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.

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.

Influences of Chemical Properties, Soil Properties, and Solution pH on Soil-Water Partitioning Coefficients of Per- and Polyfluoroalkyl Substances (PFASs).

The aim of this study was to assess the soil-water partitioning behavior of a wider range of per- and polyfluoroalkyl substances (PFASs) onto soils covering diverse soil properties. The PFASs studied include perfluoroalkyl carboxylates (PFCAs), perfluoroalkane sulfonates (PFSAs), fluorotelomer sulfonates (FTSs), nonionic perfluoroalkane sulfonamides (FASAs), cyclic PFAS (PFEtCHxS), per- and polyfluoroalkyl ether acids (GenX, ADONA, 9Cl-PF3ONS), and three aqueous film-forming foam (AFFF)-related zwitterionic PFASs (AmPr-FHxSA, TAmPr-FHxSA, 6:2 FTSA-PrB). Soil-water partitioning coefficients (log Kd values) of the PFASs ranged from less than zero to approximately three, were chain-length-dependent, and were significantly linearly related to molecular weight (MW) for PFASs with MW > 350 g/mol (R2 = 0.94, p < 0.0001). Across all soils, the Kd values of all short-chain PFASs (≤5 -CF2- moieties) were similar and varied less (<0.5 log units) compared to long-chain PFASs (>0.5 to 1.5  log units) and zwitterions AmPr- and TAmPr-FHxSA (∼1.5 to 2 log units). Multiple soil properties described sorption of PFASs better than any single property. The effects of soil properties on sorption were different for anionic, nonionic, and zwitterionic PFASs. Solution pH could change both PFAS speciation and soil chemistry affecting surface complexation and electrostatic processes. The Kd values of all PFASs increased when solution pH decreased from approximately eight to three. Short-chain PFASs were less sensitive to solution pH than long-chain PFASs. The results indicate the complex interactions of PFASs with soil surfaces and the need to consider both PFAS type and soil properties to describe mobility in the environment.

The complex effect of dissolved organic carbon on desorption of per- and poly-fluoroalkyl substances from soil under alkaline conditions.

Per- and poly-fluoroalkyl substances (PFASs) are contaminants of emerging concern, yet the understanding of factors that control their leaching and release from contaminated soils remains limited. This study aimed to investigate the impact of dissolved organic carbon (DOC) on the release of PFASs-specifically, perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), and perfluorooctanoic acid (PFOA)from soils contaminated by aqueous film forming foam (AFFF). Batch aqueous leaching experiments were conducted on AFFF-contaminated soils under alkaline solution conditions (pH 9.5, 10.5, and 12) as it enhances leaching of both PFAS and DOC. Leaching of PFOS was significantly increased under alkaline conditions. Although the leaching of PFAS generally increased with pH, PFOS appeared to be more retained under the very alkaline pH conditions used in this study. At the same solution pH, leaching of PFOS and DOC was less in Ca(OH)2 than in NaOH. The retention of PFOS under these conditions may be attributable to the shielding of the negative charge of the soil components and colloids (e.g., DOC and clay minerals) in the leachates and/or the screening of negative charges on head groups of PFOS due to the high concentration of divalent cations. Solution chemistry affected desorption of PFOS more than PFHxS and PFOA. The study highlights that the influence of DOC on PFAS leaching and transport can be very complex, and depends on leachate chemistry (e.g., pH and cation type), PFAS chemistry, the magnitude of PFAS contamination and factors that influence the solid:liquid partitioning of organic carbon in soil.

Combined effects of cadmium and zinc on growth, tolerance, and metal accumulation in Chara australis and enhanced phytoextraction using EDTA.

Chara australis (R. Br.) is a macrophytic alga that can grow in and accumulate Cd from artificially contaminated sediments. We investigated the effects of Zn independently and in combination with Cd on C. australis growth, metal tolerance, and uptake. Plant growth was reduced at concentrations ≥ 75 mg Zn (kg soil)⁻¹. Zn also increased the concentration of glutathione in the plant, suggesting alleviation of stress. Phytotoxic effects were observed at ≥ 250 mg added Zn (kg soil)⁻¹. At 1.5mg Zn (kg soil)⁻¹, the rhizoid bioconcentration factor (BCF) was >1.0 for both Cd and Zn. This is a criterion for hyperaccumulator status, a commonly used benchmark for utility in remediation of contaminated soils by phytoextraction. There was no significant interaction between Cd and Zn on accumulation, indicating that Chara should be effective at phytoextraction of mixed heavy metal contamination in sediments. The effects of the chelator, ethylenediaminetetraacetic acid (EDTA), were also tested. Moderate levels of EDTA increased Cd and Zn accumulation in rhizoids and Cd BCF of shoots, enhancing Chara's potential in phytoremediation. This study demonstrates for the first time the potential of macroalgae to remove metals from sediments in aquatic systems that are contaminated with a mixture of metals.

