Vermistabilization of excess sludge employing Eisenia fetida: Earthworm histopathological alterations and phytotoxicity evaluation.

The aim of this work was to stabilize excess sludge (ES) coming from a wastewater treatment plant (WWTP) by vermistabilization and to evaluate ecotoxicological effects over the earthworm species Eisenia fetida. Three mixtures were made up in triplicate using different volume ratios of ES and soil (S) (100% ES, 70:30% ES:S and 30:70% ES:S in wet weight basis). Earthworms were added in order to compare vermicomposting vs. natural stabilization. The mixtures were monitored over 130 days through physical, chemical, pathological and biological analysis, following quality standards depicted in the US EPA 40 CFR Part 503, local regulations and background studies. Histopathological samples were processed as biomarkers of acute and chronic toxicity on earthworms, and germination assays were performed at the end of the experiment to assess phytotoxicity. In terms of pathogen depletion comparing initial and final values from each treatment, the mixtures with higher ES proportions (70 and 100%) with earthworms were the most efficient ones registering 64.8 and 75.5% of reduction of fecal coliforms (FC) respectively, while the lowest ES proportion with earthworms (30%) showed 54.7%. Final pathogens content in all the treatments with earthworms were significantly lower (ranged from 1360 to 1760 MPN g total solids-1) than the values registered in treatments without earthworms (ranged from 2400 to 4000 MPN g total solids-1) (p < 0.05). However, none of the treatments attained class A categorization (FC ≤ 1000 MPN g total solids-1) in terms of FC. Also, values of mean cocoon production and hatched juveniles along time were significantly higher in the treatments with 100 and 70% ES (p < 0.05), while the higher mean adult biomass was detected in the treatment with 30% ES. Volatile solids decrease ranged between 8.45 and 22.34% in treatments with earthworms and all values of specific oxygen uptake rate were below 1.5 mg O2 h -1 g total solids -1. There were not negative effects over behavior or reproduction of E. fetida adults, nor the presence of external and internal injuries. Final products from mixtures with earthworms presented a humus-like structure, were odorless and reached maturity values -presenting no phytotoxicity-with significant differences between germination index values of treatments with and without earthworms (p < 0.05). Vermistabilization is a successful eco-technology to sanitize excess sludge, acquiring an added-value material and contributing to its revalorization as organic amendments or fertilizers in soils within the circular economy framework and the United Nations' Sustainability Development Goals.

Elimination of microplastics, PFAS, and PPCPs from biosolids via pyrolysis to produce biochar: Feasibility and techno-economic analysis.

Biosolids from municipal wastewater treatment contain many contaminants of emerging concern, including microplastics (MPs), per- and polyfluoroalkyl substances (PFAS), pharmaceuticals and chemicals from personal care products (PPCPs). Many of these contaminants have very slow biotic or abiotic degradation rates and have been shown to have human and ecological health impacts. Application of biosolids to agriculture, a common disposal method, can result in extended environmental contamination. An approach for eliminating the contaminants is pyrolysis, which can also generate biochar, enhancing carbon sequestration as a side-benefit. We pyrolyzed biosolid samples from an operating facility at various temperatures from 400 to 700 °C with a 2-hour residence time. We then evaluated contaminant removal, which in many cases was 100 %, with only a few residuals. No trace of PFAS was detectable even at 400 °C. Overall mass removal of PPCPs, including PFAS, was over 99.9 %. MP removal via pyrolysis ranged from 91 to 97 %. The biochar contains significant amounts of Fe and P, which make it a useful fertilizer amendment. The techno-economic analysis indicates that pyrolysis may generate significant cost savings, and revenue from the sale of biochar, sufficient to more than cover the investment and operating costs of the dryer and pyrolysis unit.

Size and polarity fractions of mobile organic matter from manure affect the sorption of sulfadiazine, caffeine and atenolol in soil.

