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Immobilisation/stabilisation is one of the most developed and studied approaches for treating soils contaminated with per- and poly-fluoroalkyl substances (PFAS). However, its application has been inhibited by insufficient understanding of the effectiveness of added soil sorbents over time. Herein, we present results on the effectiveness of select carbon-based sorbents, over 4 years (longevity) and multiple laboratory leaching conditions (durability). Standard batch leaching tests simulating aggressive, worst-case scenario conditions for leaching (i.e., shaking for 24-48 h at high liquid/solid ratios) were employed to test longevity and durability of stabilisation in clay-loam and sandy-loam soils historically contaminated with PFAS (2 and 14 mg/kg ∑ 28 PFAS). The different sorbents, which were applied at 1-6% (w/w), reduced leaching of PFAS from the soils to varying degrees. Among the 5 sorbents tested, initial assessments completed 1 week after treatment revealed that 2 powdered activated carbon (PAC) sorbents and 1 biochar were able to reduce leaching of PFAS in the soil by at least 95%. Four years after treatment, the performance of the PAC sorbents did not significantly change, whilst colloidal AC improved and was able to reduce leaching of PFAS by at least 94%. The AC-treated soils also appeared to be durable and achieved at least 95% reduction in PFAS leaching under repetitive leaching events (5 times extraction) and with minimal effect of pH (pH 4-10.5). In contrast, the biochars were affected by aging and were at least 22% less effective in reducing PFAS leaching across a range of leaching conditions. Sorbent performance was generally consistent with the sorbent's physical and chemical characteristics. Overall, the AC sorbents used in this study appeared to be better than the biochars in stabilising PFAS in the long term., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Divina Navarro reports financial support was provided by the Australian Government Department of Defence., (Crown Copyright © 2023. Published by Elsevier Ltd. All rights reserved.)

Spills of hydraulic fracturing (HF) fluids and of produced water during unconventional gas extraction operations may cause soil contamination. We studied the degradation and microbial toxicity of selected HF chemical components including two biocides (methylisothiozolinone- MIT, chloromethylisothiozolinone- CMIT), a gel-breaker aid (triethanolamine -TEA), and three geogenic chemicals (phenol, m-cresol and p-cresol) in ultrapure water, HF fluid and produced water in five different soil types (surface and subsurface soils). The degradation of the two biocides (in soils treated with HF fluid or ultrapure water) and of the three geogenic chemicals (in soils treated with produced water) was rapid (in all cases DT 50 values < 2 days in surface soils). In contrast, the loss of TEA was much slower in soils, especially in those treated with HF fluid (DT 50  > 30 days). Sorption coefficients (K oc in L/Kg) in these soils ranged from 71 to 733 for TEA, 64-408 for MIT and 11-72 for CMIT. In terms of soil microbial toxicity, exposure to HF fluid and produced water reduced microbial respiration, albeit temporarily. The overall microbial activities in surface soils contaminated with produced water had fully recovered in most soils. In contrast, the HF fluid addition to soils completely inhibited the nitrification in all soils, with little recovery over the 60 day experimental period. In the case of produced water exposure, three out of five surface soils showed complete recovery in nitrification during the study period. The functional genes for nitrogen fixation (nifH) and carbon cycling (GA1) and microbial community composition (16 S rRNA) were significantly affected by HF fluid in some soils. Overall, the study shows that the HF fluid can have significant detrimental impact on soil microbial functions, especially on nitrogen cycling. More work is needed to identify the exact cause of microbial toxicity in soils contaminated with HF fluid., (Crown Copyright © 2022. Published by Elsevier Ltd. All rights reserved.)

