Modeling the environmental fate of bracken toxin ptaquiloside: Production, release and transport in the rhizosphere.

Plants produce a diverse array of toxic compounds which may be released by precipitation, explaining their wide occurrence in surrounding soil and water. This study presents the first mechanistic model for describing the generation and environmental fate of a natural toxin, i.e. ptaquiloside (PTA), a carcinogenic phytotoxin produced by bracken fern (Pteridium aquilinum L. Kuhn). The newly adapted DAISY model was calibrated based on two-year monitoring performed in the period 2018-2019 in a Danish bracken population located in a forest glade. Several functions related to the fate of PTA were calibrated, covering processes from toxin generation in the canopy, wash off by precipitation and degradation in the soil. Model results show a good description of observed bracken biomass and PTA contents, supporting the assumption that toxin production can be explained by the production of new biomass. Model results show that only 4.4 % of the PTA produced in bracken is washed off by precipitation, from both canopy and litter. Model simulations showed that PTA degrades rapidly once in the soil, especially during summer due to the high soil temperatures. Leaching takes place in form of pulses directly connected to precipitation events, with maximum simulated concentrations up to 4.39 µg L-1 at 50 cm depth. Macropore transport is mainly responsible for the events with the highest PTA concentrations, contributing to 72 % of the total mass of PTA leached. Based on the results, we identify areas with high density of bracken, high precipitation during the summer and soils characterized by fast transport, as the most vulnerable to surface and groundwater pollution by phytotoxins.

Nitrogen amended graphene catalyses fast reduction of vinyl chloride by nano zerovalent iron.

Vinyl chloride (VC) is a dominant carcinogenic residual in many aged chlorinated solvent plumes, and it remains a huge challenge to clean it up. Zerovalent iron (ZVI) is an effective reductant for many chlorinated compounds but shows low VC removal efficiency at field scale. Amendment of ZVI with a carbonaceous material may be used to both preconcentrate VC and facilitate redox reactions. In this study, nitrogen-doped graphene (NG) produced by a simple co-pyrolysis method using urea as nitrogen (N) source, was tested as a catalyst for VC reduction by nanoscale ZVI (nZVI). The extent of VC reduction to ethylene in the presence of 2 g/L of nZVI was less than 1% after 3 days, and barely improved with the addition of 4 g/L of graphene. In contrast, with amendment of nZVI with NG produced at pyrolysis temperature (PT) of 950 °C, the VC reduction extent increased more than 10-fold to 69%. The reactivity increased with NG PT increasing from 400 °C to an optimum at 950 °C, and it increased linearly with NG loadings. Interestingly, N dosage had little effect on reactivity if NG was produced at PT of 950 °C, while a positive correlation was observed for NG produced at PT of 600 °C. XPS and Raman analyses revealed that for NG produced at lower PT (<800 °C) mainly the content of pyridine-N-oxide (PNO) groups correlates with reactivity, while for NG produced at higher PT up to 950 °C, reactivity correlates mainly with N induced structural defects in graphene. The results of quenching and hydrogen yield experiments indicated that NG promote reduction of VC by storage of atomic hydrogen, thus increasing its availability for VC reduction, while likely also enabling electron transfer from nZVI to VC. Overall, these findings demonstrate effective chemical reduction of VC by a nZVI-NG composite, and they give insights into the effects of N doping on redox reactivity and hydrogen storage potential of carbonaceous materials.

Phosphorus doped cyanobacterial biochar catalyzes efficient persulfate oxidation of the antibiotic norfloxacin.

