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1.
Sci Total Environ ; 717: 136969, 2020 May 15.
Artigo em Inglês | MEDLINE | ID: mdl-32062247

RESUMO

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.

2.
Artigo em Inglês | MEDLINE | ID: mdl-31931331

RESUMO

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.


Assuntos
Cromatografia Líquida/métodos , Glicosídeos , Indanos , Pteridium/química , Sesquiterpenos , Glicosídeos/análise , Glicosídeos/química , Indanos/análise , Indanos/química , Limite de Detecção , Modelos Lineares , Espectrometria de Massas/métodos , Compostos Fitoquímicos/análise , Compostos Fitoquímicos/química , Extratos Vegetais/química , Sesquiterpenos Policíclicos/análise , Sesquiterpenos Policíclicos/química , Reprodutibilidade dos Testes , Sesquiterpenos/análise , Sesquiterpenos/química
3.
PLoS One ; 14(6): e0218628, 2019.
Artigo em Inglês | MEDLINE | ID: mdl-31226154

RESUMO

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.


Assuntos
Carcinógenos/farmacocinética , Bovinos/metabolismo , Indanos/farmacocinética , Sesquiterpenos/farmacocinética , Animais , Inativação Metabólica , Indanos/sangue , Indanos/urina , Pteridium/química , Rúmen/metabolismo , Sesquiterpenos/sangue , Sesquiterpenos/urina
4.
Environ Pollut ; 248: 584-598, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-30836240

RESUMO

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.


Assuntos
Monitoramento Ambiental/métodos , Metais Pesados/análise , Material Particulado/análise , Chuva/química , Poluentes Químicos da Água/análise , Pequim , Urbanização
5.
Chemosphere ; 223: 723-730, 2019 May.
Artigo em Inglês | MEDLINE | ID: mdl-30802838

RESUMO

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.


Assuntos
Apatitas , Carvão Vegetal/farmacologia , Fósforo , Solo/química , Animais , Osso e Ossos/química , Carvão Vegetal/química , Fertilizantes , Temperatura
6.
Sci Total Environ ; 630: 331-339, 2018 Jul 15.
Artigo em Inglês | MEDLINE | ID: mdl-29482141

RESUMO

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.

8.
Chemosphere ; 165: 453-459, 2016 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-27677121

RESUMO

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.


Assuntos
Carcinógenos/química , Indanos/química , Pteridium/química , Sesquiterpenos/química , Poluentes do Solo/química , Concentração de Íons de Hidrogênio , Hidrólise
9.
Anal Bioanal Chem ; 408(28): 7981-7990, 2016 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-27590319

RESUMO

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.

10.
Ecotoxicology ; 25(3): 510-20, 2016 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-26831865

RESUMO

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.


Assuntos
Anfípodes/efeitos dos fármacos , Piretrinas/toxicidade , Poluentes Químicos da Água/toxicidade , Animais , Água Doce , Inseticidas/toxicidade
11.
J Environ Manage ; 151: 258-66, 2015 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-25577704

RESUMO

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.


Assuntos
Carcinógenos/análise , Indanos/análise , Pteridium/química , Sesquiterpenos/análise , Solo/química , Conservação dos Recursos Naturais , Monitoramento Ambiental , Humanos , Indanos/química , Folhas de Planta/química , Rizoma/química , Medição de Risco , Escócia , Estações do Ano , Sesquiterpenos/química
12.
Artigo em Inglês | MEDLINE | ID: mdl-24508676

RESUMO

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.)


Assuntos
Indanos/análise , Leite/química , Pteridium/química , Sesquiterpenos/análise , Animais , Bovinos , Feminino , Indanos/química , Indanos/farmacocinética , Limite de Detecção , Modelos Lineares , Reprodutibilidade dos Testes , Sesquiterpenos/química , Sesquiterpenos/farmacocinética
13.
Chemosphere ; 89(7): 863-8, 2012 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-22664389

RESUMO

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.


Assuntos
Carvão Vegetal/química , Poluentes Ambientais/química , Modelos Moleculares , Compostos Orgânicos de Estanho/química , Adsorção , Concentração de Íons de Hidrogênio , Triticum/química
14.
Environ Toxicol Chem ; 30(11): 2553-61, 2011 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-21858855

RESUMO

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.


