Eco-toxicological and climate change effects of sludge thermal treatments: Pathways towards zero pollution and negative emissions.

The high moisture content and the potential presence of hazardous organic compounds (HOCs) and metals (HMs) in sewage sludge (SS) pose technical and regulatory challenges for its circular economy valorisation. Thermal treatments are expected to reduce the volume of SS while producing energy and eliminating HOCs. In this study, we integrate quantitative analysis of SS concentration of 12 HMs and 61 HOCs, including organophosphate flame retardants (OPFRs) and per- and poly-fluoroalkyl substances (PFAS), with life-cycle assessment to estimate removal efficiency of pollutants, climate change mitigation benefits and toxicological effects of existing and alternative SS treatments (involving pyrolysis, incineration, and/or anaerobic digestion). Conventional SS treatment leaves between 24 % and 40 % of OPFRs unabated, while almost no degradation occurs for PFAS. Thermal treatments can degrade more than 93% of target OPFRs and 95 % of target PFAS (with the rest released to effluents). The different treatments affect how HMs are emitted across environmental compartments. Conventional treatments also show higher climate change impacts than thermal treatments. Overall, thermal treatments can effectively reduce the HOCs emitted to the environment while delivering negative emissions (from about -56 to -111 kg CO2-eq per tonne of sludge, when pyrolysis is involved) and producing renewable energy from heat integration and valorization.

Using the benzenepolycarboxylic acid (BPCA) method to assess activated biochars and their PFAS sorption abilities.

Activated carbon (AC) has important industrial and environmental applications as it has excellent abilities to sorb contaminants such as per- and polyfluoroalkyl substances (PFAS). Current research aims to develop activated biochars (AB) from renewable biomass to replace AC that is produced from fossil feedstock. Both AC and AB are primarily comprised of condensed aromatic carbon (ConAC), the component that is the focus of this study. ConAC is characterized to determine its relationship with biochar activation conditions and PFAS sorption, which are understudied at present. Benzenepolycarboxylic acid (BPCA) markers for ConAC were quantified in steam-activated biochars (AB-Steam) and carbon dioxide-activated biochars (AB-CO2) prepared from waste timber at different temperatures (800, 850, 900 °C) and molar ratios of feedstock-carbon:steam (0.50 - 1.25). A non-activated biochar was also included as a reference. ConAC relative to total organic carbon content was higher in AB-Steam than in AB-CO2 (92 ± 2 % vs. 81 ± 11%). The ratio of benzenehexa- (B6CA) to benzenepentacarboxylic (B5CA) acids revealed that AB-Steam also had larger ConAC clusters than AB-CO2. These findings provide novel evidence that steam activation is more effective than CO2 activation in creating ConAC. To assess how ConAC impacts AB sorption abilities, AB-Steam were used to remediate PFAS from contaminated soils. The observed strong correlations between ConAC content and sorption of long-chain PFAS suggest the importance of hydrophobic interactions between PFAS tails and ConAC. Poor correlations for short-chain PFAS, on the other hand, indicated the existence of electrostatic repulsion interactions between PFAS head groups and ConAC. Collectively, these results explain the great ability of AB-Steam to sorb PFAS from contaminated soils (up to 100% remediation). More broadly, this work demonstrates that the BPCA method can be a valuable tool to assess the quality of biochars and other carbonaceous sorbents in relation to their production conditions or contaminant sorption abilities.

Stabilization of PFAS-contaminated soil with sewage sludge- and wood-based biochar sorbents.