In this study, cyanobacterial biochars (CBs) enriched/doped with non-metallic elements were prepared by pyrolysis of biomass amended with different N, S, and P containing compounds. Their catalytic reactivity was tested for persulfate oxidation of the antibiotic norfloxacin (NOR). N and S doping failed to improve CB catalytic reactivity, while P doping increased reactivity 5 times compared with un-doped biochar. Biochars produced with organic phosphorus dopants showed the highest reactivity. Post-acid-washing improved catalytic reactivity. In particular, 950 ℃ acid-washed triphenyl-phosphate doped CB showed the largest degradation rate and reached 79% NOR mineralization in 2 h. Main attributes for P-doped CBs high reactivity were large specific surface areas (up to 655 m2/g), high adsorption, high C-P-O content, graphitic P and non-radical degradation pathway (electron transfer). This study demonstrates a new way to reuse waste biomass by producing efficient P-doped metal-free biochars and presents a basic framework for designing carbon-based catalysts for organic pollutant degradation.

Fast peroxydisulfate oxidation of the antibiotic norfloxacin catalyzed by cyanobacterial biochar.

Peroxydisulfate (PDS) is a common oxidant for organic contaminant remediation. PDS is typically activated by metal catalysts to generate reactive radicals. Unfortunately, as radicals are non-selective and metal catalysts may cause secondary contamination, alternative selective non-radical pathways and non-metal catalysts need attention. Here we investigated PDS oxidation of commonly detected antibiotic Norfloxacin (NOR) using cyanobacterial nitrogen rich biochars (CBs) as catalysts. NOR was fully degraded by CB pyrolysed at 950 °C (CB950) within 120 min. CB950 caused threefold faster degradation than low pyrolysis temperature (PT) CBs and achieved a maximum surface area normalized rate constant of 4.38 × 10-2 min-1 m-2 L compared to widely used metal catalysts. CB950 maintained full reactivity after four repeated uses. High defluorination (82%) and mineralization (>82%) were observed for CB950/PDS. CBs were active over a broad pH range (3-10), but with twice as high rates under alkaline compared with neutral conditions. NOR is degraded by organic, •OH and SO4•- radicals in low PT CBs/PDS systems, where the presence of MnII promotes radical generation. Electron transfer reactions with radicals supplemented dominate high PT CBs/PDS systems. This study demonstrates high PT biochars from algal bloom biomass may find use as catalysts for organic contaminant oxidation.

Occurrence and stability of ptesculentoside, caudatoside and ptaquiloside in surface waters.

The illudane glycosides ptesculentoside (PTE), caudatoside (CAU) and ptaquiloside (PTA) are found in bracken ferns (Pteridium sp.). PTA is known to contaminate water bodies adjacent to bracken ferns and hence contribute to water toxicity. This study for the first time reports the presence of PTE and CAU in surface waters with concentrations up to 5.3 µg L-1 and outlines their stability under semi-natural conditions using water of two diverse lakes at their natural pH or pH adjusted to 6.5, with temperature controlled at 5 or 15 °C, and in the presence or absence of microbial activity. Under the same set of tested conditions the three illudane glycosides degraded at similar rates: with half-lives of approximately two days at pH 7.4 and 15 °C, and approximately 12 days at pH 5.2-6.5 and 5 °C. The water origin had significant influence on the degradation rates, but only due to its difference in pH. In most cases, the degradation rates of all the three illudane glycosides could be predicted using the existing first-order model for PTA hydrolysis. As PTE and CAU exhibit the same leaching pattern and stability as PTA, previous predictions of bracken environmental impact are likely underestimated, as PTE and CAU have not been monitored and included in the risk assessment.

The invasive butterbur contaminates stream and seepage water in groundwater wells with toxic pyrrolizidine alkaloids.

Pyrrolizidine alkaloids (PAs) are persistent mutagenic and carcinogenic compounds produced by many common plant species. Health authorities recommend minimising human exposure via food and medicinal products to ensure consumer health and safety. However, there is little awareness that PAs can contaminate water resources. Therefore, no regulations exist to limit PAs in drinking water. This study measured a PA base concentration of ~ 70 ng/L in stream water adjacent to an invasive PA-producing plant Petasites hybridus (Asteraceae). After intense rain the PA concentration increased tenfold. In addition, PAs measured up to 230 ng/L in seepage water from groundwater wells. The dominant PAs in both water types corresponded to the most abundant PAs in the plants (senkirkine, senecionine, senecionine N-oxide). The study presents the first discovery of persistent plant toxins in well water and their associated risks. In addition, it for the first time reports monocrotaline and monocrotaline N-oxide in Petasites sp.