Effect of heavy metal co-contaminants on the sorption of thirteen anionic per- and poly-fluoroalkyl substances (PFAS) in soils.

Understanding the sorption behavior of per- and poly-fluoroalkyl substances (PFAS) in soils are essential for assessing their mobility and risk in the environment. Heavy metals often coexist with PFAS depending on the source and history of contamination. In this study, we investigated the effect of heavy metal co-contaminants (Pb2+, Cu2+ and Zn2+) on the sorption of 13 anionic PFAS with different perfluorocarbon chain length (C3-C9) in two soils with different properties. Results revealed that Pb2+, Cu2+ and Zn2+ had little effect on the sorption of most short-chain compounds, while the presence of these heavy metals enhanced the sorption of long-chain PFAS in two soils. The distribution coefficients (Kd) of several long-chain PFAS linearly increased with increasing concentrations of heavy metal, especially in the presence of Pb2+ (ΔKd/Δ [Pb2+] > 3 for PFOS and PFNA vs <1 for PFPeS and PFHxS). While several mechanisms may have contributed to the enhancement of sorption of PFAS, the heavy metals most likely contributed through enhanced hydrophobic interactions of PFAS by neutralizing the negative charge of adsorption surfaces in soils and thus making it more favorable for their partitioning onto the solid phase. Moreover, the increase in the concentrations of heavy metals led to a decrease in the pH of the system and promoted sorption of long-chain compounds, especially in soil with lower organic carbon content. Overall, this study provides evidence that the presence of co-existing heavy metal cations in soils can significantly enhance the sorption of long-chain PFAS onto soil, thereby potentially limiting their mobility in the environment.

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.

Stabilisation of PFAS in soils: Long-term effectiveness of carbon-based soil amendments.

Immobilisation/stabilisation is one of the most developed and studied approaches for treating soils contaminated with per- and poly-fluoroalkyl substances (PFAS). However, its application has been inhibited by insufficient understanding of the effectiveness of added soil sorbents over time. Herein, we present results on the effectiveness of select carbon-based sorbents, over 4 years (longevity) and multiple laboratory leaching conditions (durability). Standard batch leaching tests simulating aggressive, worst-case scenario conditions for leaching (i.e., shaking for 24-48 h at high liquid/solid ratios) were employed to test longevity and durability of stabilisation in clay-loam and sandy-loam soils historically contaminated with PFAS (2 and 14 mg/kg ∑28 PFAS). The different sorbents, which were applied at 1-6% (w/w), reduced leaching of PFAS from the soils to varying degrees. Among the 5 sorbents tested, initial assessments completed 1 week after treatment revealed that 2 powdered activated carbon (PAC) sorbents and 1 biochar were able to reduce leaching of PFAS in the soil by at least 95%. Four years after treatment, the performance of the PAC sorbents did not significantly change, whilst colloidal AC improved and was able to reduce leaching of PFAS by at least 94%. The AC-treated soils also appeared to be durable and achieved at least 95% reduction in PFAS leaching under repetitive leaching events (5 times extraction) and with minimal effect of pH (pH 4-10.5). In contrast, the biochars were affected by aging and were at least 22% less effective in reducing PFAS leaching across a range of leaching conditions. Sorbent performance was generally consistent with the sorbent's physical and chemical characteristics. Overall, the AC sorbents used in this study appeared to be better than the biochars in stabilising PFAS in the long term.

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.

Increasing ionic strength and valency of cations enhance sorption through hydrophobic interactions of PFAS with soil surfaces.