Waste-derived organics introduced to soils along with pharmaceutical active compounds (PhAC) are a crude mixture of compounds occurring in various size and polarity fractions. They affect the sorption of PhACs to soil; however, the relevant knowledge is still insufficient. The effects of different size and polarity fractions of manure-derived mobile organic matter (<63 µm) on the sorption of sulfadiazine, caffeine and atenolol to five topsoils were investigated. Mobilization of the PhACs was strongest in the presence of dissolved organic matter (mDOM, <0.45 µm), with a reduction of Kd of sulfadiazine, caffeine and atenolol by mean factors of 0.66, 0.57 and 0.41, respectively. The mobilizing effects of colloidal organic matter (0.45-10 µm) were slightly smaller. Fine particulate organic matter (10-63 µm) reduced the sorption of the PhACs in slightly acidic soils (pH 6.0), but increased it in strongly acidic soil (pH 4.3). Furthermore, hydrophobic (HO-mDOM) and hydrophilic (HI-mDOM) fractions of mDOM reduced the sorption capacity but increased the sorption nonlinearity of PhACs in soils. Effects of HO-mDOM and HI-mDOM were PhAC specific. It is suggested to consider the varying impacts of mobile fractions in animal manure and/or treated wastewater in evaluating the fate and environmental relevance of associated PhACs.

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.

Study on the fate of per- and polyfluoroalkyl substances during thermophilic anaerobic digestion of sewage sludge and the role of granular activated carbon addition.

Limited information is available on the removal of per- and polyfluoroalkyl substances (PFAS) in anaerobic digestion (AD). Τhe fate of six PFAS was studied in thermophilic bioreactors in the presence of granular activated carbon (GAC) and voltage application. Reactors with GAC exhibited lower concentrations of volatile fatty acids and higher methane production compared to those with and without the application of voltage. Analysis of PFAS in dissolved and solid phase showed that their distribution was dependent on perfluorocarbon chain length and functional group. Mass balances showed that PFAS were not removed during conventional AD or after applying voltage; however, significant removal (up to 61 ± 8 %) was observed in bioreactors with GAC for perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctane sulfonate (PFOS). Biomass characterization showed that in these bioreactors, the relative abundance of Acinetobacter and Pseudomonas was higher, indicating their potential role in PFAS biotransformation.

The state of the art in biosolids gasification.

Biosolids is a by-product of wastewater treatment that needs to be further processed. Traditional biosolids treatment and disposal technologies are inefficient under the current demanding standards. Thermochemical conversion technologies have been employed for biosolids management, with gasification being the most promising due to the production of syngas, a gaseous product that may be used for the production of energy or high-added-value substances through reforming reactions. Gasification is a complex thermochemical process; its performance and yield are strongly affected by the type of feedstock, but also by the system configuration and process conditions. Gasification usually takes place at temperatures between 700 and 1,200 °C, but it may also occur at lower temperatures (above 375 °C: supercritical water gasification) or at higher temperatures (above 3,000 °C: plasma gasification). The present review briefly presents the biosolids management practices, focusing on the gasification process and syngas treatment, while the state of the art in biosolids gasification is critically presented and discussed. A number of types of gasifiers (more frequently fluidized bed, but also fixed bed, rotary kiln, downdraft, etc.), gasifying agents, and operational conditions have been used for biosolids gasification. The key results of the study regarding biosolids gasification are: (i) the increase of temperature and equivalence ratio enhances the gasification performance, resulting in high syngas yield and quality, high cold gas efficiency, and low tar and char production; (ii) the calorific value of the obtained syngas tends to decrease with the increase of equivalence ratio; and (iii) the use of catalysts has been proven to substantially improve the gasification performance, compared to non-catalytic gasification. The proper selection of technical parameters determines the effectiveness of biosolids gasification, which is considered as a promising technology for the energy recovery from biosolids, so to upgrade wastewater treatment and improve environmental quality.

Using organic amendments in disturbed soil to enhance soil organic matter, nutrient content and turfgrass establishment.