Rare earth elements in surface specific urban runoff in Northern Beijing.

Rare earth elements (REEs) have been increasingly diffused to the environment through mining activities and the extensive use in modern commodities, vehicular activities, coal burning and various environmental and agricultural applications. Studies of REEs in urban environments are limited with no data on REEs in urban runoff. To investigate the concentration and distribution of REEs, a total of 150 runoff samples were collected from trafficked areas, rooftops and residential parking lots in a moderate to densely populated area in Beijing, China. The runoff samples were separated into dissolved and particulate phases and analyzed by ICP-MS. The REEs were mainly (>80%) found in the runoff particulate material. The sum of REEs (ΣREE) total concentrations in urban stormwater runoff samples ranged from 0.16 to 185 µg/l. The observed mean total concentration of ΣREE in the runoff samples were 3-14 folds higher and dissolved fractions 1.5 to 6 times higher than published concentrations for recipients such as sewage channels and rivers. The distribution of REEs in runoff was dominated by light REE. Cluster analysis and Pearson's correlations revealed a strong association between the individual REEs pointing to a similar source. Higher Ce concentrations compared to other REEs indicated strong influence from traffic emission particulates. The La/Sm (5.90-8.05), La/Ce (0.53-0.58) and Ce/Yb (31.0-42.7) ratios pointed to REE sources from traffic emissions and coal burning thus defining an urban fingerprint.

Fast LC-MS quantification of ptesculentoside, caudatoside, ptaquiloside and corresponding pterosins in bracken ferns.

Ptaquiloside (PTA) is an illudane glycoside partly responsible for the carcinogenicity of bracken ferns (Pteridium sp.). The PTA analogues ptesculentoside (PTE) and caudatoside (CAU) have similar biochemical reactivity. However, both compounds are highly under-investigated due to the lack of analytical standards and appropriate methods. This study presents a robust method for preparation of analytical standards of PTE, CAU, PTA, the corresponding hydrolysis products: pterosins G, A and B, and an LC-MS based method for simultaneous quantification of the six compounds in bracken. The chromatographic separation of analytes takes 5 min. The observed linear range of quantification was 20-500 µg/L for PTA and pterosin B, and 10-250 µg/L for the remaining compounds (r > 0.999). The limits of detection were 0.08-0.26 µg/L for PTE, CAU and PTA and 0.01-0.03 µg/L for the pterosins, equivalent to 2.0-6.5 µg/g and 0.25-0.75 µg/g in dry weight, respectively. The method was applied on 18 samples of dried fern leaves from 6 continents. Results demonstrated high variation in concentrations of PTE, CAU and PTA with levels prior to hydrolysis up to 3,900, 2,200 and 2,100 µg/g respectively. This is the first analytical method for simultaneous and direct measurement of all six compounds. Its application demonstrated that bracken ferns contain significant amounts of PTE and CAU relative to PTA.

Fate of ptaquiloside-A bracken fern toxin-In cattle.

Ptaquiloside is a natural toxin present in bracken ferns (Pteridium sp.). Cattle ingesting bracken may develop bladder tumours and excrete genotoxins in meat and milk. However, the fate of ptaquiloside in cattle and the link between ptaquiloside and cattle carcinogenesis is unresolved. Here, we present the toxicokinetic profile of ptaquiloside in plasma and urine after intravenous administration of ptaquiloside and after oral administration of bracken. Administered intravenously ptaquiloside, revealed a volume of distribution of 1.3 L kg-1 with a mean residence-time of 4 hours. A large fraction of ptaquiloside was converted to non-toxic pterosin B in the blood stream. Both ptaquiloside and pterosin B were excreted in urine (up to 41% of the dose). Oral administration of ptaquiloside via bracken extract or dried ferns did not result in observations of ptaquiloside in body fluids, indicating deglycosolidation in the rumen. Pterosin B was detected in both plasma and urine after oral administration. Hence, transport of carcinogenic ptaquiloside metabolites over the rumen membrane is indicated. Pterosin B recovered from urine counted for 7% of the dose given intravenously. Heifers exposed to bracken for 7 days (2 mg ptaquiloside kg-1) developed preneoplastic lesions in the urinary bladder most likely caused by genotoxic ptaquiloside metabolites.

