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Char as a carbon-rich material, can be produced under pyrolytic conditions, wildfires or prescribed burn offs for fire management. The objective of this study was to elucidate mechanistic interactions of copper (Cu 2+ ) and nickel (Ni 2+ ) with different chars produced by pyrolysis (green waste, GW; blue-Mallee, BM) and forest fires (fresh-burnt by prescribed fire, FC; aged char produced by wild fire, AC). The pyrolytic chars were more effective sorbents of Cu 2+ (∼11 times) and Ni 2+ (∼5 times) compared with the forest fire chars. Both cross-polarization (CPMAS-NMR) and Bloch decay (BDMAS-NMR) 13 C NMR spectroscopies showed that forest fire chars have higher woody components (aromatic functional groups) and lower polar groups (e.g. O -alkyl C) compared with the pyrolytic chars. The polarity index was greater in the pyrolytic chars (0.99–1.34) than in the fire-generated chars (0.98–1.15), while aromaticity was lower in the former than in the latter. Fourier transform infrared (FTIR) and Raman spectroscopies indicated the binding of carbonate and phosphate with both Cu 2+ and Ni 2+ in all chars, but with a greater extent in pyrolytic than forest fire-generated chars. These findings have demonstrated the key role of char's oxygen-containing functional groups in determining their sorption capacity for the Cu 2+ and Ni 2+ in contaminated lands. [ABSTRACT FROM AUTHOR]

BACKGROUND The nitrifying trickling filter ( NTF) is a process commonly used in wastewater treatment to remove ammonia. What is less clear is its ability to remove emerging organic contaminants. This study evaluated the potential of NTF to remove eight trace organic chemicals of concern ( CoCs), with initial concentration of caffeine, bisphenol A, benzotriazole, trimethoprim and acetaminophen 1 mg L−1, atrazine 2 mg L−1, 17α-ethynylestradiol 5 mg L−1 and N, N-diethyl-m-toluamide 10 mg L−1, using a laboratory-scale NTF system. The impact of initial nitrification rate on chemicals' removal and the impact of chemicals on nitrification rate were investigated. RESULTS The removal efficiency of a recirculating NTF for CoC removal was in the following order: caffeine (98%) > acetaminophen and N, N-diethyl-m-toluamide (58.6%) > atrazine (48.7%) > 17α-ethynylestradiol (48.3%) > benzotriazole (42.8%) > bisphenol A (26.2%) > trimethoprim (17.9%). In NTFs, biodegradation was the dominant process. In this study, the removal of caffeine was found to be the most effective, and removal of trimethoprim the least. The removal efficiency of most chemicals increased, except for benzotriazole, with increasing nitrification. The presence of CoCs might negatively affect nitrification in NTFs. CONCLUSION The research demonstrated that recirculating high rate NTF is potentially an efficient approach for removal of trace organic contaminants. © 2016 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

Background and aims: Plant uptake of active pharmaceutical ingredients (APIs) is increasingly leading to concerns about their potential exposure to humans and wildlife via dietary intake. Due to the extraordinary ability of biochars to bind organic compounds, plant uptake experiments were conducted to assess the effect of soil-amendment of three different biochars on the uptake of APIs from spiked soil. Methods: Pot experiments were undertaken to assess the extent of sorption and corresponding bioaccessibility of two APIs (carbamazepine - CBZ and propranolol -PRL) to ryegrass ( Lolium perenne) grown in an API-spiked loamy sand, with and without biochar amendment (5 t/ha equivalent). The soil was amended with three different biochars produced from eucalyptus wood and wheat residues. Results: Both APIs were taken up by ryegrass, with CBZ preferentially accumulated (14.3 mg/kg CBZ, 3.8 mg/kg PRL in unamended soil) due to its comparatively high concentration in porewater. Soil amendment with biochars increased partitioning of the two APIs by up to three- fold, with corresponding decreases in porewater (34-72 % of unamended soil) and plant tissue (17-64 %) concentrations. Conclusions: Biochars were effective in reducing the uptake of APIs into plant tissues from a contaminated soil and may be effective in the management of API residues in contaminated soils. [ABSTRACT FROM AUTHOR]

Sorption of non-ionic organic compounds to soil is usually expressed as the carbon-normalized partition coefficient ( K OC ), because it is assumed that the main factor that influences the amount sorbed is the organic carbon content of the soil. However, K OC can vary by a factor of at least ten across a range of soils. We investigated two potential causes of variation in diuron K OC – 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 K OC 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 K OC for the whole soils and K OC 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 K OC 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 K OC variability. Organic matter chemistry, determined by solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy, was correlated with K OC for the HF-treated soils. In particular, K OC 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. [ABSTRACT FROM AUTHOR]