Disturbed soils, including manufactured topsoils, often lack physical and chemical properties conducive to vegetation establishment. As a result, efforts to stabilize disturbed soils with vegetation are susceptible to failure. Urban organic waste products such as wood mulch, composted leaf and yard waste, and biosolids are widely distributed as organic amendments that enhance sustainability and plant establishment. Correct use can be determined by examining soil properties such as pH; the concentration of soluble salts (SS); and plant available nutrients - particularly N, C and P; as well as root and shoot growth. This research examined the effects of three typical organic amendments on fertility, establishment, and nutrient loss. A manufactured topsoil was used as the base soil for all treatments, including a control unamended soil (CUT), and soil amended with either mulch (MAT), composted leaf and yard waste (LAT), or biosolids (BAT). A 2 % organic matter concentration increase was sought but not achieved due to difficulty in reproducing lab results at a larger scale. Results showed that LAT improved soil fertility, particularly N-P-K concentrations while maintaining a good C:N ratio, pH, and SS concentration. BAT was the most effective at enhancing shoot growth but results suggest that improved growth rates could result in increased maintenance. Additionally, biosolids were an excellent source of nutrients, especially N-P-K and S, but diminished root growth and N leachate losses indicate that N was applied in excess of turfgrass requirements. Therefore, biosolids could be used as fertilizer, subject to recommended rates for turfgrass establishment to prevent poor root growth and waterborne N pollution. To ensure establishment efforts are successful, MAT is not recommended without a supplemental source of soluble N. Altogether, study results and conclusions could inform others seeking to improve specifications for disturbed soil where turfgrass establishment is needed to stabilize soil.

Quantifying levels of per- and polyfluoroalkyl Substances (PFAS) in water and serum after contamination from agricultural biosolid application.

The National Academies of Sciences, Engineering, and Medicine recommends per- and polyfluoroalkyl substance (PFAS) blood testing for patients with risk of elevated exposure, and the Agency for Toxic Substances and Disease Registry (ATSDR) suggests PFAS blood testing based on exposure. Barriers to PFAS blood testing include cost, access to labs, and evolving laboratory methods. We quantify water and serum PFAS levels among a highly-exposed cohort in an area with groundwater contaminated by historical agricultural biosolid application. We compare the gold standard PFAS serum test with a commercial test and results from a one-compartment toxicokinetic model. Participants were adults (n = 30) whose household (n = 19) water had levels of the sum of six PFAS > 500 ng/L. Serum PFAS were measured using liquid chromatography-tandem mass spectrometry. Demographic and water consumption data were collected via telephone. Serum PFAS results from the commercial test were accessed via medical record. Statistical analysis included descriptive statistics and bivariate plots of serum levels. Perfluorohexanoic acid, perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), perfluorobutanesulfonic acid, perfluorohexanesulfonic acid (PFHxS), and perfluorooctanesulfonic acid (PFOS) were detected in 19 wells, and PFHpA, PFOA, PFNA, perfluorodecanoic acid, perfluoroundecanoic acid, PFHxS, and PFOS were detected in at least 19 participants' serum. In well water, PFOA and PFOS levels had geometric means (GMs) of 1749 ng/L (geometric standard deviation [GSD] 2.4) and 887 ng/L (GSD 19.7), respectively. In serum, PFOA and PFOS had GMs of 116.2 µg/L (GSD 13.5) and 58.3 µg/L (GSD 13.8), respectively. Our results are comparable with and had a wider mix of PFAS than other high-exposure cohorts. There was good agreement between the commercial and gold standard tests for PFOA, PFNA, and PFHxS, and mixed agreement between the gold standard test and modeled predictions, suggesting water-based toxicokinetic models of serum PFAS may be inadequate for assessing exposure in this population.

A method for the extraction of microplastics from solid biowastes including biosolids, compost, and soil for analysis by µ-FTIR.

