Apple Bitter Rot and Glomerella Leaf Spot: A Comprehensive Review of Causal Species and Their Biology, Fungicide Sensitivities, and Management Strategies.

Bitter rot and Glomerella leaf spot (GLS) are two distinct diseases of apple fruit and foliage caused by members of the ascomycete fungal genus Colletotrichum. While GLS is restricted to subtropical and in some areas to temperate climates, bitter rot is responsible for significant yield loss worldwide, particularly during the post-harvest period. Initially thought to be caused by just two species of Colletotrichum, C. acutatum and C. gloeosporioides, advances in molecular biology and sequencing techniques enabled the identification of 25 different species capable of causing bitter rot and/or GLS of apple belongs to the C. gloeosporioides species complex (CGSC), C. acutatum species complex (CASC) and C. boninense species complex (CBSC). Three species (C. gloeosporioides, C. fructicola, and C. chrysophilum) of CGSC cause both bitter rot and GLS, 18 species (6 of CGSC and 12 of CASC) only cause bitter rot, and four species (C. aenigma and C. asianum of CGSC, C. limetticola of CASC and C. karstii of CBSC) only cause GLS. These species were found to differ in their geographical distribution, environmental and host tissue preference, pathogenicity, and fungicide sensitivities. In this review, we summarize the distribution, life cycle, and pathogenicity mechanisms of all currently known Colletotrichum species responsible for bitter rot and GLS of apple. Furthermore, we describe known apple defense mechanisms and management strategies for the control of these economically significant pathogens and identify gaps in our present understanding for future research.

The effects of chemical fungicides and salicylic acid on the apple microbiome and fungal disease incidence under changing environmental conditions.

Epiphytic and endophytic micro-organisms associated with plants form complex communities on or in their host plant. These communities influence physiological traits, development, and host susceptibility to abiotic and biotic stresses, and these communities are theorized to have evolved alongside their hosts, forming a unit of selection known as the holobiont. The microbiome is highly variable and can be influenced by abiotic factors, including applied exogenous agents. In this study, we compared the impact of chemical fungicide and salicylic acid treatments on the fungal communities of "Honeycrisp" apples at harvest over two consecutive growing years. We demonstrated variations in fungal community structure and composition by tissue type, growing season, and treatment regimes and that fungicide treatments were associated with reduced network complexity. Finally, we show that the inclusion of salicylic acid with 50% less chemical fungicides in an integrated spray program allowed a reduction in fungicide use while maintaining effective control of disease at harvest and following storage.

Why Do We Need Alternative Methods for Fungal Disease Management in Plants?

Fungal pathogens pose a major threat to food production worldwide. Traditionally, chemical fungicides have been the primary means of controlling these pathogens, but many of these fungicides have recently come under increased scrutiny due to their negative effects on the health of humans, animals, and the environment. Furthermore, the use of chemical fungicides can result in the development of resistance in populations of phytopathogenic fungi. Therefore, new environmentally friendly alternatives that provide adequate levels of disease control are needed to replace chemical fungicides-if not completely, then at least partially. A number of alternatives to conventional chemical fungicides have been developed, including plant defence elicitors (PDEs); biological control agents (fungi, bacteria, and mycoviruses), either alone or as consortia; biochemical fungicides; natural products; RNA interference (RNAi) methods; and resistance breeding. This article reviews the conventional and alternative methods available to manage fungal pathogens, discusses their strengths and weaknesses, and identifies potential areas for future research.

Why surface hydrophobicity promotes CO2 electroreduction: a case study of hydrophobic polymer N-heterocyclic carbenes.

