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Aquifer storage and recovery (ASR) is an emerging and effective management technique in reclaiming and reusing waste water. During ASR, attenuation processes such as sorption and degradation may play an important role in removing trace organic contaminants in injected waste water. This study mainly investigated the role of treated sewage effluent injectant (the waste water injected into the aquifer) on degradation of two endocrine disrupting compounds, 17β-estradiol (E2) and 17α-ethynylestradiol (EE2), in the laboratory by comparing their behavior in incubation media--aquifer sediment/ground water slurry from the Bolivar experimental ASR site in South Australia and sediment/effluent slurry. Biodegradation of the two compounds in the sediment/ground water media (1:1, w/w) and in the sediment/effluent media (1:1, w/w) were conducted under aerobic and anaerobic conditions at 20 °C. In both incubation media, E2 showed a rapid biodegradation with a DT50 value (time for 50% loss) of ∼2 days under aerobic conditions. E2 degraded slowly in both aquifer media under anaerobic conditions; however, the anaerobic degradation was noted to be somewhat faster in the sediment/effluent media. In contrast, EE2 was found to be resistant to biodegradation and remained almost unchanged within 70 days under anaerobic conditions in both incubation media. The mobility of the two compounds in the aquifer would depend on their sorption. The sorption coefficients measured on the aquifer sediment were 7.7 ± 3.4 L/kg for E2 and 10.6 ± 5.1 L/kg for EE2 using batch equilibration methods. The corresponding retardation factors were calculated to be 25 for E2 and 34 for EE2 based on the physical properties of the aquifer material in the Bolivar ASR site. This study showed that while E2 has modest sorption affinity for aquifer material, it is rapidly biodegraded with or without the supplement of effluent under... [ABSTRACT FROM AUTHOR]

Microbial reduction of Fe(lll) in illite was studied to evaluate the possibility of microbial utilization of Fe(lll) in sedimentary clays and to determine the effects of bioreduction on clay composition and structure. A subsurface bacterium (Shewanella putrefaciens CN32) and illite separates (<0.2 µm) from St. Peter Formation sandstone in 0gle County, IL, were used in laboratory experiments. Illite suspensions buffered at pH 7 with bicarbonate were inoculated with CN32 and provided with H[sub 2] as an electron donor. In selected treatments, anthraquinone-2,6-disulfonate (AQDS), was included as an electron shuttle to facilitate the bioreduction. Fe(ll) production in inoculated treatments was determined by extraction with 0.5 N HCl and compared to uninoculated controls to establish the extent of biological reduction. The resulting solids were characterized by Mössbauer spectroscopy and scanning and transmission electron microscopy (SEM and TEM). The characterization of the starting illite material revealed that it contained a minor component of goethite (α-Fe00H) in addition to fibrous illite. The starting material (both goethite and illite) contained 6% (w/ w) total Fe, and 82% of the total Fe was Fe(lll). Approximately 30% of total Fe was associated with goethite. At the end of a 30-day incubation, residual goethite and illite remained. The extent of reduction was much greater in the presence of AQDS (25%) than in its absence (0%). Modeling of Mössbauer spectra of the bioreduced material indicated that both goethite and illite were reduced but to a different extent. Additionally, TEM evidence suggested that there was a dramatic change in illite morphology upon bioreduction from fibrous needles to plates. The ability of bacteria to utilize Fe(lll) in illite has important implications for microbial functions and survival mechanisms, as well as many geological processes, in the subsurface. [ABSTRACT FROM AUTHOR]

Estrogenic compounds may enter the environment when biosolids are applied to land. In the present study, soil samples were collected over 4 mo from a field trial following addition of biosolids. The recombinant yeast estrogen screen bioassay identified estrogenic activity in the soil at all sampling times to concentrations up to 2.3 µg 17β-estradiol equivalency/kg. The present results indicate the potential for estrogenic compounds to persist in soil following biosolids application. Environ Toxicol Chem 2014;33:26-28. © 2013 SETAC [ABSTRACT FROM AUTHOR]

The article focuses on the consideration of cultural and spiritual perspectives in pharmaceuticals and personal care products (PPCPs) among indigenous people in Australia and New Zealand. It states that PPCPs has strong cultural manifestations among indigenous people through the so called Asian vulture crisis. It also explores the PPCPs workshop hosted by the Society of Environmental Toxicology and Chemistry (SETAC) in Adelaide, South Australia in 2012.