Few methods exist detailing the extraction of microplastics from organic matrices. A validated method for the successful extraction of microplastics from solid biowastes including biosolids, compost, and soil for spectroscopic analysis by micro-Fourier transform infrared spectroscopy (µ-FTIR) was developed. Solid dry biowastes were first digested with a wet peroxide oxidation (WPO) with iron (II) solution and 30% hydrogen peroxide followed by sequential density separations with ultra-pure water and 1.8 g cm-3 NaI in an optimised sediment-microplastic isolation (SMI) unit. The average recoveries for spiked microplastics were 92, 95 and 98% for bagged compost, biosolids, and soil, respectively. This method ensures a high microplastic recovery by first chemically disintegrating biowaste aggregates without employing destructive methods like milling and allows for successful density separations where the settled fraction is isolated off from the supernatant, allowing thorough rinsing of the equipment and thus a greater transferal of particles into the vacuum filtering device. Minimal processing steps reduce the instance of introducing contamination and particle loss.•Digestion as a first step to disintegrate aggregates to release entrapped microplastics•Density separation with SMI unit with the method adapted for biowastes•Minimal steps to reduce contamination and particle loss.

Impact of long-term application of biosolids to surface water nitrogen in a working forest plantation in King County, Washington.

Forest fertilization with municipal biosolids has been shown to increase tree growth and enhance forest soils. However, there are concerns that nitrogen from the biosolids could impact surface waters through movement from subsurface flow. Here we analyzed data on soil and surface water nitrogen from a working tree plantation that has used biosolids for over three decades to see if there was evidence of N movement through the soil to surface waters. GIS (Geographic Information System) was used to map application units over time and LiDAR (Light Detection and Ranging) was used to delineate watersheds. The program is located in King County Washington with biosolids provided by the King County Wastewater Treatment program. We assembled records to determine if there is any evidence of movement of NO3- through soils or any enrichment in surface waters. While soils show evidence of NO3- enrichment following biosolids application with cumulative loading rates up to 26 Mg ha-1, this is generally limited to the 'A' soil horizon and does not increase linearly with increased biosolids loading rates. There was no indication of increased surface water NO3- concentration relative to biosolids application rates, with a small trend of decreasing water NO3- over time. Surface water NO3- concentration was not correlated with the fraction of the watershed area that had been amended with biosolids, and there was no observable increase in surface water NO3- with increased frequency of biosolids applications to the tree plantations. These results suggest that the current biosolids program is sufficiently protective of ground and surface waters. These observations suggest that biosolids application can be conducted on a large scale with multiple benefits and no discernible impact to surface waters.

Analysis of effects and factors linked to soil microbial populations and nitrogen cycling under long-term biosolids application.

Information about impacts of long-term biosolids application on soil microbial populations and functional groups and N cycling is important for evaluating soil health and agroecosystem sustainability under long-term biosolids application. Mine spoil plots received annual biosolids application from 1973 to 2010 at low (16.8 Mg ha-1 yr-1), medium (33.6 Mg ha-1 yr-1), and high rates (67.2 Mg ha-1 yr-1). A no-biosolids control received chemical fertilizer at the agronomic rate. Soil samples were collected in three seasons per year spanning 2003-2005 for measuring soil moisture, pH, soil organic C (SOC), total and extractable heavy metals (Cd, Cu, Ni, Zn), NO3-, N mineralization potential (NMP), microbial biomass C (MBC), and populations of three N-cycling bacteria (NCB) groups: ammonia-oxidizing bacteria (AOB), nitrite-oxidizing bacteria (NOB), and denitrifying bacteria (DNB). Soil samples were collected again in 2008 and 2010 for quantifying total and extractable heavy metals, and in 2018 (eight years after biosolids applications ended) for measuring SOC, MBC, NMP, and microbial respiration. During 2003-2005, mean MBC was 315, 554, 794, and 1001 mg kg-1 in the control, low, medium, and high biosolids treatments, respectively. Populations of NCB did not differ among treatments. Biosolids application increased total and extractable metal concentrations but the effect of biosolids rates were much lower on extractable than total concentrations. Soil extractable Cd and Cu concentrations decreased from medium to high applications, likely due to complexing with biosolids organic matter. Partial least squares regression analysis identified a strong positive effect on MBC of SOC and a weak negative effect of Cu, explaining the strong net positive effect of biosolids on MBC. In 2018, the medium and high biosolids treatments maintained higher SOC, MBC, NMP, and microbial respiration than the control. This study provided further evidence that long-term biosolids application has positive effects on soil microbes that persist for years after ending application.