We report the use of polymer N-heterocyclic carbenes (NHCs) to control the microenvironment surrounding metal nanocatalysts, thereby enhancing their catalytic performance in CO2 electroreduction. Three polymer NHC ligands were designed with different hydrophobicity: hydrophilic poly(ethylene oxide) (PEO-NHC), hydrophobic polystyrene (PS-NHC), and amphiphilic block copolymer (BCP) (PEO-b-PS-NHC). All three polymer NHCs exhibited enhanced reactivity of gold nanoparticles (AuNPs) during CO2 electroreduction by suppressing proton reduction. Notably, the incorporation of hydrophobic PS segments in both PS-NHC and PEO-b-PS-NHC led to a twofold increase in the partial current density for CO formation, as compared to the hydrophilic PEO-NHC. While polymer ligands did not hinder ion diffusion, their hydrophobicity altered the localized hydrogen bonding structures of water. This was confirmed experimentally and theoretically through attenuated total reflectance surface-enhanced infrared absorption spectroscopy and molecular dynamics simulation, demonstrating improved CO2 diffusion and subsequent reduction in the presence of hydrophobic polymers. Furthermore, NHCs exhibited reasonable stability under reductive conditions, preserving the structural integrity of AuNPs, unlike thiol-ended polymers. The combination of NHC binding motifs with hydrophobic polymers provides valuable insights into controlling the microenvironment of metal nanocatalysts, offering a bioinspired strategy for the design of artificial metalloenzymes.

Physical and chemical properties of carbon-based sorbents that affect the removal of per- and polyfluoroalkyl substances from solution and soil.

Removal of per- and polyfluoroalkyl substances (PFASs) from water or their immobilization in soil using carbon-based sorbents is one of the cost-effective techniques. Considering the variety of carbon-based sorbents, identifying the key sorbent properties responsible for PFASs removal from solution or immobilization in the soil can assist in the selection of the best sorbents for management of contaminated sites. This study evaluated the performance of 28 carbon-based sorbents including granular and powdered activated carbon (GAC and PAC), mixed mode carbon mineral material, biochars, and graphene-based materials (GNBs). The sorbents were characterized for a range of physical and chemical properties. PFASs' sorption from an AFFF-spiked solution was examined via a batch experiment, while their ability to immobilize PFASs in soil was tested following mixing, incubation and extraction using the Australian Standard Leaching Procedure. Both soil and solution were treated with 1 % w/w sorbents. Comparing different carbon-based materials, PAC, mixed mode carbon mineral material and GAC were the most effective in sorbing PFASs in both solution and soil. Among the different physical characteristics measured, the sorption of long-chain and more hydrophobic PFASs in both soil and solution was best correlated with sorbent surface area measured using methylene blue, which highlights the importance of mesopores in PFASs sorption. Iodine number was found to be a better indicator of the sorption of short-chain and more hydrophilic PFASs from solution but was found to be poorly correlated with PFASs immobilization in soil for activated carbons. Sorbents with a net positive charge performed better than those with a net negative charge, or no net charge. This study showed that surface area measured by methylene blue and surface charge are the best indicators of sorbent performance with respect to sorption/reducing leaching of PFASs. These properties may be helpful in selecting sorbents for PFASs remediation of soils/waters.

Impacts of abiotic factors on the fungal communities of 'Honeycrisp' apples in Canada.

The maintenance of the beneficial plant microbiome to control plant pathogens is an emerging concept of disease management, and necessitates a clear understanding of these microbial communities and the environmental factors that affect their diversity and compositional structure. As such, studies investigating the microbiome of economically significant cultivars within each growing region are necessary to develop adequate disease management strategies. Here, we assessed the relative impacts of growing season, management strategy, and geographical location on the fungal microbiome of 'Honeycrisp' apples from seven different orchard locations in the Atlantic Maritime Ecozone for two consecutive growing years. Though apple fruit tissue was dominated by relatively few fungal genera, significant changes in their fungal communities were observed as a result of environmental factors, including shifts in genera with plant-associated lifestyles (symbionts and pathogens), such as Aureobasidium, Alternaria, Penicillium, Diplodia, and Mycosphaerella. Variation in fungal composition between different tissues of fruit was also observed. We demonstrate that growing season is the most significant factor affecting fungal community structure and diversity of apple fruit, suggesting that future microbiome studies should take place for multiple growing seasons to better represent the host-microbiome of perennial crops under different environmental conditions.

The efficacy of soil washing for the remediation of per- and poly-fluoroalkyl substances (PFASs) in the field.