Sustainable and effective remediation technologies for the treatment of soil contaminated with per- and polyfluoroalkyl substances (PFAS) are greatly needed. This study investigated the effects of waste-based biochars on the leaching of PFAS from a sandy soil with a low total organic carbon content (TOC) of 0.57 ± 0.04 % impacted by PFAS from aqueous film forming foam (AFFF) dispersed at a former fire-fighting facility. Six different biochars (pyrolyzed at 700-900 °C) were tested, made from clean wood chips (CWC), waste timber (WT), activated waste timber (aWT), two digested sewage sludges (DSS-1 and DSS-2) and de-watered raw sewage sludge (DWSS). Up-flow column percolation tests (15 days and 16 pore volume replacements) with 1 % biochar indicated that the dominant congener in the soil, perfluorooctane sulphonic acid (PFOS) was retained best by the aWT biochar with a 99.9 % reduction in the leachate concentration, followed by sludge-based DWSS (98.9 %) and DSS-2 and DSS-1 (97.8 % and 91.6 %, respectively). The non-activated wood-based biochars (CWC and WT) on the other hand, reduced leaching by <42.4 %. Extrapolating this to field conditions, 90 % leaching of PFOS would occur after 15 y for unamended soil, and after 1200 y and 12,000 y, respectively, for soil amended with 1 % DWSS-amended and aWT biochar. The high effectiveness of aWT and the three sludge-based biochars in reducing PFAS leaching from the soil was attributed largely to high porosity in a pore size range (>1.5 nm) that can accommodate the large PFAS molecules (>1.02-2.20 nm) combined with a high affinity to the biochar matrix. Other factors like anionic exchange capacity could play a contributing role. Sorbent effectiveness was better for long-chain than for short-chain PFAS, due to weaker, apolar interactions between the biochar and the latter's shorter hydrophobic CF2-tails. The findings were the first to demonstrate that locally sourced activated wood-waste biochars and non-activated sewage sludge biochars could be suitable sorbents for the ex situ stabilization and in situ remediation of PFAS-contaminated soil, bringing this technology one step closer to full-scale field testing.

Flame curtain kilns produce biochar from dry biomass with minimal methane emissions.

Flame curtain kilns have emerged as the preferred biochar technology for smallholders but reported methane emissions (30 g kg-1 biochar) have impeded carbon certification. Here, for flame curtain kilns we show almost no methane (0-3.6 g kg-1 biochar) emissions for dry (<15 % moisture) feedstock consisting of twigs and leaves. Wet feedstock (>40 % moisture) however generated significant methane (>500 g kg-1 biochar), underscoring that feedstock preparation is decisive for the carbon balance. Even for dry feedstock, both aerosol and CO emissions were significant (21-82 and 40-118 g kg-1 biochar, respectively). The data demonstrate that certification of low-tech biochar made from dry twigs and leaves should not be objected to on the grounds of methane. Careful selection of feedstock and potential after-combustion of the syn-gases are probably needed to avoid CO and aerosol emissions. More data are needed on methane emissions of other dry feedstocks.

The decomposition and emission factors of a wide range of PFAS in diverse, contaminated organic waste fractions undergoing dry pyrolysis.

Current treatment options for organic waste contaminated with per- and polyfluoroalkyl substances (PFAS) are generally limited to incineration, composting or landfilling, all resulting in emissions. Dry pyrolysis is a promising emerging alternative to these practices, but there is uncertainty related to the fate of PFAS during this process. The present work first developed a robust method for the determination of PFAS in complex matrices, such as sewage sludge and biochar. Then, a mass balance was established for 56 different PFAS during full-scale pyrolysis (2-10 kg biochar hr-1, 500-800 °C) of sewage sludges, food waste reject, garden waste and waste timber. PFAS were found in all wastes (56-3651 ng g-1), but pyrolysis resulted in a ≥ 96.9% removal. Residual PFAS (0.1-3.4 ng g-1) were detected in biochars obtained at temperatures up to 750 °C and were dominated by long chain PFAS. Emitted PFAS loads ranged from 0.01 to 3.1 mg tonne-1 of biochar produced and were dominated by short chain PFAS. Emissions made up < 3% of total PFAS-mass in the wastes. Remaining uncertainties are mainly related to the presence of thermal degradation products in flue gas and condensation oils.

Analysis, occurrence and removal efficiencies of organophosphate flame retardants (OPFRs) in sludge undergoing anaerobic digestion followed by diverse thermal treatments.