Microbiota recovery in a chronosquences of impoverished Cerrado soils with biosolids applications.

Mining activities put the Brazilian savannas, a global biodiversity hotspot, in danger of species and soil carbon losses. Experiments employing biosolids have been applied to rejuvenate this degraded ecosystem, but a lingering question yet to be answered is whether the microbiota that inhabits these impoverished soils can be recovered towards its initial steady state after vegetation recovery. Here, we selected an 18-year-old restoration chronosequence of biosolids-treated, untreated mining and native soils to investigate the soil microbiota recovery based on composition, phylogeny, and diversity, as well as the potential factors responsible for ecosystem recovery. Our results revealed that the soil microbiota holds a considerable recovery potential in the degraded Cerrado biome. Biosolids application not only improved soil health, but also led to 41.7 % recovery of the whole microbial community, featuring significantly higher microbiota diversity and enriched groups (e.g., Firmicutes) that benefit carbon storage compared to untreated mining and native soils. The recovered community showed significant compositional distinctions from the untreated mining or native soils, rather than phylogenetic differences, with physiochemical properties explaining 55 % of the overall community changes. This study advances our understanding of soil microbiota dynamics in response to disturbance and restoration by shedding light on its recovery associated with biosolid application in a degraded biodiverse ecosystem.

Effects on soil carbon storage from municipal biosolids application to agricultural fields.

This study investigated the influence of biosolid applications on soil carbon storage and evaluated nutrient management strategies affecting soil carbon dynamics. The research assessed alterations in soil pH, soil carbon stock, and soil nitrogen content within short-term and long-term biosolids-amended soils in Bible Hill, Nova Scotia, Canada, extending to a depth of 0-60 cm. The findings indicated an increase in soil pH with alkaline treatment biosolids (ATB) applications across both study sites, with a legacy effect on soil pH noted in the long-term biosolids-amended soil following a single ATB application over 13 years. Both sites demonstrated significant increases in soil total carbon (STC) and soil organic carbon (SOC) within the 0-30 cm soil depth after biosolid application, and soil inorganic carbon (SIC) accounted for approximately 5-10% of STC, specifically in the surface soil layer (0-15 cm). In the long-term study site, annual 14, 28 and 42 Mg ATB ha-1 treatments resulted in a substantial rise in soil carbon stock (59.5, 60.1 and 68.0 Mg C ha-1), marking a 25% increase compared to control soil. The SOC content in biosolids-amended soil showed a declining trend with increasing soil depth at both study sites. Notably, the carbon stock in the short-term site was observed in composted biosolids (COMP) > ATB > liquid mesophilic anaerobically digested biosolids (LMAD) from the 0-60 cm soil depth. Approximately 79-80% of the variation in SOC response at both sites was concentrated within the top 30 cm soil. Soil total nitrogen (STN) showed no significant differences at the short-term site, and STN in biosolids-amended soil decreased with increasing soil depth at the long-term site. Biosolids-induced C retention coefficients (BCR) for ATB remained consistent at both sites, ranging from -13% to 31.4% with a mean of 11.12%. BCR values for COMP ranged from 1.9% to 34.4% with a mean of 18.73%, while those for LMAD exhibited variability, spanning from -6.2% to 106.3% with a mean of 53.9%.

