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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., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Shervin Kabiri reports financial support was provided by Australian Research Council. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

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., (Crown Copyright © 2019. Published by Elsevier Ltd. All rights reserved.)

Fullerenes (e.g. C 60 , C 70 , etc.) present in soil may undergo changes in its retention with aging. In this study, the partitioning behavior of ( 14 C)-C 60 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 14 C across solvents and matrices were used to provide insights on C 60 behavior. In most samples, 14 C 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 14 C 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 14 C distribution, i.e. retention and potential transformation of C 60, were discussed. Over-all, results suggest that environmental exposure to C 60 and potentially transformed C 60 species, as a result of their release from soils, is likely to be low., (Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.)

Two experiments were conducted where three biochars, made from macadamia nutshell (MS), hardwood shaving (WS) and chicken litter (CL), were co-composted with chicken manure and sawdust, and also incubated with a chicken litter based commercial compost. Biochars were added at the rates of 5% and 10% in the co-composting and 10% and 20% in the incubation experiment. The rates of biochar had no consistent effect on the change in element contents of composted- or incubated-biochars. The biochar C demonstrated recalcitrance in both composting and incubation systems. Composting increased the CEC of biochars probably due to thermophilic oxidation. The increases in CEC of WS and CL were 6.5 and 2.2 times, respectively, for composting. Translocation of elements, between biochar and compost medium, occurred in both directions. In most cases, biochars gained elements under the influence of positive difference of concentrations (i.e., when compost medium had higher concentration of elements than biochar), while in some cases they lost elements despite a positive difference. Biochar lost some elements (WS: B; CL: B, Mg and S) under the influence of negative difference of concentrations. Some biochars showed strong affinity for B, C, N and S: the concentration of these elements gained by biochars surpassed the concentration in the respective composting medium. The material difference in the biochars did not have influence on N retention: all three netbag-biochars increased their N content. The cost of production of biochar-compost will be lower in co-composting than incubation, which involves two separate processes, i.e., composting and subsequent incubation., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Sorption of non-ionic organic compounds to soil is usually expressed as the carbon-normalized partition coefficient (KOC), because it is assumed that the main factor that influences the amount sorbed is the organic carbon content of the soil. However, KOC can vary by a factor of at least ten across a range of soils. We investigated two potential causes of variation in diuron KOC - organic matter-mineral interactions and organic matter chemistry - for a diverse set of 34 soils from Sri Lanka, representing a wide range of soil types. Treatment with hydrofluoric acid (HF-treatment) was used to concentrate soil organic matter. HF-treatment increased KOC for the majority of soils (average factor 2.4). We attribute this increase to the blocking of organic matter sorption sites in the whole soils by minerals. There was no significant correlation between KOC for the whole soils and KOC for the HF-treated soils, indicating that the importance of organic matter-mineral interactions varied greatly amongst these soils. There was as much variation in KOC across the HF-treated soils as there was across the whole soils, indicating that the nature of soil organic matter is also an important contributor to KOC variability. Organic matter chemistry, determined by solid-state (13)C nuclear magnetic resonance (NMR) spectroscopy, was correlated with KOC for the HF-treated soils. In particular, KOC increased with the aromatic C content (R=0.64, p=1×10(-6)), and decreased with O-alkyl C (R=-0.32, p=0.03) and alkyl C (R=-0.41, p=0.004) content., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Manufactured nanoparticles (NPs) present in consumer products could enter soils through re-use of biosolids. Among these NPs are those based on silver (Ag), which are found sulphidised (e.g. silver sulphide, Ag2S) in biosolids. Herein, our aim was to examine the release of retained Ag(0) and Ag2S NPs in soils and biosolids as facilitated by environmentally and agriculturally relevant ligands. Under natural soil conditions, exemplified by potassium nitrate and humic acid experiments, release of Ag retained in soil was limited. The highest total Ag release was facilitated by ligands that simulated root exudates (citrate) or fertilisers (thiosulphate). Released Ag was predominantly present in the colloidal phase (>3 kDa-< 0.45 μm); intact NPs only identified in Ag2S-NP extracts. For biosolids containing nanoparticulate-Ag-S, release was also enhanced by thiosulphate, though mostly as colloidal-Ag - not intact NPs. These results suggest that exposure to NPs as a result of its release from soils or biosolids will be low., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Pharmaceuticals have been detected in the soil environment where there is the potential for uptake into crops. This study explored the fate and uptake of pharmaceuticals (carbamazepine, diclofenac, fluoxetine, propranolol, sulfamethazine) and a personal care product (triclosan) in soil-plant systems using radish (Raphanus sativus) and ryegrass (Lolium perenne). Five of the six chemicals were detected in plant tissue. Carbamazepine was taken up to the greatest extent in both the radish (52 μg/g) and ryegrass (33 μg/g), whereas sulfamethazine uptake was below the limit of quantitation (LOQ) (<0.01 μg/g). In the soil, concentrations of diclofenac and sulfamethazine dropped below the LOQ after 7 days. However, all pharmaceuticals were still detectable in the pore water at the end of the experiment. The results demonstrate the ability of plant species to accumulate pharmaceuticals from soils with uptake apparently specific to both plant species and chemical. Results can be partly explained by the hydrophobicity and extent of ionization of each chemical in the soil.