This study investigated the mobilization of a wide range of per- and polyfluoroalkyl substances (PFASs) present in aqueous film-forming foams (AFFFs) in water-saturated soils through one-dimensional (1-D) column experiments with a view to assessing the feasibility of their remediation by soil desorption and washing. Results indicated that sorption/desorption of most of the shorter-carbon-chain PFASs ( C ≤ 6) in soil reached greater than 99% rapidly─after approximately two pore volumes (PVs) and were well predicted by an equilibrium transport model, indicating that they will be readily removed by soil washing technologies. In contrast, the equilibrium model failed to predict the mobilization of longer-chain PFASs ( C ≥ 7), indicating the presence of nonequilibrium sorption/desorption (confirmed by a flow interruption experiment). The actual time taken to attain 99% sorption/desorption was up to 5 times longer than predicted by the equilibrium model (e.g., ∼62 PVs versus ∼12 PVs predicted for perfluorooctane sulfonate (PFOS) in loamy sand). The increasing contribution of hydrophobic interactions over the electrostatic interactions is suggested as the main driving factor of the nonequilibrium processes. The inverse linear relationship ( R 2 = 0.6, p < 0.0001) between the nonequilibrium mass transfer rate coefficient and the Freundlich sorption coefficient could potentially be a useful means for preliminary evaluation of potential nonequilibrium sorption/desorption of PFASs in soils.

Soil contaminated with aqueous film-forming foams (AFFFs) containing per- and polyfluoroalkyl substances (PFASs) at firefighting training sites has become a major concern worldwide. To date, most studies have focused on assessing soil-water partitioning behavior of PFASs and the key factors that can affect their sorption, whereas PFASs leaching from contaminated soils have not yet been widely investigated. This study evaluated the leaching and desorption of a wide range of PFASs from twelve contaminated soils using the Australian Standard Leaching Procedure (ASLP), the U.S. EPA Multiple Extraction Procedure (MEP), and Leaching Environmental Assessment Framework (LEAF). All three leaching tests provided a similar assessment of PFAS leaching behavior. Leaching of PFASs from soils was related to C-chain lengths and their functional head groups. While short-chain (CF 2 ≤ 6) PFASs were easily desorbed and leached, long-chain PFASs were more difficult to desorb. PFASs with a carboxylate head group were leached more readily and to a greater extent than those with a sulfonate or sulfonamide head group. Leaching of long-chain PFASs was pH-dependent where leaching increased at high pH, while leaching of short-chain PFASs was less sensitive to pH. Comparing different leaching tests showed that the results using the alkaline ASLP were similar to the cumulative MEP data and the former might be more practical for routine use than the MEP. No single soil property was adequately able to describe PFAS leaching from the soils. Overall, the PFAS chemical structure appeared to have a greater effect on PFAS leaching from soil than soil physicochemical properties.

Nanopesticides are not only in an advanced state of research and development but have started to appear on the market. Industry and regulatory agencies need a consolidated and comprehensive framework and guidance for human health risk assessments. In this perspective we develop such a comprehensive framework by exploring two case studies from relevant product types: an active ingredient delivered with a nanocarrier system, and a nanoparticle as an active ingredient. For a nanocarrier system, three entities are tracked during the assessment: the nanocarrier-active ingredient complex, the empty nanocarrier remaining after the complete release of the active ingredient, and the released active ingredient. For the nanoparticle of pure active ingredient, only two entities are relevant: the nanoparticle and the released ions. We suggest important adaptations of the existing pesticide framework to determine the relevant nanopesticide entities and their concentrations for toxicity testing. Depending on the nature of the nanopesticides, additional data requirements, such as those pertaining to durability in biological media and potential for crossing biological barriers, have also been identified. Overall, our framework suggests a tiered approach for human health risk assessment, which is applicable for a range of nanopesticide products to support regulators and industry in making informed decisions on nanopesticide submissions. Brief summaries of suitable methods including references to existing standards (if available) have been included together with an analysis of current knowledge gaps. Our study is an important step towards a harmonized approach accepted by regulatory agencies for assessing nanopesticides., (© 2021. Springer Nature Limited.)