Black soldier fly-based bioconversion of biosolids: Microbial community dynamics and fate of antibiotic resistance genes.

Biosolids as by-products of wastewater treatment can contain a large spectrum of pathogens and antibiotic resistance genes (ARGs). Insect-based bioconversion using black soldier fly larvae (BSFL) is an emerging technology that has shown to reduce significant amounts of biosolids quickly and produce larvae biomass containing low heavy metal concentrations. However, to the best of our knowledge, this is the first study investigating the transfer of pathogens and ARGs from biosolids into the process' end-products, BSFL and frass. We hypothesized that BSF-based bioconversion can decrease the abundance of pathogenic bacteria and ARGs in biosolids. In this study, we performed BSFL feeding trials with biosolids blended or not blended with wheat bran, and wheat bran alone as a low bioburden diet (control). We conducted 16S rRNA amplicon sequencing to monitor changes of the BSFL-associated microbial community and the fate of biosolids-associated pathogens. A diverse set of ARGs (ermB, intl1, sul1, tetA, tetQ, tetW, and blaCTX-M-32) were quantified by qPCR and were linked to changes in substrate- and BSFL-associated microbiomes. BSF-based bioconversion of biosolids-containing substrates led to a significant reduction of the microbial diversity, the abundance of several pathogenic bacteria and the investigated ARGs (< 99 %). Feeding with a high bioburden biosolid diet resulted in a higher microbial diversity, and the accumulation of pathogenic bacteria and ARGs in the BSFL. Results of this study demonstrated that BSF-based bioconversion can be a suitable waste management technology to (1) reduce significant amounts of biosolids and (2) reduce the presence of pathogens and ARGs. However, the resulting larvae biomass would need to undergo further post-treatment to reduce the pathogenic load to allow them as animal feed.

Per- and poly-fluoroalkyl substances in agricultural contexts and mitigation of their impacts using biochar: A review.

Growing concern over the presence of per- and polyfluoroalkyl substances (PFAS) in agricultural compartments (e.g., soil, water, plants, soil fauna) has led to an increased interest in scalable and economically feasible remediation technologies. Biochar is the product of pyrolyzing organic materials (crop waste, wood waste, manures, grasses) and has been used as a low-cost adsorbent to remove contaminants including PFAS. This review frames biochar as a strategy for mitigating the detrimental impacts of PFAS in agricultural systems and discusses the benefits of this strategy within the framework of the needs and challenges of contaminant remediation in agriculture. To gauge the optimal physicochemical characteristics of biochar in terms of PFAS adsorption, principal component analysis using >100 data points from the available literature was performed. The main biochar-based PFAS treatment strategies (water filtration, soil application, mixing with biosolids) were also reviewed to highlight the benefits and complications of each. Life cycle analyses on the use of biochar for contaminant removal were summarized, and data from selected studies were used to calculate (for the first time) the global warming potential and net energy demand of various agriculturally important biochar classes (crop wastes, wood wastes, manures) in relation to their PFAS adsorption performance. This review serves to identify key gaps in our knowledge of (i) PFAS adsorption by biochars in agricultural remediation applications and (ii) environmental costs/benefits of biochars in relation to their adsorptive properties toward PFAS. The concepts introduced in this review may assist in developing large-scale biochar-based PFAS remediation strategies to help protect the agricultural food production environment.

Quantification of quaternary ammonium compounds by liquid chromatography-mass spectrometry: Minimizing losses from the field to the laboratory.