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 flowKd's were lower than batchKd's for indaziflam, but similar for fluoroethyldiaminotriazine metabolite. BatchKd's would overpredict potential offsite transport if desorption hysteresis is not taken into account. [ABSTRACT FROM AUTHOR]

Abstract: 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 32months after biochar application. Soils that were freshly amended with biochars @ 10tha−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 10tha−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 10tha−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 32months 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. [Copyright &y& Elsevier]

We investigated the occurrence and removal of four benzotriazoles (BTs) (benzotriazole: BT; 5-methyl-benzotriazole: 5-TTri; 5-chloro-benzotriazole: CBT; 5,6-dimethyl-benzotriazole: XTri) and six UV filters (benzophenone-3: BP-3; 3-(4-methylbenzylidene)camphor: 4-MBC; octyl 4-methoxycinnamate: OMC; 2-(3-t-butyl-2-hydroxy-5-methylphenyl)-5-chloro benzotriazole: UV-326; 2-(2′-Hydroxy-5′-octylphenyl)-benzotriazole: UV-329; octocrylene: OC) in a full scale municipal wastewater treatment in South Australia. BT, 5-TTri and BP-3 were found as the dominant compounds detected in the wastewater samples with average concentrations up to 5706 ± 928 ng/L, 6758 ± 1438 ng/L and 2086 ± 1027 ng/L in influent, and up to 2439 ± 233 ng/L, 610 ± 237 ng/L and 153 ± 121 ng/L in effluent, respectively. In the biosolid, 4-MBC and OC were found with the highest concentrations of 962 ± 135 ng/g and 465 ± 65 ng/g, respectively. Sorption onto sludge played a dominant role in the removal for UV filters, especially for 4-MBC, UV-326 and OC, which accounted for 54%–92% of influent loads, while biological degradation played a significant role for the other compounds. [Copyright &y& Elsevier]

Sorption and degradation of the five selected endocrine disrupting chemicals (EDCs) including bisphenol A (BPA), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), 4-tert-octylphenol (4-t-OP) and 4-n-nonylphenol (4-n-NP) have been investigated in the laboratory using sediment and groundwater from an aquifer in Bolivar, South Australia. The sorption coefficients measured on the sediment were in the following order: 4-n-NP>4-t-OP>EE2>E2>BPA. The sorption coefficients (Kf values) for the five EDCs were 3.89, 21.8, 24.2, 90.9 and 195, respectively. The alkylphenols 4-t-OP and 4-n-NP had strong binding on the sediment while BPA had a weak affinity. Degradation experiments of the five EDCs showed that E2 and 4-n-NP degraded quickly under aerobic conditions with a half-life of 2 and 7 days, respectively. EE2 degraded slowly with an estimated half-life of 81 days in the aquifer material under aerobic conditions while the other two chemicals (BPA and 4-t-OP) remained almost unchanged. Little or no degradation of the five EDCs except slow degradation for E2 was observed within 70 days under anaerobic conditions in native groundwater. [Copyright &y& Elsevier]

Hormone steroids are a group of endocrine disruptors, which are excreted by humans and animals. In this paper, we briefly review the current knowledge on the fate of these steroids in the environment. Natural estrogenic steroids estrone (E1), 17β-estradiol (E2) and estriol (E3) all have a solubility of approximately 13 mg/l, whereas synthetic steroids 17α-ethynylestradiol (EE2) and mestranol (MeEE2) have a solubility of 4.8 and 0.3 mg/l, respectively. These steroids have a moderate binding on sediments and are reported to degrade rapidly in soil and water. Estrogenic steroids have been detected in effluents of sewage treatment plants (STPs) in different countries at concentrations ranging up to 70 ng/l for E1, 64 ng/l for E2, 18 ng/l for E3 and 42 ng/l for EE2. E2 concentrations in river waters from Japan, Germany, Italy and the Netherlands ranged up to 27 ng/l. In addition, E2 concentrations ranging from 6 to 66 ng/l have also been measured in mantled karst aquifers in northwest Arkansas. This contamination of ground water has been associated with poultry litter and cattle manure waste applied on the land. Although hormone steroids have been detected at a number of sources worldwide, currently, there is limited data on the environmental behaviour and fate of these hormone steroids in different environmental media. Consequently, the exposure and risk associated with these chemicals are not adequately understood. [Copyright &y& Elsevier]