Graphical abstract Highlights • Irrigated crops showed varied impact on the hydraulic and solute exchange to the river. • Annual flow to the river under almond was 2.1 times higher than wine grapes. • 20, 60, and 40 m buffers needed for grapes, almond, and annual horticulture, respectively, to control solutes to the river. • Solute residence time was twice long for grapes compared to almonds and annual horticulture. Abstract Riparian zones are essential to preserve water quality of rivers adjacent to large areas of irrigated agriculture. We used HYDRUS (2D/3D) to quantify the long-term (8 years) influence of crops (almonds, wine grapes and potato-carrot) irrigated with recycled water on water and solute exchange at the Gawler River interface in relation to vegetation buffer widths from 10 to 110 m. We found that under almond and annual horticulture the likely average annual water flow from the irrigated area to the river was nearly twice as much (2.1 and 1.8, respectively) that under wine grapes. The hydraulic exchange at river interface for different irrigated crops was found to be sensitive to the buffer widths. For wine grapes, almonds and annual horticulture, the average annual hydraulic balance reached an equilibrium at 20, 65 and 55 m buffer widths, respectively. Furthermore, for wine grapes, with a 20 m buffer width, the average annual load of salts became negligible. This study shows that buffer widths of 20, 60, and 40 m for irrigated wine grapes, almond, and annual horticulture, respectively, are needed to restrict the migration of salts to the river. Further refinements are possible by incorporating the influence of preferential flow paths, improved water stress response functions, and addressing the data limitations for calibration of the model for solute dynamics. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Chlorine has a higher reactivity with oxazepam than with diazepam. • pH affects the kinetic rate constants by impacting the reactant species of reactants. • The C-3 of 1,4-benzodiazepine structure is the main site of attack. • Transformation products will be comparatively stable during chlorination process. Abstract The pharmaceutical benzodiazepine diazepam and its metabolite oxazepam have been detected in wastewater treatment plants effluents, surface water and treated drinking water, but their transformation during chlorination process is not well understood. We investigated the reactions of diazepam and oxazepam with free available chlorine using a high-resolution mass analyzer and theoretical calculation to elucidate the fate of benzodiazepines during water chlorination process. The obtained apparent second-order rate constants (k app) for chlorine reaction with diazepam and oxazepam varied from 0.01 to 1.7 M−1 s−1 and 0.7 to 31.6 M−1 s−1 in the pH range of 5.5–10.0, respectively. Under typical wastewater disinfection conditions of neutral pH values, free chlorine concentrations of 5 mg L−1 and contact times of up to 2 h, the corresponding half-lives for diazepam (∼180 min) and oxazepam (∼61 min) suggest that diazepam will be partly transformed during disinfection. Conversely, oxazepam will be considerably transformed during wastewater disinfection. The pH-dependency of k app for diazepam could be explained by the reactions between neutral diazepam and HClO species. The kinetic pattern for oxazepam can be well described by species-specific reactions involving oxazepam or Cl 2 and Cl 2 O species. In total, fifteen and eight transformation products were identified for chlorination of diazepam and oxazepam, respectively. The C-3 of 1,4-benzodiazepine structure was the main site of attack, leading predominantly to the oxidation and then cleavage of the C(3)-N(4) bond, as well as diazepine ring contractions. Based on mass balance estimation, the main chlorination product for diazepam and oxazepam are 7-chloro-1-methyl-5-phenyl-1,3-dihydro-2H-1,4-benzodiazepin-2,3-dione and 6-chloro-4-phenyl-2(1H)-quinazolinone, 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]