This paper aims to describe the performance of a soil washing plant (SWP) for remediating a per- and poly-fluoroalkyl substances (PFASs)-contaminated soil with a high clay content (61%). The SWP used both physical and chemical processes; fractionation of the soil particles by size and partitioning of PFASs into the aqueous phase to remove PFASs from the soil. Contaminated water was treated in series with granulated activated carbon (GAC) and ion-exchange resin and reused within the SWP. Approximately 2200 t (dry weight) of PFAS-contaminated soil was treated in 25 batches of 90 t each, with a throughput of approximately 11 t soil/hr. Efficiency of the SWP was measured by observed decreases in total and leachable concentrations of PFASs in the soil. Average removal efficiencies (RE) were up to 97.1% for perfluorocarboxylic acids and 94.9% for perfluorosulfonic acids. REs varied among different PFASs depending on their chemistry (functional head group, carbon chain length) and were independent of the total PFAS concentrations in each soil batch. Mass balance analysis found approximately 90% of the PFAS mass in the soil was transferred to the wash solution and > 99.9% of the PFAS mass in the wash solution was transferred onto the GAC without any breakthrough.

Per- and Poly-Fluoroalkyl Substances in Runoff and Leaching from AFFF-Contaminated Soils: a Rainfall Simulation Study.

The mobilization and transport of per- and poly-fluoroalkyl substances (PFASs) via surface runoff (runoff) from aqueous film-forming foam (AFFF)-contaminated soils during rainfall, flooding, or irrigation has not been thoroughly evaluated, and the effectiveness of carbonaceous sorbents in limiting PFASs in runoff is similarly unquantified. Here, laboratory-scale rainfall simulations evaluate PFAS losses in runoff and in leaching to groundwater (leachate) from AFFF-contaminated soils varying in texture, PFAS composition and concentration, and remediation treatment. Leaching dominated PFAS losses in soils with a concentration of ∑PFAS = 0.2-2 mg/kg. However, with higher soil PFAS concentrations (∑PFAS = 31 mg/kg), leachate volumes were negligible and runoff dominated losses. The concentration and variety of PFASs were far greater in leachates regardless of the initial concentrations in soil. Losses of PFASs were dependent on the C-chain length for leachates and more on the initial concentration in soil for runoff. Suspended materials did not meaningfully contribute to runoff losses. While concentrations of most PFASs declined significantly after the first rainfall event, desorption and transport in both runoff and leachates persisted over several rainfall events. Finally, results showed that sorption to AC mostly occurred during, not prior to, rainfall events and that 1% w/w AC substantially reduced losses in runoff and leachates from all soils.

Dermal Safety of Tapinarof Cream 1%: Results From 4 Phase 1 Trials.

BACKGROUND: Tapinarof (VTAMA®; Dermavant Sciences, Inc.) is a novel, non-steroidal, topical, aryl hydrocarbon receptor agonist, FDA approved for psoriasis treatment and under investigation for atopic dermatitis treatment as a 1% cream formulation for once-daily (QD) application. OBJECTIVE: Evaluate cumulative skin irritation, sensitization, and photoallergic and phototoxic potential of tapinarof cream 1% across a range of dosing frequencies and conditions. METHODS: We conducted 4 randomized, controlled, phase 1 trials of topical tapinarof cream 1% vs vehicle or other appropriate controls in healthy adults. Cumulative skin irritation was assessed following QD application for 21 days under fully occlusive patch conditions. Contact sensitization, photoallergenicity, and phototoxicity were assessed under semi-occlusive patch conditions. The contact sensitization and photoallergenicity trials used an induction phase of repeated applications followed by a 2-week rest period and a 1-time challenge, with rechallenge if responses indicated sensitization/photosensitization; the phototoxicity trial comprised a single application. Ultraviolet A and B irradiation was used to assess photoallergenicity/toxicity. RESULTS: 376 participants were randomized across the 4 trials. In the cumulative irritation trial, tapinarof cream 1% QD was classified as having a slight potential for very mild cumulative irritation under the exaggerated test conditions of repeated dosing for 21 days. There was no evidence of sensitization, photosensitization, or phototoxicity. Tapinarof was well tolerated and there was a low discontinuation rate across all trials. CONCLUSIONS: Tapinarof cream 1% was well tolerated, non-sensitizing, non-phototoxic, and non-photoallergic, with no evidence of clinically meaningful cumulative skin irritation in 4 dermal safety trials in healthy adults. TRIAL REGISTRATION: IND 104601 J Drugs Dermatol. 2022;21(10):1084-1090. doi:10.36849/JDD.6627R1.