Metals in surface specific urban runoff in Beijing.

Metals are among the most toxic pollutants in urban stormwater. To investigate the concentration of dissolved and particulate fractions, the temporal variation during rain events, the effect of wash-off surface, and to assess the pollution status of metals in urban runoff, a total of 155 samples were collected mainly from trafficked areas, roofs and parking lots in Beijing from March to November 2015. Most of the metals were found mainly in the particulate fraction (68-96%) from trafficked surfaces, while for roof runoff Cd, Fe, Mn and Zn were found more equally in dissolved and particulate fractions. Metal concentrations were higher during start of a rain event than later (p < 0.05), and also were higher the longer the period of antecedent dry days. The mean concentration of all metals in trafficked areas exceeded both the Chinese standard Level III (swimming and fishery waters) and the European standards (surface water). Mean concentrations of Cd, Mn, Zn, Al, Fe, Pb and Ni from trafficked areas were 2-10 times higher due to higher traffic intensity and substantial atmospheric deposition, while Sb was 20 times higher than in any other reported data for urban runoff. Cluster analysis (CA) and principal component analysis (PCA) together with Pearson's correlation co-efficient suggested that Cd, Cr, Cu, Mn, Ni, Pb, and Zn mainly originates from vehicular activities, while Mn and Zn in roof runoff is due to atmospheric deposition. The geo-accumulation and pollution indices show that runoff from trafficked areas are moderately to heavily polluted by most metals, except Cu and Zn. Thus, Beijing urban runoff presents an environmental risk towards lakes, bathing water and drinking water. The results can be used as basis for development of stormwater and pollution control strategies.

Low crystalline apatite in bone char produced at low temperature ameliorates phosphorus-deficient soils.

Globally, more than 30% of soils are poor in phosphorus (P) and the productivity of these soils is severely restricted without the addition of P fertiliser. With future P supplies becoming limited, it is becoming increasingly important to identify ways of optimising the use of waste materials as P fertilisers. One technology that has been promoted extensively in recent years to improve quality of degraded soils is the application of biochar. In this context, char produced from recycled animal bone is of special interest because of its high P content (∼15%). This study investigated how production temperature affects chemical P forms in bone char and the impact on soil P availability in different P-deficient soils. The major P form in dried bone meal was poorly crystalline hydroxyapatite. As the pyrolysis temperature increased to 1050 °C, the hydroxyapatite structure measured with X-ray absorption near edge structure (XANES) spectroscopy persisted. Furthermore, crystallinity increased at temperatures above 750 °C, as revealed by X-ray powder diffraction (XRD). Plant availability was highest for bone char produced between 300 °C and 500 °C in three acidic soils from three continents, and declined rapidly above 750 °C. This strongly indicated that crystallinity of hydroxyapatite limits plant availability at high pyrolysis temperatures. In a high pH soil, all materials resulted in low P availability. As pyrolysis increased the P availability in comparison with dried bone, it was concluded that bone char produced at temperatures between 300 °C and 500 °C has the potential to improve fertility of P-poor, low pH soils.

DGT technique to assess P mobilization from greenhouse vegetable soils in China: A novel approach.