• Overlooked contribution of PBMs towards the DBP formation was critically reviewed. • Elastomers, tire waste, polyelectrolytes, and MPs serve as potent DBP precursors. • Leached DOC and dissolved nitrogen from PBMs play a key role in DBP formation. • DBPs formation potential of polyelectrolytes was found as high as ∼2 mg/L. • DBPs formation potential of different microplastics ranged from 1.9 to 15,990 µg/L. Disinfection by-products (DBPs) are formed through the disinfection of water containing precursors such as natural organic matter or anthropogenic compounds (e.g., pharmaceuticals and pesticides). Due to the ever increasing use of plastics, elastomers, and other polymers in our daily lives, polymer-based materials (PBMs) are detected more frequently and at higher concentrations in water and wastewater. The present review provides a comprehensive and systematic analysis of the contribution of PBMs - including elastomers, tire waste, polyelectrolytes, and microplastics - as precursors of DBPs in water and wastewater. Literature shows that the presence of PBMs can lead to the leaching of dissolved organic matter (DOM) and subsequent formation of DBPs upon disinfection in aqueous media. The quantity and type of DBPs formed strongly depends on the type of polymer, its concentration, its age, water salinity, and disinfection conditions such as oxidant dosage, pH, temperature, and contact time. DOM leaching from elastomers and tire waste was shown to form N -nitrosodimethylamine up to concerning levels of 930 ng/L and 466,715 ng/L, respectively upon chemical disinfection under laboratory conditions. Polyelectrolytes can also react with chemical disinfectants to form toxic DBPs. Recent findings indicate trihalomethanes formation potential of plastics can be as high as 15,990 µg/L based on the maximum formation potential under extreme conditions. Our analysis highlights an overlooked contribution of DOM leaching from PBMs as DBP precursors during disinfection of water and wastewater. Further studies need to be conducted to ascertain the extent of this contribution in real water and wastewater treatment plants. [Display omitted] [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]

Organophosphorus, pyrethroid and chloronicotinyl insecticides have been used to control termites in building structures in recent years. We investigated the degradation behaviour of three insecticides (bifenthrin, chlorpyrifos and imidacloprid) at termiticidal application rates under standard laboratory conditions (25 deg. C, 60% field moisture capacity and darkness) for 24 months. The study was carried out onone soil and two bedding materials (sand-dolomite and quarry sand), which are commonly used under housing in Australia. Experiments were also conducted to examine the effect of soil moisture on the degradation of these insecticides. Insecticide residues in the samples collected at different days after application were measured by high performance liquid chromatography (HPLC). The rate of degradation of bifenthrin and imidacloprid insecticides was adequately described by a first-order kinetic model (r2 = 0.93-0.97). However, chlorpyrifos degradation was biphasic, showing an initial faster degradation followed by a slower rate. Therefore, the degradation data during the slower phase only (after a two-month period) followed the first-order law (r2 = 0.95). Soil moisture had little effect on degradation of imidacloprid and bifenthrin. Among the three insecticides, bifenthrin and imidacloprid were most stable and chlorpyrifos the least. Chlorpyrifos showed a major loss (75-90%) of residue during the 24months incubation period. In the bedding materials, simultaneous accumulation of the primary metabolite of chlorpyrifos, TCP (3,5,6-trichloro-2-pyridinol) was observed. Hydrolysis appeared to have caused the observed rapid loss of chlorpyrifos, especially in the highly alkaline bedding materials (sand-dolomite and quarry sand). [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]

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]