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

Urbanisation will be one of the 21st century's most transformative trends. By 2050, it will increase from 55% to 68%, more than doubling the urban population in South Asia and Sub-Saharan Africa. Urbanisation has multifarious (positive as well as negative) impacts on the wellbeing of humans and the environment. The 17 UN Sustainable Development Goals (SDGs) form the blueprint to achieve a sustainable future for all. Clean Water and Sanitation is a specific goal (SDG 6) within the suite of 17 interconnected goals. Here we provide an overview of some of the challenges that urbanisation poses in relation to SDG 6, especially in developing economies. Worldwide, several cities are on the verge of water crisis. Water distribution to informal settlements or slums in megacities (e.g. >50% population in the megacities of India) is essentially non-existent and limits access to adequate safe water supply. Besides due to poor sewer connectivity in the emerging economies, there is a heavy reliance on septic tanks, and other on-site sanitation (OSS) system and by 2030, 4.9 billion people are expected to rely on OSS. About 62-93% of the urban population in Vietnam, Sri Lanka, the Philippines and Indonesia rely on septic tanks, where septage treatment is rare. Globally, over 80% of wastewater is released to the environment without adequate treatment. About 11% of all irrigated croplands is irrigated with such untreated or poorly treated wastewater. In addition to acute and chronic health effects, this also results in significant pollution of often-limited surface and groundwater resources in Sub-Saharan Africa and Asia. Direct and indirect water reuse plays a key role in global water and food security. Here we offer several suggestions to mitigate water and food insecurity in emerging economies., Competing Interests: Declaration of competing interest The authors along with all co-authors are in agreement for the work being peer reviewed and possibly published and we have no undeclared competing financial interests or conflicts of interest., (Crown Copyright © 2020. Published by Elsevier B.V. All rights reserved.)

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., Competing Interests: Declaration of competing interest The authors declare no competing interests., (Crown Copyright © 2019. Published by Elsevier Ltd. All rights reserved.)

This study investigated the effect of surface charge on the sorption of perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorohexane sulfonic acid (PFHxS) onto 7 tropical soils as a function of pH. The net surface charge became less negative with decreasing pH (from 7.5 to 3.5) in all soils. The rate of change in net surface charge varied from -0.6 to -2.8 (cmol/kg)/pH unit. The effect on sorption behaviour of PFASs was variable among soils. For two soils, the average sorption increased 54- and 45-fold for PFOS, 33- and 9-fold for PFOA, and 39- and 400-fold for PFHxS, across the pH range 7.5 to 3.5. Sorption in another sandier soil showed negligible change with decreasing pH. Sorption in the other soils did not change significantly until the pH decreased to approximately 5.5. The soils with high contents of sesquioxides (Fe and Al oxides) showed the most marked increase in sorption with decreasing pH. This study demonstrated that in addition to hydrophobic interactions with OC and other processes, electrostatic interactions are also important in the sorption process for these chemicals in soils. In acidic, variably charged tropical soils there is the possibility that any PFOS, PFOA or PFHxS sorbed to the soils may become desorbed if management practices (e.g. liming) raised soil pH., (Copyright © 2019. Published by Elsevier B.V.)

Research over the last decade on emerging trace organic contaminants in aquatic systems has largely focused on sources such as treated wastewaters in high income countries, with relatively few studies relating to wastewater sources of these contaminants in low and middle income countries. We undertook a longitudinal survey of the Ahar River for a number of emerging organic contaminants (including pharmaceuticals, hormones, personal care products and industrial chemicals) which flows through the city of Udaipur, India. Udaipur is a city of approximately 450,000 people with no wastewater treatment occurring at the time of this survey. We found the concentrations of many of the contaminants within the river water were similar to those commonly reported in untreated wastewater in high income countries. For example, concentrations of pharmaceuticals, such as carbamazepine, antibiotics and non-steroidal anti-inflammatory drugs, ranged up to 1900 ng/L. Other organic contaminants, such as steroid estrogens (up to 124 ng/L), steroid androgens (up to 1560 ng/L), benzotriazoles (up to 11 μg/L), DEET (up to 390 ng/L), BPA (up to 300 ng/L) and caffeine (up to 37.5 μg/L), were all similar to previously reported concentrations in wastewaters in high income countries. An assessment of the population densities in the watersheds feeding into the river showed increasing population density of a watershed led to a corresponding downstream increase in the concentrations of the organic contaminants, with quantifiable concentrations still present up to 10 km downstream of the areas directly adjacent to the highest population densities. Overall, this study highlights how a relatively clean river can be contaminated by untreated wastewater released from an urban centre., (Crown Copyright © 2018. Published by Elsevier B.V. All rights reserved.)