Intensive phosphorus (P) inputs to plastic-covered greenhouse vegetable production (PGVP) in China has led to excessive soil P accumulation increasing the potential for leaching to surface waters. This study examined the mobility and hence the potential risk of P losses through correlations between soil solution P (PSol) and soil extractable P as determined by conventional soil P test methods (STPs) including degree of P saturations (DPSs), and diffusive gradient in thin-films (DGT P) technique. A total of 75 topsoil samples were chosen from five representative Chinese PGVPs covering a wide range of physiochemical soil properties and cultivation history. Total P and Olsen P contents varied from 260 to 4900, and 5 to 740mgkg-1, respectively, while PSol concentrations were between 0.01 and 10.8mgL-1 reflecting the large differences in vegetation history, fertilization schemes, and soil types. Overall, DGT P provided the best correlation with PSol (r2=0.97) demonstrating that DGT P is a versatile measure of P mobility regardless of soil type. Among the DPSs tested, oxalate extractable Al (DPSOx-Al) had the best correlation with PSol (r2=0.87). In the STP versus PSol relationships, STP break-points above which P mobilization increases steeply were 513µgL-1 and 190mgkg-1 for DGT P or Olsen P, respectively, corresponding to PSol concentration of 0.88mgL-1. However, for PSol concentration of 0.1mgL-1 that initiates eutrophication, the corresponding DGT P and Olsen P values were 27µgL-1 and 22mgkg-1, respectively. Over 80% of the investigated soils had DGT P and Olsen P above these values, and thus are at risk of P mobilization threatening receiving waters by eutrophication. This paper demonstrates that the DGT extracted P is a powerful measure for soluble P and hence for assessment of P mobility from a broad range of soil types.

Dissipation of pterosin B in acid soils - Tracking the fate of the bracken fern carcinogen ptaquiloside.

Bracken ferns (Pteridium spp.) are well-known for their carcinogenic properties, which are ascribed to the content of ptaquiloside and ptaquiloside-like substances. Ptaquiloside leach from the ferns and may cause contamination of drinking water. Pterosin B is formed by hydrolysis of ptaquiloside. In soil, Pterosin B is adsorbed more strongly and it is expected to have a slower turnover than ptaquiloside. We thus hypothesized that pterosin B may serve as an indicator for any past presence of ptaquiloside. Pterosin B degradation was studied in acid forest soils from bracken-covered and bracken-free areas. Soil samples were incubated with pterosin B at 3 and 8 µg g-1 for 10 days, whereas sterile (autoclaved) samples were incubated for 23 days. Pterosin B showed unexpected fast degradation in soils with full degradation in topsoils in 2-5 days. Pterosin B dissipation followed the sum of two-first order reactions. The initial fast reaction with half-lives of 0.7-3.5 h contributed 11-59% of the total pterosin B degradation, while the slow reaction was 20-100 times slower than the fast reaction. Total dissipation half-lives were shorter for loamy sand (4 h) than for sandy loam soils (28 h). No degradation of pterosin B took place under sterile conditions assuming observed dissipation during the first 3 h could be attributed to irreversible sorption. Our results demonstrate that pterosin B is microbially degraded and that pterosin B is as unstable as ptaquiloside and hence cannot be used as an indicator for former presence of ptaquiloside in soil.

UPLC-MS/MS determination of ptaquiloside and pterosin B in preserved natural water.

The naturally occurring carcinogen ptaquiloside and its degradation product pterosin B are found in water leaching from bracken stands. The objective of this work is to present a new sample preservation method and a fast UPLC-MS/MS method for quantification of ptaquiloside and pterosin B in environmental water samples, employing a novel internal standard. A faster, reliable, and efficient method was developed for isolation of high purity ptaquiloside and pterosin B from plant material for use as analytical standards, with purity verified by 1H-NMR. The chemical analysis was performed by cleanup and preconcentration of samples with solid phase extraction, before analyte quantification with UPLC-MS/MS. By including gradient elution and optimizing the liquid chromatography mobile phase buffer system, a total run cycle of 5 min was achieved, with method detection limits, including preconcentration, of 8 and 4 ng/L for ptaquiloside and pterosin B, respectively. The use of loganin as internal standard improved repeatability of the determination of both analytes, though it could not be employed for sample preparation. Buffering raw water samples in situ with ammonium acetate to pH ∼5.5 decisively increased sample integrity at realistic transportation and storing conditions prior to extraction. Groundwater samples collected in November 2015 at the shallow water table below a Danish bracken stand were preserved and analyzed using the above methods, and PTA concentrations of 3.8 ± 0.24 µg/L (±sd, n = 3) were found, much higher than previously reported. Graphical abstract Workflow overview of ptaquiloside determination.