Organophosphate flame retardants (OPFRs) are a complex group of contaminants to deal with in sewage sludge, as currently there is a lack of robust analytical methods to measure them and management strategies to remove them. To facilitate quantifications of the occurrence of OPFRs in sludge and to establish their removal efficiencies (REs%) during thermal treatments, a simple, reliable, and rapid sample preparation methodology was developed for the determination of 21 OPFRs in diverse sludge, ash and biochar matrices. Matrix-solid phase dispersion (MSPD) tailored to ultra-performance liquid chromatography (UPLC) coupled to tandem mass spectrometry (MS/MS) was applied. Under optimal conditions, 0.5 g of freeze-dried sample were dispersed in 2 g of Bondesil C18, and 1.5 g of deactivated florisil were used as clean-up sorbent. The target analytes were extracted with 5 mL of acetone. The obtained extract was ready for analysis within 20 min without the need of any further treatment. The proposed methodology was assessed, providing absolute recoveries (Abs%) ranging from 50.4 to 112 % with good method repeatability (RSDs <17.9 %). Method limits of quantification ranged from 0.10 to 14.0 ng g-1 dry weight (d.w.). The optimized methodology was applied to raw-, digested-, combusted and pyrolyzed sludge samples collected from different waste treatment plants located in Norway, where 16 out of 21 OPFRs were detected in digested sludge samples up to 2186 ng g-1 (d.w.; sum concentration of OPFRs). Diverse thermal treatments of combustion and dry pyrolysis were assessed for the removal of OPFRs from sludge. Combustion at 300 °C reduced the concentrations of OPFRs by 98 % (in the ashes formed), whereas pyrolysis at temperatures >500 °C effectively removed the OPFRs in the produced biochar. Thermal treatments, in particularly dry pyrolysis, showed potential for achieving zero pollution management and recycling of OPFR contaminated sludge.

Sewage sludge biochars as effective PFAS-sorbents.

The use of sewage sludge to produce biochar-based sorbents for per- and polyfluoroalkyl substances (PFAS) removal from water and soil may be an economically and environmentally sustainable waste management option. This study compared the sorption of six perfluorinated carboxylic acids (PFCAs) by two sewage sludge biochars (SSBCs) and one wood chip biochar (WCBC), dry pyrolyzed at 700 °C. Batch sorption tests were conducted by adding individual PFCAs and a PFCA-mixture to pure biochars and mixtures of biochar and a sandy soil (1.3% TOC). PFAS-sorption to the SSBCs exhibited log-linear biochar-water distribution coefficients (log Kd), comparable to those previously reported for commercial activated carbons (e.g., 5.73 ± 0.02 for perfluorooctanoic acid at 1 µg/L). The strong sorption of PFCAs was attributed to the SSBCs relatively high pore volumes in the pore size range that can accommodate these compounds. Sorption was attenuated by the presence of soil (by factors 3-10), by the presence of a mixture of PFCAs (by factors of 6-532) and by both together (by factors of 8-6581), indicating strongly competitive sorption between PFCA-congeners, and less severe sorption attenuation by soil organic matter. These findings could enable sustainable value chains for SSBs in soil remediation and water filtration solutions.

Industrial byproducts for the soil stabilization of trace elements and per- and polyfluorinated alkyl substances (PFASs).

The present work was the first exploration of the use of industrial byproducts from iron and titanium processing as sorbents for the stabilization of soil contamination. The main aim was to test slag waste and iron-rich charred fossil coal ("Fe-char"), as sorbents for per- and polyfluorinated alkyl substances (PFASs), as well as lead (Pb) and antimony (Sb), in four soils from a firefighting training area (PFASs) and a shooting range (Pb and Sb). Adding slag (10-20%) to shooting range soils decreased the leaching of Pb and Sb up to 50-90%. Fe-char amendment to these soils resulted in a moderate reduction in Sb leaching (20-70%) and a slightly stronger effect on Pb (40-50%). The sorption is most likely explained by the presence of Fe oxyhydroxides. These are present in the highest concentrations in the slag, probably resulting in more effective metal binding to the slag than to the Fe-char. Fe-char but not slag proved to be a strong sorbent for PFASs (reducing PFAS leaching from the soil by up to 99.7%) in soil containing low total organic carbon (TOC; 1.2%) but not in high-TOC soil (34%). The sorption coefficient KD for Fe-char was high, in the range of 104.3 to 106.5 L/kg at 1 ng/L in the low-TOC soil. The KD value increased with increasing perfluorocarbon chain length, exceeding PFAS sorption to biochar in the low ng/L concentration range. This result indicates that the mechanism behind the strong PFAS sorption to Fe-char was mainly van der Waals dispersive interactions between the hydrophobic PFAS-chain and the aromatic π-electron systems on nanopore walls within the Fe-char matrix. Overall, this study indicates that industrial byproducts can provide sustainable and cost-effective materials for soil remediation. However, the sorbent needs to be tailored to the type of soil and type of contamination.