The effect of soluble cations on sorption in soils of a range of anionic PFAS is not well studied. We investigated the role of three common cations (Na+, Ca2+, and Mg2+) at varying solution concentrations on the sorption coefficients (Kd) of 18 anionic PFAS in two contrasting soils. The effective charge of the soil suspension (Zeta potential) became less negative as the concentration of these cations increased in the soil solutions. Perfluorinated compounds showed greater sorption than polyfluorinated compounds, with sulfonates of comparable chain lengths showing higher sorption than the carboxylates. We observed that the Kd values of several PFAS in the two soils were positively correlated with the concentration of cations in solution, especially in the presence of polyvalent cations (Ca2+and Mg2+). The changes in sorption with cation concentration were more prominent for long-chain PFAS, with C > 10 PFAS being completely removed from solution at higher cation concentrations. The emerging PFAS (replacement compounds GenX and ADONA) showed negligible or little sorption (Kd < 0.6 L/kg). While several mechanisms contribute towards sorption of PFAS in the presence of cations, we conclude that the primary effect of cations is through screening of negative charges on head groups of PFAS and reorientation of molecules at the interface between organic matter surfaces and soil solution as well as charge neutralisation at soil solid surface. Screening of negative charges allows for greater hydrophobic interaction between hydrophobic tails of PFAS and soil surfaces resulting in greater sorption. Increasing cation concentrations in soil solutions could thus reduce mobility of PFAS through a soil profile.

Differences in soil mobility and degradability between water-dispersible CdSe and CdSe/ZnS quantum dots.

The relative leaching potential and degradation of water-dispersible CdSe and CdSe/ZnS quantum dots (QDs) were evaluated using small-scale soil columns. The potential of QDs to release toxic Cd(2+) and/or Se(2-)/SeO(3)(2-) ions upon degradation is of environmental concern and warrants investigation. Both classes of QDs exhibited limited soil mobility in CaCl(2), with more than 70% of the total Cd and Se species from QDs retained in the top soil after passing 10 column volumes of solution through the soil column. However, mobilization of Cd- and Se-species was observed when EDTA was used as the leaching solution. Approximately 98% of the total Cd(2+) loaded leached out from the Cd(2+)-spiked soil, while only 30% and 60% leached out from the CdSe and CdSe/ZnS QD-spiked soils, respectively. Soil column profiles and analysis of leachates suggest that intact QDs leached through the soil. Longer incubation (15 days) in soil prior to leaching indicated some degradation and/or surface modification of both QDs. These results suggest that chelating agents in the environment can enhance the soil mobility of intact and degraded QDs. It is apparent that QDs in soil, including the polymer-coated CdSe/ZnS QDs that are generally assumed to possess a higher degree of environmental stability, can undergo chemical transformations, which subsequently dictate their overall mobility.

Cd tolerance and accumulation in the aquatic macrophyte, Chara australis: potential use for charophytes in phytoremediation.

We investigated the potential use of the alga Chara australis (R. Br.) forphytore mediation of Cd-contaminated sediments in aquatic systems. Chara tolerated up to 20 mg added Cd (kg soil)⁻¹ in laboratory culture. Chlorophyll a and b levels were not affected even at Cd concentrations that suppressed growth. Levels of glutathione were suppressed at 2-35 mg added Cd (kg soil)⁻¹ to 200-350 nmol GSH (g DW)⁻¹, while control levels were 660 nmol GSH (g DW)⁻¹). Histochemical studies showed Cd occurred throughout cell walls and cytoplasm in plants grown in 5-20 mg Cd (kg soil)⁻¹. Quantification using ICP-MS showed the maximum concentration in shoots was 72 mg Cd (kg DW)⁻¹ at 35 mg added Cd (kg soil)⁻¹, while the maximum in rhizoids was 116 mg Cd (kg DW)⁻¹ at 25 mg added Cd (kg soil)⁻¹. The bioconcentration factor (BCF, concentration in plant/concentration in soil) exceeded 1.0, the critical value for hyperaccumulators, for shoots exposed to 35 mg Cd (kg soil)⁻¹ and rhizoids exposed to ≥25 mg Cd (kg soil)⁻¹. Translocation factors (TF, shoot concentration/rhizoid concentration) did not exceed 1.0 for any treatment. While Chara cannot be considered a hyperaccumulator, it shows promise for use in phytoremediation efforts.

Humic acid-induced silver nanoparticle formation under environmentally relevant conditions.