Indaziflam is a relatively new herbicide for which sorption-desorption information is lacking, and nothing is available on its metabolites. Information is needed on the multiple soil and pesticide characteristics known to influence these processes. For four soils, the order of sorption was indaziflam (N-[1R,2S)-2,3-dihydro-2,6-dimethyl-1H-inden-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: Kf = 5.9, 1/nf = 0.7, Kfoc = 447; sandy loam: Kf = 3.9, 1/nf = 0.9, Kfoc = 276) > triazine indanone metabolite (N-[(1R,2S)-2,3-dihydro-2,6-dimethyl-3-oxo-1H-inden-1-yl]-6-[(1R)-1-fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: Kf = 2.1, 1/nf = 0.8, Kfoc = 177; sandy loam: Kf = 1.7, 1/nf = 0.9, Kfoc = 118) > fluoroethyldiaminotriazine metabolite (6-[(1R-1-Fluoroethyl]-1,3,5-triazine-2,4-diamine) (sandy clay loam: Kf = 0.3, 1/nf = 0.9, Kfoc = 28; sandy loam: Kf = 0.3, 1/nf = 0.9, Kfoc = 22) = indaziflam carboxylic acid metabolite (2S,3R)-3-[[4-amino-6-[(1R)-1-fluoroethyl]-1,3,5-triazin-2-yl]amino]-2,3-dihydro-2-methyl-1H-indene-5-carboxylic acid) (sandy clay loam: Kf = 0.3, 1/nf = 0.9, Kfoc = 22; sandy loam: Kf = 0.5, 1/nf = 0.8, Kfoc = 32). The metabolites being more polar than the parent compound showed lower sorption. Desorption was hysteretic for indaziflam and triazine indanone metabolite, but not for the other two metabolites. Unsaturated transient flow Kd's were lower than batch Kd's for indaziflam, but similar for fluoroethyldiaminotriazine metabolite. Batch Kd's would overpredict potential offsite transport if desorption hysteresis is not taken into account.

This study compared the degradation of indigenous bisphenol A (BPA) and triclosan (TCS) in a biosolids-amended soil, to the degradation of spiked labelled surrogates of the same compounds (BPA-d16 and TCS-(13)C12). The aim was to determine if spiking experiments accurately predict the degradation of compounds in biosolids-amended soils using two different types of biosolids, a centrifuge dried biosolids (CDB) and a lagoon dried biosolids (LDB). The rate of degradation of the compounds was examined and the results indicated that there were considerable differences between the indigenous and spiked compounds. These differences were more marked for BPA, for which the indigenous compound was detectable throughout the study, whereas the spiked compound decreased to below the detection limit prior to the study completion. The rate of degradation for the indigenous BPA was approximately 5-times slower than that of the spiked BPA-d16. The indigenous and spiked TCS were both detectable throughout the study, however, the shape of the degradation curves varied considerably, particularly in the CDB treatment. These findings show that spiking experiments may not be suitable to predict the degradation and persistence of organic compounds following land application of biosolids., (Copyright © 2013 Elsevier B.V. All rights reserved.)

We studied the sorption-desorption behaviour of two herbicides (diuron and artrazine) in a soil rich in Fe and Al oxides (Ferrosol), either amended freshly with two different types of biochars or that contained biochars aged under field conditions. Standard batch sorption-desorption experiments were conducted on soil samples freshly amended with two biochars, (namely, poultry litter - PL and paper mill - PM sludge) as well on those collected from field 32 months after biochar application. Soils that were freshly amended with biochars @ 10 t ha(-1) showed a two (PM) to five (PL) fold increase in sorption of herbicides as compared with that in the unamended soil. For example, the fresh amendments with PL biochar at 10 t ha(-1) led to a highly significant (P<0.001) increase in the Freundlich sorption coefficient (K(f)) of atrazine; i.e. 20.71 (n=0.40) as compared with 4.02 (n=0.70) for the control soil. Sorption was reversible in the unamended soil but sorption-desorption hysteresis was prominent in the soil amended with fresh biochars. In contrast, the soil containing aged biochars (at 10 t ha(-1)) exhibited sorption-desorption properties that were statistically similar to that of the control soil, especially for atrazine. Ageing of biochars in the soil over a 32 months period reduced the sorption capacity by 47% (PM) to 68% (PL) for diuron. These findings may have implications for herbicide efficacy in biochar amended soils., (Crown Copyright © 2012. Published by Elsevier B.V. All rights reserved.)