We investigated the effects of wastewater treatment plant (WWTP) discharge on the ecology of bacterial communities in the sediment of a small, low-gradient stream in South Australia. The quantification of genes involved in the biogeochemical cycling of carbon and nitrogen was used to assess potential impacts on ecosystem functions. The effects of disturbance on bacterial community structure were assessed by PCR- denaturing gradient gel electrophoresis of 16S rRNA genes, and clone library analysis was used to phylogenetically characterize significant shifts. Significant (P < 0.05) shifts in bacterial community structures were associated with alteration of the sediment's physicochemical properties, particularly nutrient loading from the WWTP discharge. The effects were greatest at the sampling location 400 m downstream of the outfall where the stream flow is reduced. This highly affected stretch of sediment contained representatives of the gammaproteobacteria that were absent from less-disturbed sites, including Oceanospirillales and Methylococcaceae. 16S rRNA gene sequences from less-disturbed sites had representatives of the Caulobacteraceae, Sphingomonadaceae, and Nitrospirae which were not represented in samples from disturbed sediment. The diversity was lowest at the reference site; it increased with proximity to the WWTP outfall and declined toward highly disturbed (400 m downstream) sites (P < 0.05). The potential for biological transformations of N varied significantly with the stream sediment location (P < 0.05). The abundance of amoA, narG, and nifH genes increased with the distance downstream of the outfall. These processes are driven by N and C availability, as well as redox conditions. Together these data suggest cause and effect between nutrient loading into the creek, shift in bacterial communities through habitat change, and alteration of capacity for biogeochemical cycling of N. [ABSTRACT FROM AUTHOR]

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]

This paper aims to describe the performance of a soil washing plant (SWP) for remediating a per- and poly-fluoroalkyl substances (PFASs)-contaminated soil with a high clay content (61%). The SWP used both physical and chemical processes; fractionation of the soil particles by size and partitioning of PFASs into the aqueous phase to remove PFASs from the soil. Contaminated water was treated in series with granulated activated carbon (GAC) and ion-exchange resin and reused within the SWP. Approximately 2200 t (dry weight) of PFAS-contaminated soil was treated in 25 batches of 90 t each, with a throughput of approximately 11 t soil/hr. Efficiency of the SWP was measured by observed decreases in total and leachable concentrations of PFASs in the soil. Average removal efficiencies (RE) were up to 97.1% for perfluorocarboxylic acids and 94.9% for perfluorosulfonic acids. REs varied among different PFASs depending on their chemistry (functional head group, carbon chain length) and were independent of the total PFAS concentrations in each soil batch. Mass balance analysis found approximately 90% of the PFAS mass in the soil was transferred to the wash solution and > 99.9% of the PFAS mass in the wash solution was transferred onto the GAC without any breakthrough. [Display omitted] • Full-scale soil washing remediation of a high clay content, PFAS-contaminated soil. • Soil removal efficiencies were > 97% and > 95% for PFCAs and PFSAs, respectively. • Removal efficiency was independent of PFAS concentration per batch of soil washed. • The soil washing plant removed approx. 90% of the PFAS mass from untreated soils. • Washed soil was used as backfill and water within the treatment plant recycled. [ABSTRACT FROM AUTHOR]

The application of fixed bed high rate nitrifying trickling filters (NTFs) for the removal of track organic chemicals of concern (CoC) is less well known than their application to nutrient removal in water treatment. Particularly, the effect of exogenous organic carbon substrate (sucrose) loading on the performance of NTFs is not well understood. A laboratory-scale NTF system was operated in recirculation mode, with the objective of removing ammonia and CoC simultaneously. The efficiency of a high rate NTF for removal both of low concentration of ammonia (5 mg NH 4 –N L −1 ) and different concentrations of CoC in the presence of an exogenous organic carbon substrate (30 mg total organic carbon (TOC) L −1 ) was investigated. In the presence of exogenous organic carbon, the results demonstrated that the high rate NTF was able to successfully remove most of the CoCs investigated, with the removal ranging from 20.2% to 87.54%. High removal efficiencies were observed for acetaminophen (87.54%), bisphenol A (86.60%), trimethoprim (86.24%) and 17α-ethynylestradiol (80.60%). It was followed by the medium removal efficiency for N, N-diethyl-m-toluamide (61.31%) and atrazine (56.90%). In contrast, the removal of caffeine (28.43%) and benzotriazole (20.20%) was poorer in the presence of exogenous organic carbon. The removal efficiency for CoC was also compared with the results obtained in our previous study in the absence of exogenous organic carbon. The results showed that the addition of exogenous organic carbon was able to improve the removal of some of the CoC. Significant TOC percentage removals (45.68%–84.43%) and ammonia removal rate (mean value of 0.44 mg NH 4 –N L −1 h −1 ) were also achieved in this study. The findings from this study provide valuable information for optimising the efficiency of high rate NTF for the removal of ammonia, CoC and TOC. [ABSTRACT FROM AUTHOR]