The formation of silver nanoparticles (AgNPs) via reduction of silver ions (Ag(+)) in the presence of humic acids (HAs) under various environmentally relevant conditions is described. HAs tested originated from the Suwannee River (SUW), and included samples of three sedimentary HAs (SHAs), and five soils obtained across the state of Florida. The time required to form AgNPs varied depending upon the type and concentration of HA, as well as temperature. SUW and all three SHAs reduced Ag(+) at 22 °C. However, none of the soil HAs formed absorbance-detectable AgNPs at room temperature when allowed to react for a period of 25 days, at which time experiments were halted. The appearance of the characteristic surface plasmon resonance (SPR) of AgNPs was observed by ultraviolet-visible spectroscopy in as few as 2-4 days at 22 °C for SHAs and SUW. An elevated temperature of 90 °C resulted in the accelerated appearance of the SPR within 90 min for SUW and all SHAs. The formation of AgNPs at 90 °C was usually complete within 3 h. Transmission electron microscopy and atomic force microscopy images showed that the AgNPs formed were typically spherical and had a broad size distribution. Dynamic light scattering also revealed polydisperse particle size distributions. HAs appeared to colloidally stabilize AgNPs based on lack of any significant change in the spectral characteristics over a period of two months. The results suggest the potential for direct formation of AgNPs under environmental conditions from Ag(+) sources, implying that not all AgNPs observed in natural waters today may be of anthropogenic origin.

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.

Sorption behaviour of per- and polyfluoroalkyl substances (PFASs) as affected by the properties of coastal estuarine sediments.

The sorption of three perfluoroalkyl substances (PFASs), namely perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorohexane sulfonic acid (PFHxS), was determined in 19 coastal sediments. There are currently limited data on the sorption behaviour of these chemicals in marine or estuarine sediments and the properties controlling their sorption have not been well established. The median average PFOS Kd value (30.4 L/kg) was >8 times that for PFOA (3.3 L/kg) and PFHxS (2.8 L/kg). Highly significant (P < .001) linear relationships were found between values for sorption coefficients (Kd) for all three chemicals (PFOS, PFOA and PFHxS) to the estuarine sediments and organic carbon (OC) content with r2 values ranging from 0.87 to 0.91. The nature of the constituents of OC was determined by nuclear magnetic resonance (NMR) for a subset (10) of the sediments to assess whether the strong relationship between sorption and OC was due solely to an increasing amount of OC or to particular OC fractions. The NMR analysis could not provide strong evidence for one OC fraction type explaining the variation in sorption of the three PFASs. Further investigation using partial least squares of the whole spectra also did not show any particular OC components could explain the Kd variation. This data suggests that variation in sorption in these sediments was primarily due to the varying OC content and not its chemistry.

Mineralisation and release of 14C-graphene oxide (GO) in soils.

Graphene-based nanomaterials (GNMs) have been touted as miracle materials due to their extraordinary properties that can benefit many industries, including in agriculture and for environmental remediation. While improvement in nutrient delivery and the ability to adsorb environmental contaminants have been demonstrated, what happens to GNMs in soil is a question that has not been addressed. The main aim of this study was to investigate their degradation in soil to have a better understanding of their environmental fate. Using radioisotope techniques, this study assessed the potential mineralisation and release of graphene oxide (GO), one of the most commonly used forms of graphene. Results revealed that the conversion of GO to carbon dioxide was negligible (<2%) in microbially-active soils. GO remaining in soil was also not readily released by water extractions. The lack of mineralisation and release is indicative of GO's high (bio)degradation stability which is likely due to its limited availability resulting from its rapid homo/hetero-aggregation. Over-all, the results provide new and important information on the environmental fate of graphene nanomaterials applied to soils.

Sorption of PFOA onto different laboratory materials: Filter membranes and centrifuge tubes.