Quaternary Ammonium Compounds (QACs) are widely used in household, medical and industrial settings. As a consequence, they are ubiquitously found in the environment. Although significant efforts have been put into the development of sensitive and reproducible analytical methods, much less effort has been dedicated to the monitoring of QACs upon sample storage and sample preparation. Here we studied the effect of storage, concentration, and extraction procedures on the concentrations of QACs in samples. Thirteen QACs selected amongst benzalkonium compounds (BACs), dialkyldimethylammonium compounds (DADMACs) and alkyltrimethylammonium compounds (ATMACs) were quantified in aqueous and solid samples using LC-MS/MS. Most QACs adsorbed on container walls could be recovered using a short washing step with MeOH containing 2 % v/v formic acid. Concentrations of QACs from aqueous solutions using solid phase extraction (SPE) with Strata-X cartridges and elution with acidified MeOH utilized to wash the emptied containers gave highly satisfactory recoveries (101-111 %). Good recoveries (89-116 %) were also obtained when extracting a spiked organic-rich synthetic soil using accelerated solvent extraction (ASE) with acidified MeOH at low solid/solvent ratio (0.4 g/20 mL). Applying the recommended methodologies to real samples collected from a Canadian wastewater treatment plant (WWTP) gave QAC concentrations in the ranges of 0.01-30 µg/L, < 1.2 µg/L, and 0.05-27 mg/kg for the influent, effluent and biosolids samples, respectively.

Terrestrial bioassays for assessing the biochemical and toxicological impact of biosolids application derived from wastewater treatment plants.

Wastewater treatment plants (WWTP) are facilities where municipal wastewater undergoes treatment so that its organic load and its pathogenic potential are minimized. Sewage sludge is a by-product of this process and when properly treated is preferentially called "biosolids". These treatments may include some or most of the following: thickening, dewatering, drying, digestion, composting, liming. Nowadays it is almost impossible to landfill biosolids, which however can well be used as crop fertilizers. Continuous or superfluous biosolids fertilization may negatively affect non-target organisms such as soil macro-organisms or even plants. These effects can be depicted through bioassays on terrestrial animals and plants. It has been shown that earthworms have been affected to various degrees on the following endpoints: pollutants' bioaccumulation, viability, reproduction, avoidance behavior, burrowing behavior. Collembola have been affected on viability, reproduction, avoidance behavior. Other terrestrial organisms such as nematodes and diplopods have also shown adverse health effects. Phytotoxicity have been caused by some biosolids regimes as measured through the following endpoints: seed germination, root length, shoot length, shoot biomass, root biomass, chlorophyll content, antioxidant enzyme activity. Very limited statistical correlations between pollutant concentrations and toxicity endpoints have been established such as between juvenile mortality (earthworms) and As or Ba concentration in the biosolids, between juvenile mortality (collembola) and Cd or S concentration in the biosolids, or between phytotoxicity and some extractable metals in leachates or aquatic extracts from the biosolids; more correlations between physicochemical characteristics and toxicity endpoints have been found such as between phytotoxicity and ammonium N in biosolids or their liquid extracts, or between phytotoxicity and salinity. An inverse correlation between earthworm/collembola mortality and stable organic matter has also been found. Basing the appropriateness of biosolids only on chemical analyses for pollutants is not cost-effective. To enable risk characterization and subsequent risk mitigation it is important to apply a battery of bioassays on soil macro-organisms and on plants, utilizing a combination of endpoints and established protocols. Through combined analytical quantification and toxicity testing, safe use of biosolids in agriculture can be achieved.

Activation of sawdust biochar with water and wastewater treatment residuals for sorption of perfluorooctanesulfonic acid in water.