Dearomatization of Cyclic Diphenylhydrazines: Harnessing the o-Semidine Rearrangement for the Synthesis of Spirocyclic Tetrahydroquinolines.

The synthesis of novel tetrahydroquinoline-containing spirocycles has been achieved through an acid-promoted dearomatization of cyclic diarylhydrazines. The reaction, proceeding through a dearomative o-semidine rearrangement, furnishes a stable, yet reactive spirocyclohexadieniminium ion, which can further be used as an electrophile or a diene in a one-pot sequence. These transformations efficiently produce novel diazaspirocycles and allow for further synthetic elaboration of the cyclohexadienamine products.

Establishing a quality management framework for commercial inoculants containing arbuscular mycorrhizal fungi.

Microbial inoculants containing arbuscular mycorrhizal (AM) fungi are potential tools in increasing the sustainability of our food production systems. Given the demand for sustainable agriculture, the production of such inoculants has potential economic value and has resulted in a variety of commercial inoculants currently being advertised. However, their use is limited by inconsistent product efficacy and lack of consumer confidence. Here, we propose a framework that can be used to assess the quality and reliability of AM inoculants. First, we set out a range of basic quality criteria which are required to achieve reliable inoculants. This is followed by a standardized bioassay which can be used to test inoculum viability and efficacy under controlled conditions. Implementation of these measurements would contribute to the adoption of AM inoculants by producers with the potential to increase sustainability in food production systems.

Assessment of Mobilization Potential of Per- and Polyfluoroalkyl Substances for Soil Remediation.

This study investigated the mobilization of a wide range of per- and polyfluoroalkyl substances (PFASs) present in aqueous film-forming foams (AFFFs) in water-saturated soils through one-dimensional (1-D) column experiments with a view to assessing the feasibility of their remediation by soil desorption and washing. Results indicated that sorption/desorption of most of the shorter-carbon-chain PFASs (C ≤ 6) in soil reached greater than 99% rapidly─after approximately two pore volumes (PVs) and were well predicted by an equilibrium transport model, indicating that they will be readily removed by soil washing technologies. In contrast, the equilibrium model failed to predict the mobilization of longer-chain PFASs (C ≥ 7), indicating the presence of nonequilibrium sorption/desorption (confirmed by a flow interruption experiment). The actual time taken to attain 99% sorption/desorption was up to 5 times longer than predicted by the equilibrium model (e.g., ∼62 PVs versus ∼12 PVs predicted for perfluorooctane sulfonate (PFOS) in loamy sand). The increasing contribution of hydrophobic interactions over the electrostatic interactions is suggested as the main driving factor of the nonequilibrium processes. The inverse linear relationship (R2 = 0.6, p < 0.0001) between the nonequilibrium mass transfer rate coefficient and the Freundlich sorption coefficient could potentially be a useful means for preliminary evaluation of potential nonequilibrium sorption/desorption of PFASs in soils.

Tapinarof Cream 1% for Extensive Plaque Psoriasis: A Maximal Use Trial on Safety, Tolerability, and Pharmacokinetics.