Suspended particles only marginally reduce pyrethroid toxicity to the freshwater invertebrate Gammarus pulex (L.) during pulse exposure.

Current ecotoxicological research on particle-associated pyrethroids in freshwater systems focuses almost exclusively on sediment-exposure scenarios and sediment-dwelling macroinvertebrates. We studied how suspended particles influence acute effects of lambda-cyhalothrin and bifenthrin on the epibenthic freshwater amphipod Gammarus pulex (L.) using brief pulse exposures followed by a 144 h post exposure recovery phase. Humic acid (HA) and the clay mineral montmorillonite (MM) were used as model sorbents in environmentally realistic concentrations (5, 25 and 125 mg L(-1)). Mortality of G. pulex was recorded during the post exposure recovery phase and locomotor behavior was measured during exposure to lambda-cyhalothrin. We found that HA in concentrations ≥25 mg L(-1) adsorbed the majority of pyrethroids but only reduced mortality of G. pulex up to a factor of four compared to pyrethroid-only treatments. MM suspensions adsorbed a variable fraction of pyrethroids (10% for bifenthrin and 70% for lambda-cyhalothrin) but did not significantly change the concentration-response relationship compared to pure pyrethroid treatments. Behavioral responses and immobilisation rate of G. pulex were reduced in the presence of HA, whereas behavioral responses and immobilisation rate were increased in the presence of MM. This indicates that G. pulex was capable of sensing the bioavailable fraction of lambda-cyhalothrin. Our results imply that suspended particles reduce to only a limited extent the toxicity of pyrethroids to G. pulex and that passive uptake of pyrethroids can be significant even when pyrethroids are adsorbed to suspended particles.

Land management of bracken needs to account for bracken carcinogens--a case study from Britain.

Bracken ferns are some of the most widespread ferns in the World causing immense problems for land managers, foresters and rangers. Bracken is suspected of causing cancer in Humans due to its content of the carcinogen ptaquiloside. Ingestion of bracken, or food and drinking water contaminated with ptaquiloside may be the cause. The aim of this study was to monitor the content of ptaquiloside in 20 bracken stands from Britain to obtain a better understanding of the ptaquiloside dynamics and to evaluate the environmental implications of using different cutting regimes in bracken management. The ptaquiloside content in fronds ranged between 50 and 5790 µg/g corresponding to a ptaquiloside load in the standing biomass of up to 590 mg/m(2) in mature fronds. Ptaquiloside was also found in the underground rhizome system (11-657 µg/g) and in decaying litter (0.1-5.8 µg/g). The amount of ptaquiloside present in bracken stands at any given time is difficult to predict and did not show any correlations with edaphic growth factors. The content of ptaquiloside turned out to be higher in fronds emerging after cutting compared to uncut fronds. Environmental risk assessment and bracken management must therefore be based on actual and site specific determinations of the ptaquiloside content. Care must be taken to avoid leaching from cut ferns to aquifers and other recipients and appropriate precautionary measures must be taken to protect staff from exposure to bracken dust.

Determination of ptaquiloside and pterosin B derived from bracken (Pteridium aquilinum) in cattle plasma, urine and milk.