Recent research has found biochar to be a cost-effective adsorbent for removal of perfluoroalkyl substances in water. To promote cleaner production and sustainable waste management, this study explored the potential to produce activated biochars by co-pyrolyzing sawdust with iron-rich biosolids and polyaluminum sludge. The maximum capacity to adsorb perfluorooctanesulfonic acid (PFOS) reached 27.2 mg g-1 with biosolids-activated biochar and 19.2 mg g-1 with aluminum sludge-activated biochar, compared to 6.2 mg g-1 with sawdust biochar. The increased adsorption capacities were attributed to electrostatic interactions between the anionic PFOS and metal functionalities on the biochar surface. In contrast, hydrophobic interaction was the dominant adsorption mechanism of sawdust biochar. The presence of dissolved organic matter at 5-50 mg L-1 was found to inhibit adsorption of PFOS in water, while pH as low as 3.0 and sodium chloride concentrations up to 100 mM enhanced removal of PFOS by all the three adsorbents. In batch adsorption tests at environmentally relevant PFOS dosages and adsorbent dosage of 0.25 g L-1, the biosolids-sawdust biochar and Al sludge-sawdust biochar removed 71.4% and 66.9% of PFOS from drinking water and 77.9% and 87.9% of PFOS from filtrate of sludge digestate, respectively. The biosolids-sawdust biochar additionally removed Fe, although the Al sludge-sawdust biochar released Al into the alkaline drinking water and filtrate. Overall, this study proved co-pyrolyzing sawdust and Fe-rich biosolids to be an effective approach to activate sawdust biochar for enhanced removal of PFOS while recycling wastewater treatment residuals and sawdust.

Defluorination of PFAS by Acidimicrobium sp. strain A6 and potential applications for remediation.

Acidimicrobium sp. strain A6 is a recently discovered autotrophic bacterium that is capable of oxidizing ammonium while reducing ferric iron and is relatively common in acidic iron-rich soils. The genome of Acidimicrobium sp. strain A6 contains sequences for several reductive dehalogenases, including a gene for a previously unreported reductive dehalogenase, rdhA. Incubations of Acidimicrobium sp. strain A6 in the presence of perfluorinated substances, such as PFOA (perfluorooctanoic acid, C8HF15O2) or PFOS (perfluorooctane sulfonic acid, C8HF17O3S), have shown that fluoride, as well as shorter carbon chain PFAAs (perfluoroalkyl acids), are being produced, and the rdhA gene is expressed during these incubations. Results from initial gene knockout experiments indicate that the enzyme associated with the rdhA gene plays a key role in the PFAS defluorination by Acidimicrobium sp. strain A6. Experiments focusing on the defluorination kinetics by Acidimicrobium sp. strain A6 show that the defluorination kinetics are proportional to the amount of ammonium oxidized. To explore potential applications for PFAS bioremediation, PFAS-contaminated biosolids were augmented with Fe(III) and Acidimicrobium sp. strain A6, resulting in PFAS degradation. Since the high demand of Fe(III) makes growing Acidimicrobium sp. strain A6 in conventional rectors challenging, and since Acidimicrobium sp. strain A6 was shown to be electrogenic, it was grown in the absence of Fe(III) in microbial electrolysis cells, where it did oxidize ammonium and degraded PFAS.

Ammonium-based bioleaching of toxic metals from sewage sludge in a continuous bioreactor.

The broader reuse of sewage sludge as a soil fertilizer or conditioner is impeded by the presence of toxic metals. Bioleaching, a process that leverages microbial metabolisms and metabolites for metal extraction, is viewed as an economically and environmentally feasible approach for metal removal. This study presents an innovative bioleaching process based on microbial oxidation of ammonia released from sludge hydrolysis, mediated by a novel acid tolerant ammonia-oxidizing bacteria (AOB), Ca. Nitrosoglobus. Over a span of 1024 days, a laboratory-scale bioleaching reactor processing anaerobically digested (AD) sludge achieved an in-situ pH of 2.5 ± 0.3. This acidic environment facilitated efficient leaching of toxic metals from AD sludge, upgrading its quality from Grade C to Grade A (qualified for unrestricted use), according to both stabilization and contaminants criteria. The improved quality of AD sludge could potentially reduce sludge disposal expenses and enable a broader reuse of biosolids. Furthermore, this study revealed a pH-dependent total ammonia affinity of Ca. Nitrosoglobus, with a higher affinity constant at pH 3.5 (67.3 ± 20.7 mg N/L) compared to pH 4.5-7.5 (7.6 - 9.6 mg N/L). This finding indicates that by optimizing ammonium concentrations, the efficiency of this novel ammonium-based bioleaching process could be significantly increased.