We studied the sorption behaviour of fullerene nano-C(60) particles (nC(60)) in soil from binary solvent mixtures of ethanol-water in order to critically evaluate the previous reports in the literature that the partitioning mechanism explains the soil sorption of fullerene C(60) as hydrophobic molecules. The sorption of nC(60) particles was studied in a range of solvent mixtures by changing volume fractions of ethanol from 20 to 100 percent. Sorption and particle characteristics were found to be very different in ethanol : water mixtures above and below 60% ethanol. In the range of 20-60% ethanol, sorption increased from 1.2 to 14.6 L kg(-1) accompanied by a change in zeta (ζ) potential from -32.4 to -7.2 mV. This observation can be attributed to hydrophilic interactions that negatively charged nC(60) particles undergo with soil colloids and water molecules. From 60% to 100% ethanol volume fractions, hydrophobic interactions of weakly charged nanoparticles may control the overall extent of soil sorption. The findings of this study indicate the importance of hydrophilic forces in controlling the sorption behaviour of nC(60) particles which are stabilized in water dominated solvent mixtures. The validity of the partitioning mechanism and K(OC) modelling approach in describing and estimating the sorption of nC(60) particles in soil (previously suggested in the literature) are, therefore, questioned.

Imidazolinones are chiral herbicides, comprised of two enantiomers with differential herbicidal activity. In this study, the selective degradation of enantiomers of the three imidazolinone herbicides, imazapyr, imazethapyr and imazaquin, was determined in a variety of soils selected to cover a broad range of physico-chemical characteristics. The R(+) enantiomer of all three herbicides, which has greater herbicidal activity (up to eight times), was found to degrade faster than the less active S(-) enantiomer. The enantiomer fraction (EF) was used as a descriptor of enantio-selectivity of the imidazolinone herbicides. The EF values increased with increasing incubation time for imidazolinones with a fast initial phase followed by a slower phase. While the enantio-selectivity was not significant in acidic soils (pH(w) 5.02 and 5.20), it was highly significant (P<0.001) in alkaline soils (pH(w) 7.6, 8.2 and 8.7). Significant positive correlations of EF values of imazapyr (P<0.001, R(2)=0.41), imazethapyr (P<0.002, R(2)=0.47) and imazaquin (P<0.001, R(2)=0.54) were found with the soil pH(w) ranging from 5.02 to 8.7. However, no correlation of EF was found with other soil properties. In addition to showing enantioselective degradation of the three herbicides in the soils studied, the study highlighted that for imidazolinones the herbicidally more active enantiomer can be preferably degraded by microorganisms., (Crown Copyright (c) 2010. Published by Elsevier Ltd. All rights reserved.)

An efficient and sensitive method for simultaneous determination of 38 pesticides in agricultural drainage waters and soils has been developed and validated. Water samples were extracted using solid-phase extraction with C18 cartridges while solid samples (suspended particle matter and soil) were extracted by using the quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction method. The target pesticides were analyzed by using gas chromatography-mass spectrometry with electron impact ionization. The proposed method allowed a simultaneous determination and confirmation of a large number of pesticides in agricultural drainage waters, suspended particle matters and soils/sediments with a good reproducibility and low detection limits. The developed method was applied to a survey of pesticides in a vegetable growing area of Guangzhou, China. The pesticides commonly found in the area were butachlor, carbofuran, dichlorvos, fipronil, isocarbophos and pyridaben.

Biochar derived from partial combustion of vegetation is ubiquitous and potentially effective in sequestration of environmental contaminants. Biochars were prepared by burning of red gum (Eucalyptus spp.) woodchips at 450 and 850 degrees C (labeled as BC450 and BC850). These two biochars were found to possess markedly different properties in terms of surface area and porosity. Short-term equilibration tests (24 hr) were conducted to assess the sorption-desorption behavior of pyrimethanil in the soil amended with various amounts of biochar of each type, with a special focus on the desorption behavior of the sorbed pesticide through four times successive desorption by dilution. Sorption coefficient and isotherm nonlinearity of the amended soils progressively increased with the content of biochar in the soil. Biochar BC850 with higher surface area and microporosity showed a stronger effect on the reversibility of sorption pesticide. The soils amended with 5% BC450 and 1% BC850 had nearly the same sorption capacity for pyrimethanil; however, their desorption processes were very different with 13.65% and 1.49% of the sorbed pesticide being released, respectively. This study suggested that biochar in soil could be an important factor for immobilization of a pesticide and thus affecting its environment fate in soil.

The effect of solvent-conditioning on the sorption of diuron and phenanthrene was investigated. The organic carbon-normalized sorption coefficients (K(OC)) for diuron and phenanthrene (determined from single initial concentrations of 0.8mgL(-1) and 1.5mgL(-1), respectively) were consistently higher following solvent-conditioning of a whole soil with five organic solvents (acetonitrile, acetone, methanol, chloroform and dichloromethane). The relative increase in K(OC) was inversely related to the polarity of the conditioning solvent (i.e. greater increases in K(OC) were observed for the least polar solvents: chloroform and dichloromethane). The effect of solvent-conditioning on the sorption properties of the same soil that had been lipid-extracted using accelerated solvent extraction (ASE) was also investigated. Since lipid extraction involves treatment with a non-polar solvent (95:5 dichloromethane:methanol) one may have expected no further increase in K(OC) on solvent-conditioning. On the contrary, the lipid-extracted soil exhibited very similar increases in K(OC) as the whole soil. This demonstrated that lipid removal and solvent-conditioning, which both increased K(OC) for this soil, are quite separate phenomena.