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

Fullerenes (e.g. C 60 , C 70 , etc.) present in soil may undergo changes in its retention with aging. In this study, the partitioning behavior of ( 14 C)-C 60 aged up to 12 weeks was investigated in biosolids-amended soil. Spiked samples were subjected to sequential partitioning using water, methanol, and toluene followed by total combustion of solids; the distribution of 14 C across solvents and matrices were used to provide insights on C 60 behavior. In most samples, 14 C only partitioned in toluene with the remaining (non-extractable) activity detected in the solid phase. In all biosolids-amended soil samples, an increase in non-extractable 14 C were observed for those exposed to light (vs dark) with the greatest difference observed in biosolids + sand samples. Possible processes that contribute to the observed 14 C distribution, i.e. retention and potential transformation of C 60, were discussed. Over-all, results suggest that environmental exposure to C 60 and potentially transformed C 60 species, as a result of their release from soils, is likely to be low., (Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.)

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., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Ferrate(VI) (Fe(VI)) has been known to react with emerging organic contaminants containing electron-rich organic moieties, such as phenols, anilines, olefins, reduced sulfur and deprotonated amines. Oxidation of fluoroquinolone antibiotics, ciprofloxacin (CIP) and enrofloxacin (ENR), by Fe(VI) were investigated for their reaction products and toxicity changes as well as biodegradability of these products. Ten products were identified for both CIP and ENR reactions with Fe(VI) using a high-resolution accurate-mass Orbitrap mass analyzer. Structural changes to the CIP and ENR molecule included dealkylation, formation of alcohols and amides in piperazine ring and oxygen transfer to the double bond in quinolone structure. An enamine formation mechanism was tentatively proposed to facilitate the interpretation of CIP and ENR oxidation pathways. Toxicity evaluation using Microbial Assay for toxicity Risk Assessment (MARA) bioassay indicated that Fe(VI) oxidation products of CIP and ENR contributed negligible antibacterial potency and Fe(VI) oxidation treatment can remove the residual toxicity of CIP and ENR impacted source waters. The Fe(VI) oxidation treatment resulted in formation of relatively more biodegradable products (based on in silico assessment) than their corresponding parent compounds. The results showed that Fe(VI) has a good potential to degrade fluoroquinolone antibiotics and their antimicrobial potency in natural waters., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Two pesticide risk indicators, Pesticide Impact Rating Index (PIRI) and Environmental Potential Risk Indicator for Pesticides (EPRIP), were used to determine the likelihood of off-site transport to surface water of pesticides used in a cherry (Prunus avium cultivars) and an apple (Malus domestica cultivars) orchard. The predictions of off-site transport of some of the pesticides were verified against actual pesticide concentrations in surface water continuously monitored over two years. To our knowledge, only one other study in the published literature has attempted this. Of the chemicals monitored there was good agreement between the predictions and the field measurements from the apple orchard, but less so for the cherry orchard. In both risk indicators the attenuation factor based on the width of the buffer strip over-estimated the effectiveness of the buffer strip. There was good agreement between the EPRIP and PIRI risk assessment except for ethephon which EPRIP rated a higher risk than PIRI and dithianon which EPRIP rated a lower risk than PIRI. A strong correlation was found between the field observations and the EPRIP predicted environmental concentrations for the majority of cases. This study showed that even simple risk indicators (e.g. PIRI and EPRIP) can be good predictors for a first tier risk assessment of pesticide transport to neighbouring water bodies., (Crown Copyright © 2016. Published by Elsevier B.V. All rights reserved.)