Ptaquiloside (PTA) is a toxin from bracken fern (Pteridium sp.) with genotoxic effects. Hydrolysis of PTA leads to the non-toxic and aromatised indanone, pterosin B (PTB). Here we present a sensitive, fast, simple and direct method, using SPE cartridges to clean and pre-concentrate PTA and PTB in plasma, urine and milk followed by LC-MS quantification. The average recovery of PTA in plasma, urine, and milk was 71, 88 and 77%, respectively, whereas recovery of PTB was 75, 82 and 63%. The method LOQ for PTA and PTB in plasma was 1.2 and 3.7ngmL(-1), 52 and 33ngmL(-1) for undiluted urine and 5.8 and 5.3ngmL(-1) for milk. The method is repeatable within and between days, with RSD values lower than 15% (PTA) and 20% (PTB). When PTA and PTB spiked samples were stored at -18°C for 14 days both compounds remained stable. In contrast, the PTA concentration was reduced by 15% when PTA spiked plasma was left for 5h at room temperature before SPE clean-up, whereas PTB remained stable. The method is the first to allow simultaneous quantification of PTA and PTB in biological fluids in a relevant concentration range. After intravenous administration of 0.092mg PTA per kgbw in a heifer, the plasma concentration was more than 300ngmL(-1) PTA and declined to 9.8ngmL(-1) after 6h, PTB was determined after 10min at 50ngmL(-1.)

Adsorption of mono- and di-butyltin by a wheat charcoal: pH effects and modeling.

Understanding adsorption processes of butyltins (BTs) such as monobutyltin (MBT) and dibutyltin (DBT) by black carbons is important for the evaluation of BT exposure risks to organisms and humans. However, relevant knowledge is scarce. In this study, the acidity constants pK(a,1)=2.3, pK(a,2)=3.5 and pK(a,3)=5.9 for MBT and pK(a,1)=3.0 and pK(a,2)=5.1 for DBT are estimated via potentiometric titration. Additionally, adsorption isotherms of BTs to a wheat charcoal were determined. The adsorption behavior was observed to be pH-dependent due to BT speciation and the pH-dependent surface charge of the charcoal. MBT adsorption to the charcoal decreases with increasing pH from 4 to 8, while the highest adsorption occurs at pH 6 for DBT. Adsorption of the BTs is successfully described in the pH range of 3-10 by using a newly developed pH-dependent Dual Langmuir model. The model has the potential to predict the interaction of BT species with charcoal, which can contribute to the risk assessments of BTs in the environment.

Toxicity and uptake of TRI- and dibutyltin in Daphnia magna in the absence and presence of nano-charcoal.

Butyltins (BTs), such as tributyltin (TBT) and dibutyltin (DBT), are toxic to aquatic organisms, but the presence of the strong adsorbent, black carbon (BC), can markedly influence BT toxicity and uptake in organisms. In the present study, the acute toxicity and uptake of TBT and DBT in the crustacean, Daphnia magna, were investigated with and without addition of nano-charcoal at different pHs and water hardnesses. The results showed that the toxicity of TBT and DBT increased by lowering the pH from 8 to 6. This reflects a relatively higher toxicity of cationic BT species than of the neutral species. At pH 6, by enhancing the water hardness of the media from 0.6 to 2.5 mM, the toxicity of TBT and DBT consistently decreased due to competitive binding of bivalent cations (Mg²âº, Ca²âº) to biotic ligands of D. magna. Furthermore, the toxicity of TBT to D. magna significantly decreased in the presence of nano-charcoal compared with experiments without nano-charcoal at pH 6 and 8, while no significant decrease in toxicity of DBT was observed in the presence of nano-charcoal. This can be attributed to the insignificant decrease of free DBT concentration in the presence of nano-charcoal compared with that for TBT. Conversely, it was observed that more TBT and DBT were taken up in D. magna in the presence of nano-charcoal due to the uptake of TBT or DBT associated with nano-charcoal by Daphnia in gut systems, as seen by light microscopy. This indicated that only free nonadsorbed BTs were toxic to D. magna, at least during short periods of exposure.