Assuntos
Carvão Vegetal/química , Daphnia/efeitos dos fármacos , Nanopartículas/química , Compostos Orgânicos de Estanho/toxicidade , Compostos de Trialquitina/toxicidade , Adsorção , Animais , Daphnia/metabolismo , Concentração de Íons de Hidrogênio , Modelos Químicos , Compostos Orgânicos de Estanho/farmacocinética , Testes de Toxicidade , Compostos de Trialquitina/farmacocinética , Água/química , Poluentes Químicos da Água/farmacocinética , Poluentes Químicos da Água/toxicidade
15.
Environ Pollut ; 159(10): 3071-7, 2011 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-21555174

RESUMO

Metabolic profiling in plants can be used to differentiate between treatments and to search for biomarkers for exposure. A methodology for processing Ultra-High-Performance Liquid Chromatography-Diode-Array-Detection data is devised. This methodology includes a scheme for selecting informative wavelengths, baseline removal, retention time alignment, selection of relevant retention times, and principal component analysis (PCA). Plant crude extracts from rapeseed seedling exposed to sublethal concentrations of glyphosate are used as a study case. Through this approach, plants exposed to concentrations down to 5 µM could be distinguished from the controls. The compounds responsible for this differentiation were partially identified and were different from those specific for high exposure samples, which suggests that two different responses to glyphosate are elicited in rapeseed depending on the level of exposure. The PCA loadings indicate that a combination of other metabolites could be more sensitive than the response of shikimate to detect glyphosate exposure.


Assuntos
Brassica rapa/metabolismo , Monitoramento Ambiental/métodos , Glicina/análogos & derivados , Herbicidas/toxicidade , Metaboloma , Plântula/metabolismo , Biomarcadores/metabolismo , Brassica rapa/efeitos dos fármacos , Cromatografia Líquida de Alta Pressão , Glicina/toxicidade , Metabolômica , Plântula/efeitos dos fármacos
16.
Environ Toxicol Chem ; 30(8): 1785-92, 2011 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-21590795

RESUMO

Cyclotides are bioactive, stable mini-proteins produced in high amounts in Violaceae and Rubiaceae with promising pharmaceutical and agrochemical applications. Environmental issues must be addressed before large-scale plant cultivation of cyclotides for pharmaceutical or pesticidal purposes can commence. The objective of the present study was to investigate sorption of the cyclotide kalata B2 (kB2), because knowledge of cyclotide biogeochemistry will aid our understanding of environmental fate. The octanol-water partitioning coefficient was determined to be 2.8 ± 0.6 (log K(OW) = 0.4 ± 0.1). Sorption of kB2 by montmorillonite, goethite, and humic acid was investigated at different concentrations and under varying acidity and reached equilibrium within minutes. The kB2 sorption at a solution concentration of 0.2 mg/L to montmorillonite was high (120 mg/g) compared to humic acid (0.60 mg/g) and goethite (0.03 mg/g). Kalata B2 intercalated the interlayer space of montmorillonite. The sorption isotherm for humic acid was linear up to a solution concentration of 0.8 mg/L and concave for montmorillonite and goethite up to an equilibrium solution concentration of 1.5 mg/L. Sorption to goethite was unaffected by pH, but sorption to montmorillonite and humic acid at pH near the isoelectric point (pI) was threefold the sorption when pH > the isoelectric point, suggesting that electrostatic interaction/repulsion between kB2 and sorbents play an important role. The strong sorption to montmorillonite reduces exposure to below toxic threshold values. In addition, the transport risk of soluble cyclotides is reduced, but particle-bound cyclotides may be transported to recipient aquatic sediments with the associated risk of adversely affecting sediment-dwelling organisms.


Assuntos
Bentonita/química , Ciclotídeos/química , Substâncias Húmicas , Compostos de Ferro/química , Minerais/química , Extratos Vegetais/química , Solo/química , Poluentes Químicos da Água/química , Adsorção , Meio Ambiente , Gleiquênias/química , Medição de Risco , Rubiaceae/química
17.
Environ Toxicol Chem ; 30(5): 1190-6, 2011 May.
Artigo em Inglês | MEDLINE | ID: mdl-21337607