The sorption behaviour of three perfluoroalkyl substances (PFASs), namely perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorohexane sulfonic acid (PFHxS), was determined on 28 tropical soils. Tropical soils are often highly weathered, richer in sesquioxides than temperate soils and may contain variable charge minerals. There are little data on sorption of PFASs in tropical soils. The highest K d values were found for PFOS with mean values ranging from 0 to 31.6 L/kg. The K d values for PFOA and PFHxS ranged from 0 to 4.9 L/kg and from 0 to 5.6 L/kg, respectively. While these values are in the range of literature sorption data, the average K d values for PFOS and PFOA from the literature were 3.7 times and 3.6 times higher, respectively, than those measured in this study. Stepwise regression analysis did explain some of the variance, but with different explanatory variables for the different PFASs. The main soil properties explaining sorption for PFOS and PFOA were oxalate-extractable Al and pH, and for PFHxS was pH. Image 1 • Sorption values for PFOS, PFOA and PFHxS were determined for 28 tropical soils. • PFOS sorption values were approximately 3.7 times lower than mean literature values. • PFOA sorption values were approximately 3.6 times lower than mean literature values. • Sorption of PFOA and PFOS was explained by pH and oxalate-extractable Al. [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]

Studies were undertaken to assess sorption of seven endocrine-disrupting chemicals (EDCs), namely, estrone (E1), 17β-estradiol (E2), estriol (E3), 17α-ethynylestradiol (EE2), bisphenol A (BPA), 4-tert-octyl phenol (4-t-OP), and 4-n-nonyl phenol (4-n-NP) on four soils (from sandy to clay soil) with different physicochemical properties and biodegradation of five EDCs (BPA, E2, EE2, 4-t-OP, and 4-n-NP) in a loam soil associated with wastewater reuse. We also characterized the biotransformation of E2 to E1 in the loam soil under aerobic and anaerobic conditions. Sorption test using a batch equilibrium method demonstrated that alkylphenols (4-t-OP and 4-n-NP) had the strongest sorption onto soils, followed by estrogens (EE2, E2, E1, E3) and BPA. This laboratory study showed that all five EDCs, including the degradation product E1, were degraded rapidly in the soil within 7 d under aerobic conditions. However, under anaerobic conditions in the soil, little or no degradation of the five EDCs was noted except for E2, which showed slow degradation during the 70-d study. The calculated half-lives for E2 under anaerobic conditions were 24 d in the soil. Estradiol was found to be biotransformed to E1 under both aerobic and anaerobic conditions. The study suggested that the five EDCs as well as E1, which may be present in reclaimed wastewater, would not persist in well-aerated soil. But these EDCs persisting in anaerobic soil may affect soil and groundwater quality and ecosystem. [ABSTRACT FROM AUTHOR]

Batch experiments were conducted to evaluate the sorption-desorption behaviour of 14C-labelled carboxylic acids (citric and oxalic) and amino acids (glutamic, alanine, phenylalanine and lysine) on pure minerals (kaolinite, illite, montmorillonite, ferrihydrite and goethite). The sorption experiments were complemented by ATR-FTIR spectroscopy to gain possible mechanistic insight into the organic acids-mineral interactions. In terms of charge, the organic solutes ranged from strongly negative (i.e., citric) to positively charged solutes (i.e., lysine); similarly the mineral phases also ranged from positively to negatively charged surfaces. In general, sorption of anionic carboxylic and glutamic acids was higher compared to the other compounds (except lysine). Cationic lysine showed a stronger affinity to permanently charged phyllosilicates than Fe oxides. The sorption of alanine and phenylalanine was consistently low for all minerals, with relatively higher sorption and lower desorption of phenylalanine than alanine. Overall, the role of carboxylic functional groups for the sorption and retention of these carboxylic and amino acids on Fe oxides (and kaolinite) and of amino group on 2:1 phyllosilicates was noticeable. Mineral properties (surface chemistry, specific surface area), chemistry of the organic compounds (pKa value, functional groups) and the equilibrium pH of the system together controlled the differences in sorption-desorption patterns. The results of this study aid to understand the effects of mineralogical and chemical factors that affect naturally occurring low molecular weight organic compounds sorption under field conditions. [ABSTRACT FROM AUTHOR]

Abstract: 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. [Copyright &y& Elsevier]

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 13C 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. [Copyright &y& Elsevier]

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 13C 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. [Copyright &y& Elsevier]