We investigated the effectiveness of two types of biochars in reducing the bioavailability of two soil-applied insecticides (chlorpyrifos and carbofuran) to Spring onion (Allium cepa). The biochars prepared from the pyrolysis of Eucalyptus spp. wood chips at 450 and 850 degrees C (BC850) were thoroughly mixed into the soil to achieve 0%, 0.1%, 0.5% and 1% by soil weight. A spring onion crop was grown for 5 wk in the biochar-amended soils spiked with 50 mgkg(-1) of each pesticide. The loss of both pesticides due to degradation and or sequestration in soils decreased significantly with increasing amounts of biochars in soil. Over 35 d, 86-88% of the pesticides were lost from the control soil, whereas it was only 51% of carbofuran and 44% of chlorpyrifos from the soil amended with 1.0% BC850. Despite greater persistence of the pesticide residues in biochar-amended soils, the plant uptake of pesticides decreased markedly with increasing biochar content of the soil. With 1% of BC850 soil amendment, the total plant residues for chlorpyrifos and carbofuran decreased to 10% and 25% of that in the control treatment, respectively. The BC850 was particularly effective in reducing phytoavailability of both pesticides from soil, due to its high affinity for and ability to sequester pesticide residues.

Both visible near-infrared (VNIR) and mid-infrared (MIR) spectroscopy have been claimed to better predict pesticide sorption in soils than other methods. We compared the performances of VNIR and MIR spectroscopy for predicting both organic carbon content (foc) and the sorption affinity (Kd) of diuron in 112 surface soils from South Australia. Separate calibration models were developed between VNIR and MIR spectra, and foc and Kd using partial least-squares (PLS) regression. MIR clearly outperformed VNIR for predictions of both foc and Kd in soils. Correlation (R2) and accuracy (RPD) indices were 0.4 and 1.3 for the VNIR-PLS model versus 0.8 and 2.3 for the MIR-PLS model, respectively, for Kd prediction. PLS loadings for sorption prediction were compared in terms of the soil information they contained. While VNIR loading did not include any direct spectral information regarding soil minerals, MIR loading included peaks associated with sand, clays, and carbonates. Perhaps by better predicting foc and integrating the effects of OC as well as minerals, the MIR-PLS model provided a better prediction for diuron Kd values in our calibration set.

The sorption of carbaryl (1-naphthyl methyl carbamate) and ethion [O,O,O',O'-tetraethyl S,S'-methylene bis(phosphorodithioate)] was studied in whole soils as well as after treatment of soil with 2% hydrofluoric acid (HF) to remove paramagnetic materials and to oxidize most forms of labile carbon by photo-oxidation with high energy (UV) on < 53 microm fractions. The sorption coefficient (K(d)) values for carbaryl and ethion in soils did not follow the order of their organic carbon (OC) content, and specially their char content However, the K(oc) values in < 53 microm fractions after hydrofluoric acid/photo-oxidation with high energy (hydrofluoric acid/ultraviolet; HF/UV) treatment were found to be much higher than those in bulk untreated soils. The effect of organic matter chemistry was determined by correlating K(oc) values of contaminants in bulk soils or 53 microm fractions against sample aromaticity. A poor correlation of K(oc) in bulk soil and aromatic C values of both carbaryl and ethion was observed. However, the correlation between the K(oc) and the aromatic fraction of C after the HF/UV treatment improved significantly, reflecting the contribution of char fraction of carbon in soils towards sorption of pesticides. The increase in sorption after HF/UV treatment suggested that the sorption potential of biochars, which are expected to contribute significantly to contaminant sorption due to their high surface area, can remain masked by the organo-mineral interactions of char in whole soils. This has implications for the modification of surfaces of the freshly applied biochars in soils due to organo-mineral interactions.

The influence of lipids on the sorption of diuron and phenanthrene to soils was investigated. Accelerated solvent extraction (ASE) was used to extract lipids from twelve soil horizons. Extractable lipids accounted for 3-13% of organic C. The organic carbon-normalized sorption coefficients (K(OC)) for diuron and phenanthrene were consistently higher for the lipid-extracted soils than for the whole soils (average of 31% for diuron and 29% for phenanthrene), indicating that lipids compete for or block sorption sites on the organic matter. Sorption experiments on one pair of HF-treated soils indicated that the blocking effects of minerals and lipids are independent, since lipid extraction and HF-treatment combined increased K(OC) by more than either treatment alone. Lipids extracted from whole and HF-treated soils were very similar in composition, consisting predominantly of long-chain polymethylene structures. K(OC) of the lipid itself was lower than for any of the whole soils and soil fractions (lipid extracted and HF-treated) for diuron, but higher for phenanthrene. Solid-state (13)C NMR spectra of the HF-treated soils before and after lipid extraction indicated that 15-20% of alkyl C was removed by ASE and that no other structures were affected.