There is a growing awareness among farmers about the importance of soil for sustaining crop production and providing beneficial ecosystem services. Over the last 2 decades, global herbicide use has increased as farmers have shifted to more sustainable conservation tillage practices and have adopted herbicide-tolerant crop cultivars. The implications of increased herbicide use for soil biology are being questioned, but a comprehensive review on this topic is lacking. In this chapter we outline the chemistry and use of the major herbicide classes, and review the soil functions relevant to crop production. We then collate and critically evaluate the evidence for herbicide effects on soil biota and activity. In general, most studies suggest that the impacts of herbicide application on soil function are only minor and/or temporary. However, there are some instances where findings consistently suggest effects that could significantly alter soil function. These include disruptions to earthworm ecology in soils exposed to glyphosate and atrazine; inhibition of soil N-cycling (including biological N2-fixation, mineralization and nitrification) by sulfonylurea herbicides in alkaline or low organic matter soils; and site-specific increases in disease resulting from the application of a variety of herbicides. Issues with extrapolating these findings to broadacre farming include the lack of a consistent framework for assessing herbicide risk to soil biology, the relevance of the magnitude of herbicide impacts compared with the impacts of other soil management practices such as tillage or crop rotation, the complexity of herbicide formulations and mixtures, and the limited number of long-term field studies. [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]

The detection of a range of active pharmaceutical ingredients (APIs) in the soil environment has led to a number of publications demonstrating uptake by crops, however very few studies have explored the potential for impacts on plant development as a result of API uptake. This study investigated the effect of carbamazepine and verapamil (0.005-10 mg/kg) on a range of plant responses in zucchini (Cucurbita pepo). Uptake increased in a dose-dependent manner, with maximum leaf concentrations of 821.9 and 2.2 mg/kg for carbamazepine and verapamil, respectively. Increased carbamazepine uptake by zucchini resulted in a decrease in above (<60%) and below (<30%) ground biomass compared to the controls (p < 0.05). At soil concentrations >4 mg/kg the mature leaves suffered from burnt edges and white spots as well as a reduction in photosynthetic pigments but no such effects were seen for verapamil. For both APIs, further investigations revealed significant differences in the concentrations of selected plant hormones (auxins, cytokinins, abscisic acid and jasmonates), and in the nutrient composition of the leaves in comparison to the controls (p < 0.05). This is some of the first research to demonstrate that the exposure of plants to APIs is likely to cause impacts on plant development with unknown implications. [ABSTRACT FROM AUTHOR]

Attenuation of pharmaceuticals due to natural sunlight is expected to be an important removal pathway in wastewater treatment plants using treatment lagoon systems. In this work, the photolysis of two antidepressants, amisulpride and desipramine, has been investigated in both ultrapure water and wastewater under simulated solar irradiation. Results showed that for amisulpride short irradiation times ( t 1/2 approximately 3 h in pure water and 4 h in wastewater) were adequate to degrade the parent compound while a longer exposure period was required for desipramine ( t 1/2 of approximately 36 h in pure water), although its degradation is enhanced almost three times by indirect photolysis in wastewaters. A significant number of transformation products (TPs) were identified for both pharmaceuticals by high-resolution mass spectrometry. In general, TPs formed are not persistent although acute toxicity tests for desipramine and its TPs showed an increase of the mixture toxicity after solar irradiation, suggesting that some TPs may be more toxic than the parent compound. In wastewaters collected from treatment lagoons, only amisulpride and one of its major TPs, TP 357, were detected. This indicates that long solar exposure times may be necessary for an effective elimination of these substances in lagoon systems or that photolysis may not be the main removal pathway for these particular compounds. [ABSTRACT FROM AUTHOR]