BACKGROUND: Tapinarof is a novel topical therapeutic aryl hydrocarbon receptor modulating agent in development for the treatment of psoriasis and atopic dermatitis. OBJECTIVE: This multicenter, open-label trial assessed the safety, tolerability, pharmacokinetics (PK), and efficacy of tapinarof cream 1% once daily (QD) under maximal use conditions in extensive plaque psoriasis. METHODS: Adults with a baseline Physician Global Assessment (PGA) score of ≥ 3 and body surface area (BSA) involvement ≥ 20% received tapinarof cream 1% QD for 29 days. Safety and tolerability assessments included adverse events (AEs) and local tolerability scales. PK parameters were calculated using non-compartmental analysis. Efficacy assessments included change in PGA, Psoriasis Area and Severity Index score, and %BSA affected. RESULTS: Twenty-one patients were enrolled. Common AEs were folliculitis, headache, back pain, and pruritus (none led to discontinuation). Tapinarof plasma exposure was low, with the majority of concentrations being below detectable limits. At day 29, 14 patients (73.7%) had a ≥ 1-grade improvement in PGA score and six patients (31.6%) had a ≥ 2-grade improvement; four patients (21.1%) achieved treatment success (PGA 0 or 1 and ≥ 2-grade improvement). CONCLUSION: Tapinarof cream 1% QD was well tolerated, with limited systemic exposure and significant efficacy at 4 weeks in patients with extensive plaque psoriasis. ClinicalTrials.gov Identifier NCT04042103.

Comparing the Leaching Behavior of Per- and Polyfluoroalkyl Substances from Contaminated Soils Using Static and Column Leaching Tests.

Soil contaminated with aqueous film-forming foams (AFFFs) containing per- and polyfluoroalkyl substances (PFASs) at firefighting training sites has become a major concern worldwide. To date, most studies have focused on assessing soil-water partitioning behavior of PFASs and the key factors that can affect their sorption, whereas PFASs leaching from contaminated soils have not yet been widely investigated. This study evaluated the leaching and desorption of a wide range of PFASs from twelve contaminated soils using the Australian Standard Leaching Procedure (ASLP), the U.S. EPA Multiple Extraction Procedure (MEP), and Leaching Environmental Assessment Framework (LEAF). All three leaching tests provided a similar assessment of PFAS leaching behavior. Leaching of PFASs from soils was related to C-chain lengths and their functional head groups. While short-chain (CF2 ≤ 6) PFASs were easily desorbed and leached, long-chain PFASs were more difficult to desorb. PFASs with a carboxylate head group were leached more readily and to a greater extent than those with a sulfonate or sulfonamide head group. Leaching of long-chain PFASs was pH-dependent where leaching increased at high pH, while leaching of short-chain PFASs was less sensitive to pH. Comparing different leaching tests showed that the results using the alkaline ASLP were similar to the cumulative MEP data and the former might be more practical for routine use than the MEP. No single soil property was adequately able to describe PFAS leaching from the soils. Overall, the PFAS chemical structure appeared to have a greater effect on PFAS leaching from soil than soil physicochemical properties.

Development of an organomineral fertiliser formulation that improves tomato growth and sustains arbuscular mycorrhizal colonisation.

Achieving sustainable agricultural development requires the efficient use of nutrient resources for crop production. Recovering nutrients from animal manures may play a key role in achieving this. Animal manures typically have low nutrient concentrations, and in ratios that are often not ideal for balanced crop nutrition. Here, combinations of organic and inorganic phosphorus (P) were formulated as granular products (organomineral fertilisers) with granule size suitable for transport and spreading. The fertilisers were produced by granulating powdered chicken litter with MAP and urea powders making the following formulations: 0:4, 1:3, 2:2, 3:1, 4:0. The kinetics of NH4+-N and P release from the fertilisers, and the effects on tomato growth and nutrition, as well as arbuscular mycorrhizal formation in roots following fertiliser application, were determined. Cumulative NH4+-N release ceased within 12 h, and was lower in the formulations with higher proportions of chicken litter. The cumulative P released reached approximately 80% of total P in all formulations, and the time to obtain maximum P dissolution was 19 days in the formulation that contained only chicken litter. The organomineral fertilisers increased tomato shoot growth by 15-28% compared to the chicken litter only, MAP only and MAP/urea formulations. Reasonable levels of mycorrhizal colonisation of tomato roots was achieved with the organomineral fertilisers. The results demonstrated that optimum plant growth does not depend solely on immediately available P, and that timing of nutrient supply to match plant demand is important. The combination of chicken litter with MAP sustained nutrient supply and improved plant growth. Taken together, organomineral fertiliser formulations are potential alternatives to inorganic P fertilisers that can improve crop growth and nutrition, while provide a sustainable use for animal production wastes.