Even though it is well established that soil C content is the primary determinant of the sorption affinity of soils for non-ionic compounds, it is also clear that organic carbon-normalized sorption coefficients (K(OC)) vary considerably between soils. Two factors that may contribute to K(OC) variability are variations in organic matter chemistry between soils and interactions between organic matter and soil minerals. Here, we quantify these effects for two non-ionic sorbates-diuron and phenanthrene. The effect of organic matter-mineral interactions were evaluated by comparing K(OC) for demineralized (HF-treated) soils, with K(OC) for the corresponding whole soils. For diuron and phenanthrene, average ratios of K(OC) of the HF-treated soils to K(OC) of the whole soils were 2.5 and 2.3, respectively, indicating a substantial depression of K(OC) due to the presence of minerals in the whole soils. The effect of organic matter chemistry was determined by correlating K(OC) against distributions of C types determined using solid-state (13)C NMR spectroscopy. For diuron, K(OC) was positively correlated with aryl C and negatively correlated with O-alkyl C, for both whole and HF-treated soils, whereas for phenanthrene, these correlations were only present for the HF-treated soils. We suggest that the lack of a clear effect of organic matter chemistry on whole soil K(OC) for phenanthrene is due to an over-riding influence of organic matter-mineral interactions in this case. This hypothesis is supported by a correlation between the increase in K(OC) on HF-treatment and the soil clay content for phenanthrene, but not for diuron.

This study explored the potential of mid-infrared spectroscopy (MIR) with partial least-squares (PLS) analysis to predict sorption coefficients (Kd) of pesticides in soil. The MIR technique has the advantage of being sensitive to both the content and the chemistry of soil organic matter and mineralogy, the important factors in the sorption of nonionic pesticides. MIR spectra and batch Kd values of atrazine were determined on a set of 31 soil samples as reference data for PLS calibration. The samples, with high variability in soil organic carbon content (SOC), were chosen from 10 southern Australian soil profiles (A1, A2, B, and C in one case). PLS calibrations, developed for the prediction of Kd from the MIR spectra and reference Kd data, were compared with predictions from Koc-based indirect estimation using SOC content. The reference Kd data for the 31 samples ranged from 0.31 to 5.48 L/kg, whereas Koc ranged from 30 to 680 L/kg. Both coefficients generally increased with total SOC content but showed a relatively poor coefficient of determination (R2 = 0.53; P > 0.0001) and a high standard error of prediction (SEP =1.22) for the prediction of Kd from Koc. This poor prediction suggested that total SOC content alone could explain only half of the variation in Kd. In contrast, the regression plot of PLS predicted versus measured Kd resulted in an improved correlation, with R2 = 0.72 ( P > 0.0001) and standard error of cross-validation (SECV) = 0.63 for three PLS factors. With the advantages of MIR-PLS in mind, (i) more accurate prediction of Kd, (ii) an ability to reflect the nature and content of SOC as well as mineralogy, and (iii) high repeatability and throughput, it is proposed that MIR-PLS has the potential for an improved and rapid assessment of pesticide sorption in soils.

The potential of mid-infrared (MIR) spectroscopy in combination with partial least-squares (PLS) regression was investigated to predict the soil sorption (distribution) coefficient (K(d)) of a nonionic pesticide (diuron). A calibration set of 101 surface soils collected from South Australia was utilized for reference sorption data and MIR spectra. Principal component analysis (PCA) was performed on the spectra to detect spectral outliers. The MIR-PLS model was developed and validated by dividing the initial data set into four validation sets. The model resulted in a coefficient of determination (R2) of 0.69, a standard error (SE) of 5.57, and a residual predictive deviation (RPD) of 1.63. The normalized sorption coefficient for the organic compound (K(oc)) approach, on the other hand, resulted in R2, SE, and RPD values of 0.42, 7.26, and 1.25, respectively. However, the significant statistical difference between the two models was mainly due to two outliers detected via PCA. Apart from spectral outliers, the performance of the two models was essentially similar for the rest of the calibration set. Outlier detection by the MIR-PLS model may gainfully be employed as a tool for improving prediction of K(d). The MIR-based model can provide a direct estimation of K(d) values based on the integrated properties of organic and mineral matter reflected in the infrared spectra.