Abstract: 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 (r 2 =0.59, significance level 0.001) and negatively correlated with O-alkyl C (r 2 =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. [Copyright &y& Elsevier]

The aim of this study was to establish partitioning coefficients (K d) 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 K d 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 K d values in some soils could not be explained by the MLR model. Modelling of K d prediction in soils with PLSR and diffuse reflectance (mid) infrared Fourier transform spectroscopy (DRIFT) showed comparable success in explaining the predictions of K d 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 K d 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. Unlabelled Image • Measured data on K d values for 100 Australian soils for PFOA • Key soil properties identified to predict sorption using MLR and DRIFT-PLSR • Sorption decreases with increasing depth in soil profile. • DRIFT-PLSR offers a better model to predict K d from soil properties than MLR. [ABSTRACT FROM AUTHOR]

Abstract 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. Highlights • Sorption of PFOA onto lab-ware can cause analytical bias during routine procedures. • Filtration of PFOA solutions can lead to underestimation of dissolved concentrations. • Sorption losses of PFOA onto polypropylene tubes was greater than on glass tubes. • Sorption losses decreased when concentrations of PFOA in test solutions increased. [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]

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. [ABSTRACT FROM AUTHOR]

• Long-term fate of PFAS in the vadose zone was analysed through numerical modelling. • Climate-driven physical flow processes can explain observed retention of PFAS in vadose zone. • PFAS downward flux confined to short periods of high soil saturation following discrete rain events. • Periods of enhanced PFAS downward movement coincide with low air-water interface retention. • Sorption to sediments and air-water interface reduce PFAS migration rate by 60%. Contamination through per-and poly-fluoroalkyl substances (PFAS) have occurred globally in soil and groundwater systems at military, airport and industrial sites due to the often decades-long periodic application of firefighting foams. At PFAS contaminated sites, the unsaturated soil horizon often serves as a long-term source for sustained PFAS contamination for both groundwater and surface water runoff. An understanding of the processes controlling future mass loading rates to the saturated zone from these source zones is imperative to design efficient remediation measures. In the present study, hydrochemical data from a site where PFAS transport was observed as a result of the decades-long application of AFFF were used to develop and evaluate conceptual and numerical models that determine PFAS mobility across the vadose zone under realistic field-scale conditions. The simulation results demonstrate that the climate-driven physical flow processes within the vadose zone exert a dominating control on the retention of PFAS. Prolonged periods of evapotranspiration exceeding rainfall under the semi-arid conditions trigger periods of upward flux and evapoconcentration, leading to the observed persistence of PFAS compounds in the upper ca. 2 metres of the vadose zone, despite cessation of AFFF application to soils since more than a decade. Physico-chemical retention mechanisms, namely sorption to the air-water interface (AWI) and sediment surfaces, contribute further to PFAS retention. The simulations demonstrate how PFAS downward transport is effectively confined to short periods following discrete rain events when soils display a high degree of saturation. During these periods, AWI sorption is at a minimum. In addition, high PFAS concentrations measured and simulated below the source zone reduce the effect of the AWI further due to a decrease in surface tension associated with elevated PFAS concentrations. Consequently, time-integrated PFAS migration and retardation illuminates that the field-relevant PFAS transport rates are predominantly controlled by the physical flow processes with a lower relative importance of AWI and sediment sorption adding to PFAS retention. [Display omitted] [ABSTRACT FROM AUTHOR]

Abstract: This study investigated the sorption–desorption behaviour of four pesticides by a by-product from mineral sand mining, commonly referred to as neutralised used acid (NUA). In batch studies the average amount of pesticide removed after 6h was 69% for atrazine, 89% for diuron, 61% for 2,4-D and 83% for chlorpyrifos. The lower sorption of 2,4-D to NUA compared with the other pesticides studied is most likely to be due to the high pH of the solutions (7.8 to 8.8) which would have resulted in 2,4-D being predominantly in an anionic form. The presence of other pesticides only significantly decreased the amount of 2,4-D sorbed from 59% to 34% when present in a mixture. Little (2 to 17%) diuron, chlorpyrifos, atrazine or 2,4-D were found to desorb from the NUA. The presence of nitrate or phosphate had minimal effect on the amount of diuron or atrazine sorbed to the NUA. However, all phosphate and nitrate treatments significantly (P<0.05) decreased the amount of 2,4-D sorbed (<50%) compared with when 2,4-D was present alone (65%). This study has shown that NUA has potential to be used as a sorbent for pesticides. [Copyright &y& Elsevier]