Measurement and reporting of concentrations of contaminants of emerging concern such as per- and polyfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA), is an integral part of most investigations. Occurrence of sorption losses of PFAS analytes onto particular laboratory-ware (e.g. glass containers) has been suggested in the published literature but has not been investigated in detail. We examined sorption losses from aqueous PFOA solutions in contact with different commonly-used materials in filter units and centrifuge tubes (glass and plastics). Sorption of PFOA onto different filter membrane types ranged from 21-79% indicating that filtration can introduce a major source of error in PFOA analysis; pre-treatment of filter membranes with phosphate or methanol solutions did not improve PFOA recovery. Substantial adsorption of PFOA was also observed on tubes made from polypropylene (PP), polystyrene (PS), polycarbonate (PC), and glass where losses observed were between 32-45%, 27-35%, 16-31% and 14-24%, respectively. Contrary to suggestions in the literature, our results indicated that the greatest sorption losses for PFOA occurred on PP, whereas losses on glass tubes were much lower. Variations in ionic strength and pH did not greatly influence PFOA recovery. When PFOA concentrations were increased, the percent recovery of PFOA increased, indicating that binding sites on tube-walls were saturable. This study draws attention towards analytical bias that can occur due to sorption losses during routine procedures, and highlights the importance of testing the suitability of chosen laboratory-ware for specific PFAS analytes of interest prior to experimental use.

Predicting partitioning of radiolabelled 14C-PFOA in a range of soils using diffuse reflectance infrared spectroscopy.

The aim of this study was to establish partitioning coefficients (Kd) of perfluorooctanoic acid (PFOA) in a wide range of soils and determine if those values can be predicted from soil properties using multiple linear regression (MLR) and from infrared spectra of soils using partial least squares regression (PLSR). For 100 different soils, the Kd values of spiked radiolabelled 14C-PFOA ranged from 0.6 to 14.8 L/kg and significantly decreased with soil depth (p < 0.05) due to soil properties that change with depth. The MLR modelling revealed that PFOA sorption was significantly (p < 0.05) influenced, in decreasing order, by organic carbon (OC) content, silt-plus-clay content and soil pH. Soils were partitioned into all soils and surface soils alone. The MLR models using OC, silt-plus-clay content and pH together explained most of the variation in sorption in all soils as well as surface soils alone (0-15 cm). However, correlations between soil properties and Kd values in some soils could not be explained by the MLR model. Modelling of Kd prediction in soils with PLSR and diffuse reflectance (mid) infrared Fourier transform spectroscopy (DRIFT) showed comparable success in explaining the predictions of Kd values, including some of the outliers identified in the MLR model. The PLSR loading weights suggested that quartz, and possibly pyrophyllite minerals, were inversely correlated with the Kd values. Given that MLR requires a-priori characterisation of a range of soil properties and PLSR-DRIFT is a method based on the direct relationship between spectra and soil components, mid-infrared spectroscopy may be a more economical and rapid technique to predict the solid-liquid partitioning of PFOA in soils.

Ecological Risk Assessment of Nano-enabled Pesticides: A Perspective on Problem Formulation.

Plant protection products containing nanomaterials that alter the functionality or risk profile of active ingredients (nano-enabled pesticides) promise many benefits over conventional pesticide products. These benefits may include improved formulation characteristics, easier application, better targeting of pest species, increased efficacy, lower application rates, and enhanced environmental safety. After many years of research and development, nano-enabled pesticides are starting to make their way into the market. The introduction of this technology raises a number of issues for regulators, including how does the ecological risk assessment of nano-enabled pesticide products differ from that of conventional plant protection products? In this paper, a group drawn from regulatory agencies, academia, research, and the agrochemicals industry offers a perspective on relevant considerations pertaining to the problem formulation phase of the ecological risk assessment of nano-enabled pesticides.

Fate of radiolabeled C60 fullerenes in aged soils.

Fullerenes (e.g. C60, C70, etc.) present in soil may undergo changes in its retention with aging. In this study, the partitioning behavior of (14C)-C60 aged up to 12 weeks was investigated in biosolids-amended soil. Spiked samples were subjected to sequential partitioning using water, methanol, and toluene followed by total combustion of solids; the distribution of 14C across solvents and matrices were used to provide insights on C60 behavior. In most samples, 14C only partitioned in toluene with the remaining (non-extractable) activity detected in the solid phase. In all biosolids-amended soil samples, an increase in non-extractable 14C were observed for those exposed to light (vs dark) with the greatest difference observed in biosolids + sand samples. Possible processes that contribute to the observed 14C distribution, i.e. retention and potential transformation of C60, were discussed. Over-all, results suggest that environmental exposure to C60 and potentially transformed C60 species, as a result of their release from soils, is likely to be low.