Stabilization of PFAS-contaminated soil with activated biochar.

Biochars are considered potential sustainable sorbents to reduce the leaching of per- and polyfluoroalkyl substances (PFAS) from contaminated soils. However, biochar characteristics must probably be optimized to achieve useful sorption capacity. In the present work, eight waste timber biochars were produced, including biochars activated to different degrees, at different temperatures, and using both steam and CO2. In laboratory batch experiments, the eight biochars were amended to soil samples from two different horizons, with low and high total organic carbon (TOC, 1.6% and 34.2%, respectively), of a heavily PFAS-contaminated soil (1200-3800 µg kg-1 PFAStot), at varying doses (0, 0.1, 0.5, 1.0 and 5.0%). With a 5% amendment to the low-TOC soil, all eight biochars resulted in strongly reduced leachate PFAS concentrations (by 98-100%). At the same amendment dose in the high-TOC soil, leachate concentration reductions were more modest (23-100%). This was likely due to a strong PFAS-sorption to the high-TOC soil itself, as well as biochar pore clogging in the presence of abundant organic matter, resulting in fewer sorption sites available to PFAS. Reduction in PFAS leaching was proportional to the degree of activation and activation temperature. Thus, lower amendment doses of activated biochars were needed to reduce PFAS leaching to the same level as with the non-activated biochar. Activation however, came at a tradeoff with biochar yield. Furthermore, the adsorption ability of these biochars increased proportionally with PFAS-fluorocarbon chain length, demonstrating the role of hydrophobic interactions in reduction of PFAS leaching. Development of internal surface area and porosity was proposed as the main factor causing the improved performance of activated biochars. This study shows that woody residues such as waste timber can be used to produce effective sorbents for the remediation of PFAS-contaminated soil. It also highlights the desirability of sorbate and matrix-specific optimization of biochar production.

Environmental and economic impacts of biochar production and agricultural use in six developing and middle-income countries.

The feasibility of using biowaste for the production of biochar and its use in agriculture depends on its environmental and economic performance. This paper quantifies environmental and economic life cycle impacts of biochar production and agricultural use in six developing and middle-income countries (Ethiopia, Indonesia, Kenya, Peru, Vietnam, and China). Two types of production technologies typical for rural and urban areas were investigated (flame curtain kiln and gasifier, respectively), and comparisons were made with composting (either home composting or windrow composting) as alternative biowaste management systems. The results showed that both pyrolysis systems performed better than composting and both were expected to bring environmental benefits. The largest environmental benefits were observed for the gasifier systems, mainly due to the substitution of electricity production from the grid. Damage to ecosystems and human health ranged from -1 × 10-7 to -2 × 10-8 species×yr and from -1 × 10-5 to -5 × 10-6 DALY per kg of biowaste treated, respectively (negative scores indicating environmental benefits). However, net economic benefits were only achieved when low-cost simple kilns were used in countries with low labor cost, like Ethiopia, Kenya and Vietnam (net profit from 0.01 to 0.08 USD per kg of biowaste treated). Further, high investment and operating costs and relatively small electricity revenue from substituting the grid electricity resulted in gasifier scenarios being economically unsustainable (net loss from 0.29 to 1.58 USD per kg of biowaste treated). Thus, there are trade-offs between positive environmental impacts for society and net market loss for the individual decision-maker (company or individual farmer) that should be considered when making decisions regarding the implementation of biochar technology in developing and middle-income countries. The use of simple kilns in countries with relatively low labor costs appears to be favorable.