Organic matter has long been recognized as the main sorbent phase in soils for hydrophobic organic compounds (HOCs). In recent times, there has been an increasing realization that not only the amount, but also the chemical composition, of organic matter can influence the sorption properties of a soil. Here, we show that the organic carbon-normalized sorption coefficient (K(OC)) for diuron is 27-81% higher in 10 A11 horizons than in 10 matching A12 horizons for soils collected from a small (2ha) field. K(OC) was generally greater for the deeper (B) horizons, although these values may be inflated by sorption of diuron to clays. Organic matter chemistry of the A11 and A12 horizons was determined using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. K(OC) was positively correlated with aryl C (r2=0.59, significance level 0.001) and negatively correlated with O-alkyl C (r2=0.84, significance level <0.001). This is only the second report of correlations between whole soil K(OC) and NMR-derived measures of organic matter chemistry. We suggest that this success may be a consequence of limiting this study to a very small area (a single field). There is growing evidence that interactions between organic matter and clay minerals strongly affect K(OC). However, because the soil mineralogy varies little across the field, the influence of these interactions is greatly diminished, allowing the effect of organic matter chemistry on K(OC) to be seen clearly. This study in some way reconciles studies that show strong correlations between K(OC) and the chemistry of purified organic materials and the general lack of such correlations for whole soils.

Charcoal derived from the partial combustion of vegetation is ubiquitous in soils and sediments and can potentially sequester organic contaminants. To examine the role of charcoal in the sorption and desorption behaviors of diuron pesticide in soil, synthetic charcoals were produced through carbonization of red gum (Eucalyptus spp.) wood chips at 450 and 850 degrees C (referred to as charcoals BC450 and BC850, respectively, in this paper). Pore size distribution analyses revealed that BC850 contained mainly micropores (pores approximately 0.49 nm mean width), whereas BC450 was essentially not a microporous material. Short-term equilibration (< 24 h) tests were conducted to measure sorption and desorption of diuron in a soil amended with various amounts of charcoals of both types. The sorption coefficients, isotherm nonlinearity, and apparent sorption-desorption hysteresis markedly increased with increasing content of charcoal in the soil, more prominently in the case of BC850, presumably due to the presence of micropores and its relatively higher specific surface area. The degree of apparent sorption-desorption hystersis (hysteresis index) showed a good correlation with the micropore volume of the charcoal-amended soils. This study indicates that the presence of small amounts of charcoal produced at high temperatures (e.g., interior of wood logs during a fire) in soil can have a marked effect on the release behavior of organic compounds. Mechanisms of this apparent hysteretic behavior need to be further investigated.

To better understand the environmental fate of pesticides in Sri Lankan soils, we studied the sorption behavior of two commonly used pesticides (carbofuran and diuron) in 43 surface soils representing a range of soil physicochemical properties from dry and wet zones of Sri Lanka. For carbofuran, the K(d) (L/kg) values varied from 0.11 to 4.1 (mean, 0.83; median, 0.62) and K(oc) ranged from 7.3 to 120.6 (mean, 41.65; median, 36.1), whereas for diuron K(d) values varied from 0.5 to 75 (mean, 9.6; median, 5.15) and K(oc) ranged from 55.3 to 962 (mean, 407; median, 328). A comparison of sorption data on these tropical soils with published studies (mostly European and north American soils) showed that the ranges of sorption coefficients from Sri Lankan soils were within the wide range of K(oc) values reported in the literature. However, these values for both pesticides in soils from dry zones of Sri Lanka were consistently higher (up to two times) than those from the wet zone. The wide range of K(oc) values in Sri Lankan soils may be due to the possible difference in the nature of soil organic carbon, which needs to be further investigated.

The sorption behavior of diuron, imidacloprid, and thiacloprid was investigated using 22 soils collected in triplicate from temperate environments in Australia and tropical environments in Australia and the Philippines. Within the temperate environment in Australia, the soils were selected from a range of land uses. The average KOC values (L/kg) for imidacloprid were 326, 322, and 336; for thiacloprid, the values were 915, 743, and 842; and for diuron, the values were 579, 536, and 618 for the Ord (tropical), Mt. Lofty (temperate), and Philippines (tropical) soils, respectively. For all soils, the sorption coefficients decreased in the following order: thiacloprid > diuron > imidacloprid. There were no significant differences in sorption behavior between the tropical soils from the Philippines and the temperate soils from Australia. Sorption was also not significantly related with soil characteristics, namely, organic carbon (OC) content, clay content, and pH, for any of the three chemicals studied. When the data were sorted into separate land uses, the sorption of all three chemicals was highly correlated (P < 0.001) with OC for the rice soils from the Philippines. Sorption coefficients for all three chemicals were highly correlated with OC in temperate, native soils only when one extreme value was removed. The relationships between sorption of all three chemicals and OC in temperate, pasture soils were best described by a polynomial. Sorption coefficients for imidacloprid and thiacloprid determined in the temperate pasture soils remained fairly consistent as the OC content increased from 3.3 to 5.3%, indicating that, although the total OC in the pasture soils was increasing, the component of OC involved with sorption of these two compounds may have been remaining constant. This study demonstrated that the origin of the soils (i.e., temperate vs tropical) had no significant effect on the sorption behavior, but in some cases, land use significantly affected the sorption behavior of the three pesticides studied. The impact of land use on the nature of soil OC will be further investigated by NMR analysis.