Abstract: We investigated the biodegradation of three selected benzotriazoles (BTs), namely benzotriazole (BT), 5-methyl-benzotriazole (5-TTri) and 5-chloro-benzotriazole (CBT), in aquifer materials. Biodegradation experiments were conducted in microcosms with fresh groundwater and aquifer sediment materials under aerobic and anaerobic (nitrate, sulfate, and Fe (III) reducing) conditions. All three BTs were degraded by microorganisms in aquifer materials under aerobic and anaerobic conditions. Under aerobic conditions, BT and 5-TTri were found to be degraded fastest with their half-lives of 43days and 31days, respectively, among the redox conditions used. Under anaerobic conditions, CBT was found to be degraded better with its half-life of 21days under nitrate reducing conditions than under aerobic conditions with its half-life of 47days. The two BT derivatives 5-TTri and CBT could be biotransformed into BT via demethylation and dechlorination reactions, respectively. [Copyright &y& Elsevier]

Abstract: Soil organic matter (SOM) is a complex mixture containing a variety of organic molecular structures. As a consequence, interpretation of the infrared (IR) spectra of SOM is difficult and ambiguous and there is a necessity to establish more reliable IR spectral band assignments. We investigated a novel approach to identify IR spectral bands based on correlation with more easily interpreted nuclear magnetic resonance (NMR) spectra. The IR spectra of HF-treated soils were obtained in both near- and mid-infrared (NIR and MIR) regions and generalized two-dimensional (2D) correlation spectroscopy was employed as the computational correlation tool. 2D NMR/NIR and 2D NMR/MIR heterospectral correlation analyses were performed, separately. We found that NIR spectroscopy could identify aliphatic carbon in SOM as a broad peak occupying the entire NIR region. On the other hand, the MIR spectra contained stronger and more distinct signals than NIR from most of the major carbon types. Bands due to aromatic carbon and carboxyl groups were identified in the regions 4000–3500cm−1 and 850–500cm−1, respectively, and bands due to aliphatic carbon appeared around 3500–2600cm−1 and 2000–1000cm−1. Most (but not all) of these assignments are consistent with assignments based on MIR spectra of model compounds. These findings will assist in developing new IR spectroscopy tools for characterizing the chemistry of SOM more accurately and, perhaps, for monitoring its changes more sensitively. [Copyright &y& Elsevier]

Abstract: Soil variability has implications in farm workability, nutrient and pesticide management, and sustainability. The aims of this study were to investigate how management practises and topography influence the variability of key soil properties and to test the efficacy of various analytical techniques for predictive high resolution soil mapping. We sampled soil properties measured in an intensively managed orchard in the Adelaide Hills, South Australia using a stratified sampling design for alleys and tree-lines in order to distinguish potential management effects (extrinsic factors) from effects of natural soil variability (intrinsic factors). Key soil properties were determined using standard techniques and predictions using mid-infrared partial least-squares (MIR-PLS). Total organic carbon and electrical conductivity (EC) were significantly lower in the tree-line than in the alley. The distribution of coarse fraction (>2mm) was also very different between tree-line and alley, most likely because of ripping during orchard establishment. Terrain parameters had varying effect on distribution of soil properties. The degree of correlation between soil properties and terrain parameters was influenced by the different management regimes in the alley and the tree-line. Within-field management practises impose marked short-range variability in soil properties. Soil sampling in intensively managed orchards in which there has been major landform modification must be stratified. [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]