Removal of a persistent antiepileptic drug carbamazepine (CBZ) in aqueous solutions was investigated by using solar photolysis combined with free available chlorine (FAC). The combination of chlorination with simulated or natural sunlight markedly enhanced removal of CBZ in 10 mM phosphate buffer solution (pH 7.0) and river water (pH 7.0) compared with sunlight or FAC alone. Further analysis indicated that the observed enhancements in CBZ removal can be attributed to the in situ hydroxyl radical (HO) and ozone (O3) production during FAC photolysis. During 70 min simulated sunlight photolysis combined with FAC treatment, HO reaction contributed to 35.8% removal of CBZ and O3 reaction contributed to 40.6% removal, while only 5.3% of CBZ was removed by HOCl reaction. The oxidation products of CBZ, epoxide CBZ, 10,11-dihydro-10,11-dihydroxy CBZ, 1-(2-benzaldehyde)-4-hydro-(1H,3H)-quinazoline-2-one (BQM), 1-(2-benzaldehyde)-(1H,3H)-quinazoline-2,4-dione (BQD) and 4-aldehyde-9-acridone, were mainly formed from the HO and O3 attack at the double bond on the central heterocyclic ring of CBZ. Formation of these oxidation products did not cause any increase or decrease in toxicity to microbial species tested through Microbial Assay for Toxicity Risk Assessment (MARA). The initial FAC concentration and pH had a major influence on the removal process of CBZ during FAC photolysis, while temperature had a minor effect only. The combination of chlorination with natural sunlight could provide an effective approach for removal of CBZ and other contaminants during water treatment., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Canola (Brassica napus L.) is the third largest field crop in Australia by area sown. Genetically modified (GM) and non-GM canola varieties released or being developed in Australia include Clearfield® (imidazolinone tolerant), TT (triazine tolerant), InVigor® (glufosinate-ammonium tolerant), Roundup Ready® - RR® (glyphosate tolerant) and Hyola® RT® (tolerant to both glyphosate and triazine). We used two risk assessment approaches - the Environmental Impact Quotient (EIQ) and the Pesticide Impact Rating Index (PIRI) - to compare the environmental risks associated with herbicides used in the canola varieties (GM and non-GM) that are currently grown or may be grown in the future. Risk assessments found that from an environmental impact viewpoint a number of herbicides used in the production of TT canola showed high relative risk in terms of mobility and ecotoxicity of herbicides. The EIQ field use rating values for atrazine and simazine in particular were high compared with those for glyphosate and trifluralin. Imazapic and imazapyr, which are only used in Clearfield® canola, had extremely low EIQ field use rating values, likely reflecting the very low application rates used for these chemicals (0.02 to 0.04kg/ha) compared with those used for atrazine and simazine (1.2 to 1.5kg/ha). The PIRI assessment showed that irrespective of the canola variety grown, trifluralin posed a high toxicity risk to fish (Rainbow trout, Oncorhynchus mykiss), algae and Daphnia sp. While the replacement of trifluralin with propyzamide had little effect on the mobility score, it greatly decreased the ecotoxicity score to fish, algae and Daphnia sp. due to the lower LC50 values for propyzamide compared with trifluralin. This study has shown that based on likelihood of off-site transport of herbicides in surface water and potential toxicity to non-target organisms, the GM canola varieties have no advantage over non-herbicide tolerant (non HT) or Clearfield® canola., (Crown Copyright © 2016. Published by Elsevier B.V. All rights reserved.)

This special issue presents a collection of papers covering the environmental fate, effects, and risk of pesticides in tropical environments, which is expected to facilitate improved management of pesticides. Environmental monitoring programs of surface and ground waters in the tropics, including areas of high ecological value, have detected several relatively polar pesticides at concentrations that are of ecological concern. Novel monitoring techniques have the capacity to reveal the spatial and temporal extent of such risks. To best manage these pesticides, their sorption, dissipation rates, leaching, and runoff potential need to be better understood. On these aspects, important insights have been provided by several studies within this issue. Improved understanding of the environmental fate, effects, and risks through studies presented in this special issue is crucial for minimizing the nontarget impacts of pesticides on biodiversity-rich tropical regions.

Perfluoroalkyl substances (PFASs) have received great attention from the public and scientific community due to their potential adverse impacts on the ecosystem and human health. We investigated the occurrence and distribution of 16 PFASs from 2 classes of PFASs-perfluoroalkyl carboxylic acids and perfluoroalkane sulfonic acids-in the archived surface sediments of five major rivers (Yellow River, Hai River, Liao River, Zhujiang River, and Dongjiang River) in northern and southern China. The study was also performed during the wet and dry seasons. Perfluorooctanoic acid and perfluorooctane sulfonic acid were the most frequently detected (detection frequency = 100 and 63 %, respectively) in the sediments of the five rivers; the concentrations ranged from 0.08 to 0.99 ng/g dry weight (dw) and were lower than the limit of detection (

