PFASs not included in the target list. The mean total concentration of the 34 PFAS (Σ34PFAS) was 211 ± 31 ng/L, and short-chain (C4-C7) perfluorocarboxylic acids (PFCAs) accounted for 56-60% of the total. Moreover, we found that Σ34PFAS only accounted for 12% ± 4% of EOF detected in the leachate. Our results demonstrate that waste stockpiles are previously unexplored sources of PFASs in the environment, and the dominance of short-chain PFCAs is consistent with observed profiles of contaminants in landfill leachates.

Combined leaching and plant uptake simulations of PFOA and PFOS under field conditions.

Per- and polyfluoroalkyl substances (PFASs) are used in industrial production and manufacturing but were repeatedly detected in agricultural soils and therefore in cash crops in recent years. Dissipation of perfluoroalkyl acids (PFAAs), a sub-group of PFASs, in the environment was rather attributed to the formation of non-extractable residues (NER) than to degradation or transformation. Currently, there are no models describing the fate of PFAAs in the soil-plant continuum under field conditions, which hampers an assessment of potential groundwater and food contamination. Therefore, we tested the ability of the pesticide-leaching model MACRO to simulate the leaching and plant uptake of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in a field lysimeter using two concepts of adsorption: a kinetic two-side sorption concept usually applied for pesticide leaching (scenario I) and the formation of NER (scenario II). The breakthrough of substances could be simulated adequately in scenario II only. Scenario I, however, was not able to reproduce sampled leaching concentrations. Plant uptake was simulated well in the first year after contamination but lacked adequacy in the following years. The model results suggest that more than 90% of PFOA and PFOS are in the pool of NER after 8 years, which is more compared with other studies. However, since NER formation was hypothesized to be a kinetic process and our study used a PFASs leaching time series over a period of 8 years, the results are reasonable. Further research is required on the formation of NER and the uptake of PFAAs into plants in order to gain a better model performance and extend the simulation approach to other PFAAs.

Using carbonized low-cost materials for removal of chemicals of environmental concern from water.

Adsorption on low-cost biochars would increase the affordability and availability of water treatment in, for example, developing countries. The aim of this study was to identify the precursor materials and hydrochar surface properties that yield efficient removal of compounds of environmental concern (CEC). We determined the adsorption kinetics of a mixture containing ten CECs (octhilinone, triclosan, trimethoprim, sulfamethoxasole, ciprofloxacin, diclofenac, paracetamol, diphenhydramine, fluconazole, and bisphenol A) to hydrochars prepared from agricultural waste (including tomato- and olive-press wastes, rice husks, and horse manure). The surface characteristics of the hydrochars were evaluated via diffuse reflectance infrared spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and N2-adsorption. Kinetic adsorption tests revealed that removal efficiencies varied substantially among different materials. Similarly, surface analysis revealed differences among the studied hydrochars and the degree of changes that the materials undergo during carbonization. According to the DRIFTS data, compared with the least efficient adsorbent materials, the most efficient hydrochars underwent more substantial changes during carbonization.

Correction to: Influence of pyrolysis temperature and production unit on formation of selected PAHs, oxy-PAHs, N-PACs, PCDDs, and PCDFs in biochar-a screening study.

The correct presentation of Figs. 1, 3 and Table 3 are shown in this paper.

Influence of pyrolysis temperature and production unit on formation of selected PAHs, oxy-PAHs, N-PACs, PCDDs, and PCDFs in biochar-a screening study.

The influence of reactor type and operating conditions of the pyrolysis unit on the final concentration of toxic contaminants in biochar remains unclear. Therefore, we determined the concentrations of polycyclic aromatic hydrocarbons (PAHs), oxygenated polycyclic aromatic hydrocarbons (oxy-PAHs), nitrogen-containing polycyclic aromatic compounds (N-PACs), polychlorinated dibenzo-p-dioxins (PCDDs), and dibenzofurans (PCDFs) in biochars produced from three different feedstocks (softwood, wheat straw, and anaerobic digestate). Different scaled pyrolysis units (one batch and two continuous units) at two different temperatures (550 and 700 °C) were considered. The results revealed that the type of biomass had a significant influence on the PAH, oxy-PAH, and N-PAC content of the biochars. The configuration and type of the pyrolysis unit influenced only the wheat straw pyrolyzed at 550 °C. PCDDs and PCDFs occurred at very low levels in the biochars. In terms of PAH, PCDD, and PCDF content, the biochars assessed in this study represent a low risk to the environment, regardless of the temperature and type and size of the pyrolysis unit.