Abstract: We examined the biodegradability of three benzotriazoles (benzotriazole: BT, 5-methylbenzotriazole: 5-TTri and 5-chlorobenzotriazole: CBT) under aerobic and anaerobic (nitrate, sulfate, and Fe (III) reducing) conditions. All three benzotriazoles were degraded by microorganisms under aerobic and anaerobic conditions. Both the biodegradation efficiency and biodegradation products were dependent on the predominant terminal electron-accepting condition. Among the redox conditions studied, the shortest biodegradation half lives for BT and 5-TTri were 114 days and 14 days, respectively, under aerobic condition. The shortest half-life for CBT was 26 days under Fe (III) reducing condition. The longest biodegradation half lives for BT and CBT were 315 days and 96 days, respectively, under sulfate reducing condition, while that of 5-TTri was 128 days under nitrate reducing condition. These results suggest that aerobic biodegradation is the dominant natural attenuation mechanism for BT and 5-TTri, while the most favorable process for CBT was anaerobic biodegradation. This study demonstrated that different predominant terminal electron-acceptors present in natural environment play a key role on the biodegradation of BT, 5-TTri and CBT, leading to specific biodegradability. This could have significant implications on in-situ biodegradation of the selected benzotriazoles in aerobic and anaerobic waters, soils and sediments. [Copyright &y& Elsevier]

Abstract: A new method using gas chromatography–tandem mass spectrometry (GC–MS/MS) was developed for the determination of four benzotriazoles, i.e. benzotriazole (BT), 5-methylbenzotriazole (5-TTri), 5-chlorobenzotriazole (CBT), 5,6-dimethylbenzotriazole (XTri), and six UV filters, i.e. 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), and octocrylene (OC) in ground water, effluent and biosolid samples. Solid phase extraction (SPE) and pressurized liquid extraction (PLE) were applied as the preconcentration method for water samples (ground water and effluent) and biosolid samples, respectively. The optimized method allowed us to quantify all target compounds with the method detection limits ranging from 0.29 to 11.02ng/L, 0.5 to 14.1ng/L and 0.33 to 8.23ng/g in tap water, effluent and biosolid samples, respectively. The recoveries of the target analytes in tap water, effluent and biosolid samples were 70–150%, 82–127% and 81–133%, respectively. The developed analytical method was applied in the determination of these target compounds in ground water, effluent and biosolid samples collected from Bolivar sewage treatment plants in South Australia. In effluent samples, the target compounds BT, 5-TTri, CBT, XTri and BP-3 tested were detected with the maximum concentration up to 2.2μg/L for BT. In biosolid samples, eight out of ten compounds tested were found to be present at the concentrations ranging between 18.7ng/g (5-TTri) and 250ng/g (4-MBC). [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]

This study investigated the potential aging and plant bioaccumulation of three perfluoroalkyl acids (PFAAs), perfluorosulphonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorohexanesulphonic acid (PFHxS) in 20 soils over a six-month period. Sorption coefficients (Log K d) ranged from 0.13–1.28 for PFHxS, 0.17–1.06 for PFOA and 0.98–2.03 for PFOS, respectively, and bioaccumulation factors (Log BAFs) ranged from 0.29–1.24, 0.22–1.46 and 0.05–0.65 for PFHxS, PFOA and PFOS, respectively. Over the six-month period, K d values significantly increased for PFHxS and PFOA but the magnitude of the increase was very small and did not translate into differences in plant PFAA-concentrations between aged and freshly spiked treatments. The K d and BAF values were modelled by multiple linear regression (MLR) to soil physico-chemical properties and by partial least squares regression to soil spectra acquired by mid-infrared spectroscopy (DRIFT−PLSR). Modelling of each PFAA was influenced by different soil properties, including organic carbon, pH, CEC, exchangeable cations (Ca2+, Mg2+, Na+ and K+) and oxalate extractable Al. BAF values were not strongly correlated to any soil property but were inversely correlated to K d values. Our results indicate that limited aging occurred in these soils over the six-month period. ga1 • PFOS, PFOA and PFHxS appear to retain bioavailability in soil over time. • PFHxS was the most, and PFOS the least, bioaccumulative PFAA across a range of soils. • PFAA bioaccumulation in plant shoots was mainly dependent on organic carbon content. • Across soils, bioaccumulation was inversely related to PFAA partitioning. [ABSTRACT FROM AUTHOR]

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]

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. Image 1 • Mineralisation is not a major pathway for graphene oxide in soils. • Graphene oxide that enter the soil environment is not readily released. • Homo/heteroaggregation of graphene oxide limit their availability in soil. [ABSTRACT FROM AUTHOR]

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.)