The effect of biochar, lime and ash on maize yield in a long-term field trial in a Ultisol in the humid tropics.

A multi-season field trial was carried out to investigate the effect of the amendment of biochar, lime, ash and washed biochar on the growth of maize. A degraded, strongly acidic Ultisol (pHKCl 3.60), with a relatively high exchangeable aluminium content (2.4 cmolc/kg) and a low exchangeable calcium content (0.99 cmolc/kg), was used. Soil was treated once at the beginning of the field trial and crop growth was monitored over seven planting seasons (PS). All treatments increased maize yield. The average increases were; seven times for biochar, five times for lime, five times for washed biochar and eight times for ash treatment, when compared to the control across all PS. The effect of biochar, lime and ash treatments on maize yield were sustained over the seven PS. Soil pHKCl was significantly increased (p < 0.05 level) following the addition of all of the amendment materials. All treatments significantly reduced the concentration of Al3+ when compared to the control (p < 0.05), with the lowest concentrations for the lime and ash treatments. The ash treatment also increased the concentration of macronutrients (K, P and Mg) to the greatest extent. Results showed that there was a clear liming effect at play. The better performance of biochar compared to lime, despite lime having the highest pH and the lowest Al3+ concentration, can be explained by the additional K, Mg and P the biochar adds to the soil. Results also showed a clear nutrient addition effect where ash added the most nutrients. Overall, this work supports the fact that small scale farmers in Indonesia should produce biochar from their waste agricultural materials. Doing so not only provides an increase in crop productivity, but also sequesters carbon resulting in the best overall environmental benefit.

Waste timber pyrolysis in a medium-scale unit: Emission budgets and biochar quality.

Pyrolysis of organic waste or woody materials yields a stable carbonaceous product that can be mixed into soil and is often termed "biochar". During pyrolysis carbon-containing gases are emitted, mainly volatile organic carbon species, carbon monoxide and aerosols. In modern pyrolysis units, gases are after-combusted, which reduces emissions substantially. However, emission data for medium- to large-scale pyrolysis units are scant, both regarding gases, aerosols, heavy metals and polycyclic aromatic hydrocarbons (PAH). Making biochar from lightly contaminated waste timber (WT) is a promising waste handling option as it results in the potential valorization of such residues into e.g. sorbents for contaminant stabilization. For this process to be environmentally sustainable, emissions during the process need to be low and the resulting biochar of sufficient quality. To investigate both issues, we pyrolyzed three batches of WT and one reference batch of clean wood/leaves in a representative medium-scale pyrolysis unit (Pyreg-500, 750 t/year) with after-combustion of the pyrolysis gases, and measured the gas, aerosol, metal and PAH emissions, as well as the characteristics and contamination levels of the resulting biochar, including contaminant leaching. Mean emission factors for the WT were (g/kg biochar); CO = 7 ±â€¯2, non-methane volatile organic compounds (NMVOC) = 0.86 ±â€¯0.14, CH4 = 0, aerosols (PM10) = 0.6 ±â€¯0.3, total products of incomplete combustion (PIC) = 9 ±â€¯3, PAH-16 = (2.0 ±â€¯0.2) ·â€¯10-5, As (most abundant metal) = (2.3 ±â€¯1.9) ·â€¯10-3 and NOX = 0.65 ±â€¯0.10. There were no significant differences in emission factors between the pyrolysis of WT and the reference respectively, except for PM10, NMVOC, and PAH-16, which were significantly lower for WT than for the clean wood/leaves. The WT biochar did not satisfy premium or basic European Biochar Certificate criteria due to high levels of zinc and PAH. However, leachable metal contents were <0.1% of total contents. Still, use of the WT-biochar without further improvement or investigation would be limited to ex situ use, not improving soil fertility or in situ remediation.