Thermal decomposition of municipal solid waste fly ash and desorption of polychlorinated dibenzo-p-dioxins and furans from fly ash surfaces.

Surfaces of fly ashes from three Swedish MSW incinerating plants were extensively characterized to better predict their involvement in the generation of persistent organic pollutants. The ashes were then subjected to thermal treatment at 400 °C in sealed glass ampoules to track the decomposition polychlorinated dibenzo-p-dioxins and furans (PCDD and PCDF). Temperature programmed desorption experiments in the 30-900 °C range also enabled monitoring of thermally decomposing ashes by Fourier Transform Infrared (FTIR) spectroscopy as well as thermally desorbing effluent gases by mass spectrometry. In addition, one ash was doped with 13C-labelled PCDD and PCDF to evaluate the potential of the experimental setup for elucidating the thermal desorption of the organic molecules. It was found that in ashes with high carbon content PCDD and PCDF decomposition were led pronounced, and that PCDD degraded more readily than PCDF.

14th congress of combustion by-products and their health effects-origin, fate, and health effects of combustion-related air pollutants in the coming era of bio-based energy sources.

The 14th International Congress on Combustion By-Products and Their Health Effects was held in Umeå, Sweden from June 14th to 17th, 2015. The Congress, mainly sponsored by the National Institute of Environmental Health Sciences Superfund Research Program and the Swedish Research Council for Environment, Agricultural Sciences and Spatial Planning, focused on the "Origin, fate and health effects of combustion-related air pollutants in the coming era of bio-based energy sources". The international delegates included academic and government researchers, engineers, scientists, policymakers and representatives of industrial partners. The Congress provided a unique forum for the discussion of scientific advances in this research area since it addressed in combination the health-related issues and the environmental implications of combustion by-products. The scientific outcomes of the Congress included the consensus opinions that: (a) there is a correlation between human exposure to particulate matter and increased cardiac and respiratory morbidity and mortality; (b) because currently available data does not support the assessment of differences in health outcomes between biomass smoke and other particulates in outdoor air, the potential human health and environmental impacts of emerging air-pollution sources must be addressed. Assessment will require the development of new approaches to characterize combustion emissions through advanced sampling and analytical methods. The Congress also concluded the need for better and more sustainable e-waste management and improved policies, usage and disposal methods for materials containing flame retardants.

In-filter PCDF and PCDD formation at low temperature during MSWI combustion.

This case study investigated PCDF and PCDD emissions from a 65 MW waste-to-energy plant to identify why an air pollution control system remodeling to accommodate increased production resulted in increased TEQ concentrations. Pre- and post-filter gases were collected simultaneously in four sample sets with varying filter temperatures and with/without activated carbon injection. Samples were analyzed to determine total PCDF and PCDD concentrations, as well as homologue profiles, and concentrations of individual congeners (some remained co-eluted). The total post filter PCDD concentrations where found to increase while the concentrations of PCDF and 2,3,7,8-substituted congeners declined. An investigation of the individual congener concentrations revealed that the increase of PCDD concentrations were due to a few congeners, suggesting a single formation route. The study also concludes that vital information about the formation could be obtained by not restricting the analysis to just the 2,3,7,8-substituted congeners.

Accurate sampling of PCDD/F in high temperature flue-gas using cooled sampling probes.

In a laboratory-scale combustion reactor, flue-gas samples were collected at two temperatures in the post-combustion zone, 700°C and 400°C, using two different water-cooled sampling probes. The probes were the cooled probe described in the European Standard method EN-1948:1, referred to as the original probe, and a modified probe that contained a salt/ice mixture to assist the cooling, referred to as the sub-zero probe. To determine the efficiency of the cooling probes, internal temperature measurements were recorded at 5cm intervals inside the probes. Flue-gas samples were analyzed for polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs). Samples collected at 700°C using the original cooling probe showed higher concentrations of PCDD/Fs compared to samples collected using the sub-zero probe. No significant differences were observed between samples collected at 400°C. The results indicated that artifact formation of PCDD/Fs readily occurs during flue-gas sampling at high temperatures if the cooling within the probe is insufficient, as found for the original probe at 700°C. It was also shown that this problem could be alleviated by using probes with an enhanced cooling capacity, such as the sub-zero probe. Although this may not affect samples collected for regulatory purposes in exit gases, it is of great importance for research conducted in the high-temperature region of the post-combustion zone.