Using 77Se-Labelled Foliar Fertilisers to Determine How Se Transfers Within Wheat Over Time.

Foliar selenium (Se) fertilisation has been shown to be more efficient than soil-applied fertilisation, but the dynamics of absorption and translocation have not yet been explored. An experiment was undertaken to investigate time-dependent changes in the absorption, transformation, and distribution of Se in wheat when 77Se-enriched sodium selenate (Sefert) was applied to the leaves at a rate of 3.33 µg Se per kg soil (equivalent to 10 g ha-1) and two growth stages, namely stem elongation, Zadoks stage 31/32 (GS1), and heading stage, Zadoks stage 57 (GS2). The effect of urea inclusion in foliar Se fertilisers on the penetration rates of Se was also investigated. Wheat was harvested at 3, 10, and 17 days and 3, 10, and 34 days after Se applications at GS1 and GS2, respectively. Applying foliar Se, irrespective of the formulation, brought grain Se concentration to a level high enough to be considered adequate for biofortification. Inclusion of N in the foliar Se solution applied at an early growth stage increased recoveries in the plants, likely due to improved absorption of applied Se through the young leaves. At a later growth stage, the inclusion of N in foliar Se solutions was also beneficial as it improved the assimilation of applied inorganic Se into bioavailable selenomethionine, which was then rapidly translocated to the grain. The practical knowledge gained about the optimisation of Se fertiliser formulation, method, and timing of application will be of importance in refining biofortification programs across different climatic regimes.

Screening fertilizers for their phosphorus runoff risk using laboratory methods.

Losses of phosphorus (P) from fertilized fields may result in degradation of water quality. Various initiatives are under evaluation to minimize water contamination, including the adoption of less soluble or coated P fertilizer formulations aiming to mitigate losses of P in runoff. Field-based rainfall simulators are traditionally used to evaluate P runoff, but using these is time consuming, labor intensive, and costly given the complex apparatus and analyses involved. We hypothesized that laboratory-based methods could be useful to evaluate the risk of P runoff from fertilizers. In order to identify a rapid, inexpensive, and efficient screening process, we compared two laboratory-scale measurements, one in water (based on electrical conductivity measurements) and one in soil (based on visualization of P diffusion in soil), with runoff results from field-, glasshouse-, and laboratory-based rainfall simulators, using coated soluble phosphate fertilizers. The laboratory-based methods assessing the P release rate in water and in soil correlated closely (r ≥ .96) with the losses of P obtained in the three rainfall simulators regardless of the type of coating or solubility of the fertilizer. The faster and inexpensive electrical conductivity and diffusion visualization methodologies were useful to rank the fertilizers by P release to runoff. Hence, these tools may be useful for screening fertilizer formulations with respect to their runoff risk.

Durability of sorption of per- and polyfluorinated alkyl substances in soils immobilized using common adsorbents: 2. Effects of repeated leaching, temperature extremes, ionic strength and competing ions.