Abstract: We investigated how the sorption affinity of diuron (3′-(3,4-dichlorophenyl)-1,1-dimenthyl-urea), a moderately hydrophobic herbicide, is affected by soil properties, topography and management practices in an intensively managed orchard system. Soil-landscape analysis was carried out in an apple orchard which had a strong texture contrast soil and a landform with relief difference of 50m. Diuron sorption (K d ) affinity was successfully predicted (R 2 =0.79; p <0.001) using a mid-infrared – partial least squares model and calibrated against measured data using a conventional batch sorption technique. Soil and terrain properties explained 75% of the variance of diuron K d with TOC, pHw, slope and WI as key variables. Mean diuron K d values were also significantly different (p <0.05) between alley and tree line and between the different management zones. Soil in the tree line generally had lower sorption capacity for diuron than soil in the alleys. Younger stands, which were found to have lower TOC than in the older stands, also had lower diuron K d values. In intensively managed orchards, sorption affinity of pesticides to soils was not only affected by soil properties and terrain attributes but also by management regime. [Copyright &y& Elsevier]

Biodegradation and adsorption of selected endocrine-disrupting chemicals (EDCs), namely estrogens (E2 and EE2) and phenolic compounds (BPA, 4-t-OP and 4-n-NP), in aquifer materials was investigated in the laboratory in order to understand the behaviour and fate of these chemicals associated with reclaimed water during managed aquifer recharge. Biodegradation experiments were conducted in microcosms with aquifer material and groundwater mixture, or with aquifer material and effluent mixture in the presence of glucose under both aerobic and anoxic conditions. All five selected compounds were degraded by microorganisms in both types of aquifer material–water mixtures under aerobic and anoxic conditions. Under aerobic conditions, EE2 was found to degrade faster in the aquifer material supplemented with effluent with a half-life of 15 days compared with that of 26 days in the aquifer material and groundwater microcosm. No significant difference between the two aquifer material–water mixtures was found for the other four compounds with half-lives ranging between 0.2 and 4.1 days. Under anoxic conditions, however, little biodegradation was observed for the selected EDCs except for E2, which degraded in the aquifer material in the presence of both water types. [Copyright &y& Elsevier]

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 K d 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 (K d) 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 K d variation. This data suggests that variation in sorption in these sediments was primarily due to the varying OC content and not its chemistry. Unlabelled Image • Sorption values for PFOS, PFOA and PFHxS were determined for 19 estuarine sediments. • Median PFOS sorption values were approximately >8 times those for PFOA and PFHxS. • Sorption of all three PFASs was explained by increasing OC content in sediments. • No specific fraction(s) of OC could explain the variation in sorption of the PFASs. [ABSTRACT FROM AUTHOR]

We studied sorption potential for a range of herbicides using eleven waste materials (mill muds) containing organic matter (47.6 to 65.1%) produced by sugar mills and applied as soil conditioners by farmers. Sorption/desorption behaviour of five herbicides commonly used in sugarcane production (imazapic, atrazine, hexazinone, diuron and metribuzin) was studied on these mill muds, as is and after adding these to three soils at different rates (5–25%, dry weight basis). All mill muds had significant sorption capacity, especially for diuron, atrazine and metribuzin which was 6 to 26 times higher than the soil with 3.5% organic carbon (OC). Generally, sorption of the five herbicides assessed in all mill muds followed the order diuron > atrazine = metribuzin > hexazinone = imazapic. Eight out of 11 mill muds had similar sorption capacity for any given herbicides. Amending soils with selected mill muds significantly enhanced their sorption efficiency, depending on the rate of application especially in soil with low OC. Generally, application of mill muds at 5% w / w or 40 tons/ha increased sorption of studied herbicides by 2 to 10 folds. Soil amendment with mill muds also reduced the rate and extent of desorption of herbicides- especially mobile herbicides like metribuzin. Nearly 79% release of metribuzin was observed after three desorption steps in amended soil (at 5% w / w), whereas in unamended soil, 100% of metribuzin was released during first desorption step. The study demonstrates that wastes produced by sugar mills may have recycling use in enhancing the retention of mobile herbicides in soils with low OC content. Unlabelled Image • Organic waste (mill muds) from sugar mills could serves as sorbent of herbicides. • Sorption/desorption of five herbicides on 11 different mill muds was studied. • A 5% w / w application of mill muds to soils increased herbicide retention up to tenfold. • Soil amendment with mill muds significantly reduced the release of mobile herbicides. • Mill mud can be reused to minimise their off-site transport to the Great Barrier Reef. [ABSTRACT FROM AUTHOR]