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

Active pharmaceutical ingredients (APIs) can enter the natural environment during manufacture, use and/or disposal, and consequently public concern about their potential adverse impacts in the environment is growing. Despite the bulk of the human population living in Asia and Africa (mostly in low- or middle-income countries), limited work relating to research, development and regulations on APIs in the environment have so far been conducted in these regions. Also, the API manufacturing sector is gradually shifting to countries with lower production costs. This paper focuses mainly on APIs for human consumption and highlights key differences between the low-, middle- and high-income countries, covering factors such as population and demographics, manufacture, prescriptions, treatment, disposal and reuse of waste and wastewater. The striking differences in populations (both human and animal), urbanization, sewer connectivity and other factors have revealed that the environmental compartments receiving the bulk of API residues differ markedly between low- and high-income countries. High sewer connectivity in developed countries allows capture and treatment of the waste stream (point-source). However, in many low- or middle-income countries, sewerage connectivity is generally low and in some areas waste is collected predominantly in septic systems. Consequently, the diffuse-source impact, such as on groundwater from leaking septic systems or on land due to disposal of raw sewage or septage, may be of greater concern. A screening level assessment of potential burdens of APIs in urban and rural environments of countries representing low- and middle-income as well as high-income has been made. Implications for ecological risks of APIs used by humans in lower income countries are discussed., (© 2014 The Author(s) Published by the Royal Society. All rights reserved.)

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

Nanopesticides or nano plant protection products represent an emerging technological development that, in relation to pesticide use, could offer a range of benefits including increased efficacy, durability, and a reduction in the amounts of active ingredients that need to be used. A number of formulation types have been suggested including emulsions (e.g., nanoemulsions), nanocapsules (e.g., with polymers), and products containing pristine engineered nanoparticles, such as metals, metal oxides, and nanoclays. The increasing interest in the use of nanopesticides raises questions as to how to assess the environmental risk of these materials for regulatory purposes. Here, the current approaches for environmental risk assessment of pesticides are reviewed and the question of whether these approaches are fit for purpose for use on nanopesticides is addressed. Potential adaptations to existing environmental risk assessment tests and procedures for use with nanopesticides are discussed, addressing aspects such as analysis and characterization, environmental fate and exposure assessment, uptake by biota, ecotoxicity, and risk assessment of nanopesticides in aquatic and terrestrial ecosystems. Throughout, the main focus is on assessing whether the presence of the nanoformulation introduces potential differences relative to the conventional active ingredients. The proposed changes in the test methodology, research priorities, and recommendations would facilitate the development of regulatory approaches and a regulatory framework for nanopesticides.

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

Owing of their wide-range of commercial applications, fullerene (C60) nanoparticles, are likely to reach environments through the application of treated sludge (biosolids) from wastewater treatment plants to soils. We examined the release behaviour of C60 from contaminated biosolids added to soils with varying physicochemical characteristics. Incubation studies were carried out in the dark for up to 24 weeks, by adding biosolids spiked (1.5mg/kg) with three forms of C60 (suspended in water, in humic acid, and precipitated/particulate) to six contrasting soils. Leaching of different biosolids+soil systems showed that only small fractions of C60 (<5% of applied amount) were released, depending on incubation time and soil properties (particularly dissolved organic carbon content). Release of C60 from unamended soils was greater (at least twice as much) than from biosolids-amended soils. The form of C60 used to spike the biosolids had no significant effect on the release of C60 from the different systems. Contact time of C60 in these systems only slightly increased the apparent release up to 8 weeks, followed by a decrease to 24 weeks. Mass balance analysis at the completion of the experiment revealed that 20-60% of the initial C60 applied could not be accounted for in these systems; the reasons for this are discussed., (Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.)

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

Sorption and degradation of the five selected endocrine disrupting chemicals (EDCs) including bisphenol A (BPA), 17 beta-estradiol (E2), 17 alpha-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.

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), 17beta-estradiol (E2) and estriol (E3) all have a solubility of approximately 13 mg/l, whereas synthetic steroids 17alpha-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.