The transport and bioavailability of cadmium is governed mainly by its adsorption-desorption reactions with minerals such as goethite--a common iron oxide mineral in variable charged and highly weathered tropical soils. Soil factors such as pH, temperature, solution Cd concentration, ionic strength and ageing affect Cd adsorption on goethite. The desorption behaviour of Cd from goethite at low concentrations is not fully understood. This study investigates the adsorption-desorption of Cd at low Cd concentrations (Cd adsorbed on goethite from 20 to 300 microM Cd solutions) in Na and Ca nitrate solutions of 0.03 M nominal ionic strengths. Synthetic goethite prepared by ageing a ferric hydroxide gel at high pH and room temperature was used for Cd adsorption and desorption studies. For desorption experiment 10 successive desorptions were made for the whole range of initial Cd concentrations (20-300 microM) in the presence of 0.01 M Ca(NO3)2 or 0.03 M NaNO3 solutions. Cadmium adsorption was found to be higher in Na+ than Ca2+ probably due to the competition of Ca2+ ions with Cd2+ ions for adsorption sites on the surfaces of goethite. The effect of index cation on Cd adsorption diminished with increase in pH from 5.0 to 6.0. Cadmium desorption decreased with increase in pH from 5.0 to 6.0 in both Na and Ca systems. After 10 successive desorptions with 0.03 M NaNO3 at the lowest initially adsorbed Cd approximately 45%, 20% and 7% of the adsorbed Cd was desorbed at pH 5.0, 5.5 and 6.0, respectively. The corresponding desorptions in the presence of 0.01 M Ca(NO3)2 were 49%, 22% and 8%, respectively. The Freundlich parameter, k, based on each progressive step of desorption at different adsorbed concentration increased with increasing desorption step, which may indicates that a fraction of Cd was resistant to desorption. Low Cd desorbability from goethite may be due to its specific adsorption and/or possibly as a result of Cd entrapment in the cracks or defects in goethite structure.

Fullerenes (e.g. C 60 , C 70 , etc.) present in soil may undergo changes in its retention with aging. In this study, the partitioning behavior of ( 14 C)-C 60 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 14 C across solvents and matrices were used to provide insights on C 60 behavior. In most samples, 14 C 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 14 C 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 14 C distribution, i.e. retention and potential transformation of C 60, were discussed. Over-all, results suggest that environmental exposure to C 60 and potentially transformed C 60 species, as a result of their release from soils, is likely to be low. [ABSTRACT FROM AUTHOR]

Highlights: [•] Release of C60 is influenced by soil type. [•] Systems with elevated concentrations of DOC release relatively more C60. [•] Different forms of C60 have similar release behaviour. [•] Non-photoactivated formation of hydrophilic C60 appears to be a possibility in soil. [•] Apparent release of C60 from contaminated biosolids applied to soils will be limited. [Copyright &y& Elsevier]

Triclocarban and triclosan are two antimicrobial agents widely used in many personal care products. Their biodegradation behaviour in soil was investigated by laboratory degradation experiments and environmental fate modelling. Quantitative structure–activity relationship (QSAR) analyses showed that triclocarban and triclosan had a tendency to partition into soil or sediment in the environment. Fate modelling suggests that either triclocarban or triclosan “does not degrade fast” with its primary biodegradation half-life of “weeks” and ultimate biodegradation half-life of “months”. Laboratory experiments showed that triclocarban and triclosan were degraded in the aerobic soil with half-life of 108 days and 18 days, respectively. No negative effect of these two antimicrobial agents on soil microbial activity was observed in the aerobic soil samples during the experiments. But these two compounds persisted in the anaerobic soil within 70 days of the experimental period. [Copyright &y& Elsevier]

To have an effective barrier against invading termites around building structures and to assess the potential risks to the urban environment and human beings, we need to understand the fate of termiticides applied in urban soil. The movement and degradation of a new termiticide, fipronil, were investigated in Australian soils following standard termiticide treatment methods (surface application under slab and trenching treatments along walls). Surface application studies in three field sites showed slow dissipation and little movement for fipronil in all three soils under the simulated slab during a three-year period. The greatest mass of the chemical residues remained in the quartzite sand layer (thickness, 5 cm), and only small amounts of these were found to have migrated into the soil layers (depth, 0-15 cm) underneath the quartzite sand layer. Of the three metabolites (desulfinyl, sulfide, and sulfone) found in the soils, the sulfone derivative had the highest concentration. Persistence of fipronil was affected by application rate. The time for 50% loss of the total toxic components (fipronil plus its metabolites) in the quartzite sand layer (thickness, 5 cm) ranged from 200 to 326 d for the low rate (0.15 g active ingredient/m2) and from 633 to 674 d for the high application rate (3 g active ingredient/m²). One-year trenching studies at two sites in Adelaide (Roseworthy Farm [RF] and Terretfield [TF]; South Australia, Australia) showed that vertical movement and dissipation of fipronil occurred in the soils. The average concentration of fipronil in the trenches (depth, 0-30 cm) decreased from 33.7 to 14.9 mg/kg in the loam soil at the RF site and from 39.4 to 14.6 mg/kg in the clay soil at the TF site over the year. With time under the natural weather condition, fipronil and its derivatives were found in the deeper soil sections without treatment (depth, 20-30 cm). However, laboratory studies using repacked soil columns showed low mobility in the loam soil from the RF site and a variably charged clay soil from Malanda (Queensland, Australia) under intermittent wetting and drying conditions. [ABSTRACT FROM AUTHOR]