Persistent use of aqueous film-forming foams containing per- and polyfluoroalkyl substances (PFASs) in firefighting has led to severe contamination of soil and aquifers at training sites, which makes remediation of such sites a necessity. We investigated the persistence of binding of PFASs to a mixed-mode remediation agent including repeated leaching, and the effects of competing ions and temperature extremes. The sorbent (RemBind®) was added to PFAS-contaminated soils and standard leaching procedures - the U.S. EPA Multiple Extraction Procedure and the U.S. EPA Leaching Environmental Assessment Framework were applied to quantify desorption of PFASs from remediated and unremediated soils. Possible desorption by competing anions such as orthophosphate (H2PO4-) and humic acid (HA) were assessed, and effects of temperature extremes and ionic strength were also investigated. These are the main environmental factors that could potentially affect desorption of PFASs over time at a typical site. Desorption of PFASs from unremediated soils was related to C-chain length with short-chain PFASs easily desorbed and leached. PFASs with carboxylic head groups leached faster than those with a sulfonic acid head group. The sorbent retained PFASs strongly and reduced desorption and leaching from remediated soils by 92 to 99.9%. There were no detrimental effects on desorption of PFASs from temperature extremes or changes in ionic strength. In remediated soils, effects of competing ions were also absent or minimal. However, in unremediated soils increasing concentrations of orthophosphate and HA increased leaching of some long-chain PFASs. While short-term laboratory desorption experiments cannot exactly mimic long-term field conditions, these results provide site owners and regulatory authorities with a high level of confidence that PFASs binding by RemBind® is predicted to be persistent in the long term. However, to give the greatest level of confidence, these simulations should be validated under field conditions for at least several years.

Durability of sorption of per- and polyfluorinated alkyl substances in soils immobilised using common adsorbents: 1. Effects of perturbations in pH.

The global problem of groundwater being contaminated with per- and polyfluoroalkyl substances (PFASs) originating from highly contaminated soils has created a need to remediate these locations. In situ immobilisation of PFASs in soil by applying sorbents is often a preferred low-cost technique to reduce their mobility and leaching to groundwater, but the long-term efficacy of sorbents has not yet been investigated. In this study, the longevity of remediation of two different soils by two common sorbents (RemBind®, and pulverized activated carbon, Filtrasorb™ 400) was assessed. Regulatory agencies often rely on standardised leaching procedures to assess the risk of contaminant mobility in soils. Hence, the Australian Standard Leaching Procedure and the U.S. EPA Leaching Environmental Assessment Framework were applied to quantify the desorption/leaching of a wide range of PFASs from unremediated and remediated soils under a range of pH conditions (pH 2 to 12). Ease of desorption and subsequent leaching from the unremediated soils was related to C-chain length; while short-chain PFASs were easily desorbed and leached, long-chain PFASs were more difficult to desorb. Desorption of long-chain PFASs was also pH dependent in unremediated soils, with desorption being greater at high pH. Both sorbents retained PFASs strongly in the remediated soils (> 99% for most PFASs) across a broad range of pH conditions, with only small differences between the sorbents in terms of efficacy. Both sorbents showed better retention of PFASs under low pH conditions. Remediation of PFAS-contaminated soils with these sorbents could be considered robust and durable in terms of changes in soil pH, with little risk of subsequent PFASs desorption under normal environmental pH conditions. Ultimately, to give regulators and site owners the greatest level of confidence that immobilisation is stable for the longer term, it should also be tested under repeated cycles of leaching and under different conditions.

An investigation into the long-term binding and uptake of PFOS, PFOA and PFHxS in soil - plant systems.

This study investigated the potential aging and plant bioaccumulation of three perfluoroalkyl acids (PFAAs), perfluorosulphonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorohexanesulphonic acid (PFHxS) in 20 soils over a six-month period. Sorption coefficients (Log Kd) ranged from 0.13-1.28 for PFHxS, 0.17-1.06 for PFOA and 0.98-2.03 for PFOS, respectively, and bioaccumulation factors (Log BAFs) ranged from 0.29-1.24, 0.22-1.46 and 0.05-0.65 for PFHxS, PFOA and PFOS, respectively. Over the six-month period, Kd values significantly increased for PFHxS and PFOA but the magnitude of the increase was very small and did not translate into differences in plant PFAA-concentrations between aged and freshly spiked treatments. The Kd and BAF values were modelled by multiple linear regression (MLR) to soil physico-chemical properties and by partial least squares regression to soil spectra acquired by mid-infrared spectroscopy (DRIFT-PLSR). Modelling of each PFAA was influenced by different soil properties, including organic carbon, pH, CEC, exchangeable cations (Ca2+, Mg2+, Na+ and K+) and oxalate extractable Al. BAF values were not strongly correlated to any soil property but were inversely correlated to Kd values. Our results indicate that limited aging occurred in these soils over the six-month period.