A high-performance liquid chromatography method with diode-array detection (HPLC-DAD) is described for the determination of three neonicotinoid insecticides imidacloprid, thiacloprid, and thiamethoxam in soil and water. The soil samples were extracted with acetonitrile, while the water samples were extracted using C18 cartridges. The mean recoveries plus standard deviations for spiked soil samples were 82 ± 4.2% for thiamethoxam, 99 ± 4.2% for imidacloprid and 94 ± 1.4% for thiacloprid. The recoveries for water samples ranged from 87 ± 3.4% for thiamethoxam to 97 ± 3.9% for imidacloprid and 97 ± 2.6% for thiacloprid. The limits of quantitation (LOQ) were 0.1, 0.1, 0.01 mg/kg in soil (5 g), and 2, 2, 0.5 µg/L in water (50 mL) for thiamethoxam, imidacloprid, and thiacloprid, respectively. [ABSTRACT FROM AUTHOR]

Widespread usage of per- and polyfluoroalkyl substances (PFASs) has caused major environmental contamination globally. The hydrophilic and hydrophobic properties of PFASs affect the sorption behaviour and suggest organic carbon may not be the only factor affecting sorption. We reviewed the quality of all data published in peer-reviewed literature on sorption of PFASs to critically evaluate the role organic carbon (OC) and other properties have in sorption of PFASs in soils or sediments. The largest data sets available were for perfluorooctanoic acid (PFOA, n = 147) and perfluorooctane sulfonic acid (PFOS, n = 178), and these analyses showed very weak correlations between sorption coefficient (K d ) and OC alone (R 2  = 0.05–0.07). When only laboratory-derived K d values of PFASs and OC were analysed, the R 2 values increased for PFOA (R 2  = 0.24, n = 42), PFOS (R 2  = 0.38, n = 69), perfluorononanoic acid (PFNA, R 2  = 0.77 n = 12), and perfluorodecanoic acid (PFDA, R 2  = 0.78, n = 13). However, the relationships were heavily skewed by one or two high OC values. Similarly there was no significant relationship between K d values and pH for PFOS (R 2  = 0.06) and PFOA (R 2  = 0.07), across a range of environmental pH values. Our analyses showed sorption behaviour of a range of PFASs could not be explained by a single soil or sediment property. Multiple regression models better explained the sorption behaviour of a number of PFASs. Regressions of OC and pH together explained a significant proportion of the variation in K d values for 9 out of 14 PFASs and 8 of these regressions had ≥10 data points. This review highlighted that at least OC, pH and clay content are properties having significant effect on sorption. There is a clear need for more data and studies with thorough characterisation of soils or sediments to better understand their role in PFASs sorption. Current assessments based on OC alone are likely to be erroneous. [ABSTRACT FROM AUTHOR]

Reuse of treated wastewater for irrigation of crops is growing in arid and semi-arid regions, whilst increasing amounts of biosolids are being applied to fields to improve agricultural outputs. Due to incomplete removal in the wastewater treatment processes, pharmaceuticals present in treated wastewater and biosolids can contaminate soil systems. Benzodiazepines are a widely used class of pharmaceuticals that are released following wastewater treatment. Benzodiazepines are represented by a class of compounds with a range of physicochemical properties and this study was therefore designed to evaluate the influence of soil properties on the sorption behaviour and subsequent uptake of seven benzodiazepines (chlordiazepoxide, clonazepam, diazepam, flurazepam, oxazepam, temazepam and triazolam) in two plant species. The sorption and desorption behaviour of benzodiazepines was strongly influenced by soil type and hydrophobicity of the chemical. The partitioning behaviour of these chemicals in soil was a key controller of the uptake and accumulation of benzodiazepines by radish ( Raphanus sativus ) and silverbeet ( Beta vulgaris). Benzodiazepines such as oxazepam that were neutral, had low sorption coefficients (K d ) or had pH-adjusted log octanol-water partition coefficients (log D ow , pH 6.3) values close to 2 had the greatest extent of uptake. Conversely, benzodiazepines such as flurazepam that had an ionised functional groups and greater K d values had comparatively limited accumulation in the selected plant species. Results also revealed active in-plant metabolism of benzodiazepines, potentially analogous to the known metabolic transformation pathway of benzodiazepines in humans. Along with this observed biological transformation of benzodiazepines in exposed plants, previously work has established the widespread presence of the plant signalling molecule γ-amino butyric acid (GABA), which is specifically modulated by benzodiazepines in humans. This highlights the need for further assessment of the potential for biological activity of benzodiazepines following their plant uptake. [ABSTRACT FROM AUTHOR]