RESUMO

Bioactive compounds produced by plants are easily transferred to soil and water and may cause adverse ecosystem effects. Cyclotides are gene-encoded, circular, cystine-rich mini-proteins produced in Violaceae and Rubiaceae in high amounts. Based on their biological activity and stability, cyclotides have promising pharmaceutical and agricultural applications. We report the toxicity of the cyclotides: kalata B1, kalata B2, and cycloviolacin O2 extracted from plants to green algae (Pseudokirchneriella subcapitata), duckweed (Lemna minor L.), lettuce (Lactuca sativa L.), and bacteria extracted from soil measured as [³H]leucine incorporation. Quantification by liquid chromatography-mass spectrometry demonstrated up to 98% loss of cyclotides from aqueous solutions because of sorption to test vials. Sorption was prevented by adding bovine serum albumin (BSA) to the aqueous media. Cyclotides were toxic to all test organisms with EC50 values of 12 through 140 µM (algae), 9 through 40 µM (duckweed), 4 through 54 µM (lettuce), and 7 through 26 µM (bacteria). Cycloviolacin O2 was the most potent cyclotide in all assays examined. This report is the first to document toxic effects of cyclotides in plants and soil bacteria and to demonstrate that cyclotides are as toxic as commonly used herbicides and biocides. Hence, cyclotides may adversely affect soil and aquatic environments, which needs to be taken into account in future risk assessment of cropping systems for production of these highly bioactive compounds.


Assuntos
Bactérias/efeitos dos fármacos , Ciclotídeos/toxicidade , Extratos Vegetais/toxicidade , Microbiologia do Solo , Poluentes Químicos da Água/toxicidade , Araceae/efeitos dos fármacos , Produtos Biológicos/toxicidade , Clorófitas/efeitos dos fármacos , Relação Dose-Resposta a Droga , Alface/efeitos dos fármacos
18.
Chemosphere ; 79(4): 434-40, 2010 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-20189217

RESUMO

Acephate is poorly sorbed to soil, thus the risk of leaching to the aquatic environment is high if it is not quickly degraded. The effect of soil moisture, temperature, microbial activity and application rate on acephate degradation has been studied in three Malaysian soils to examine and identify critical variables determining its degradation and mineralization kinetics. First-order kinetics could be used to describe degradation in all cases (r(2)>0.91). Acephate degraded faster in air-dry (t((1/2)) 9-11 d) and field capacity (t((1/2)) 10-16d) soils than in the wet soils (t((1/2)) 32-77 d). The activation energy of degradation was in the range 17-28 kJ mol(-1) and significantly higher for the soil with higher pH and lower clay and iron oxide contents. Soil sterilization caused a 3- to 10-fold decrease in degradation rates compared to non-sterile soils (t((1/2)) 53-116 d) demonstrating that acephate degradation is mainly governed by microbial processes. At 5-fold increase in application rates (25 microg g(-1)), half-life increased slightly (t((1/2)) 13-19 d) or was unaffected. Half-life from acephate mineralization was similar to those from degradation but much longer at the 5-fold increase in acephate application rates (t((1/2)) 41-96 d) demonstrating that degradation of metabolites is rate limiting. Thus, application of acephate should be restricted or avoided during wet seasons with heavy rainfall and flooded soil as in paddy cultivation. Sandy soils with low microbial activity are more prone to acephate leaching than clay soils rich in humic matter.


Assuntos
Inseticidas/metabolismo , Compostos Organotiofosforados/metabolismo , Poluentes do Solo/metabolismo , Biodegradação Ambiental , Umidade , Inseticidas/química , Cinética , Malásia , Compostos Organotiofosforados/química , Fosforamidas , Microbiologia do Solo , Poluentes do Solo/química , Temperatura
19.
J Environ Qual ; 39(2): 734-43, 2010.
Artigo em Inglês | MEDLINE | ID: mdl-20176846

RESUMO

Phosphate (P(i)) release due to Fe(III) oxide dissolution is well documented for soils undergoing reduction. The P(i) sorption properties of soils in anoxic conditions are, however, still under consideration. In this investigation, P(i) sorption to strictly anoxic soils was compared with oxic conditions to assess the potential of lowland soils to function as traps for P(i) when flooded with drainage water. Batch sorption experiments were performed on seven minerogenic soils. Sorption to the anoxic soils was conducted after anoxic incubation, resulting in reduction of 36 to 93% of the dithionite-extractable Fe(III) (Fe(BD)). Langmuir fitted P(i) sorption isotherms showed a P(i) release of up to 1.1 mmol kg(-1) in six soils when P(i) concentrations in the matrix (P(sol)) were lower than 10 microM. Phosphate desorption was attributed to dissolution of amorphous iron oxides, and higher pH under anoxic conditions. The point of zero net sorption (EPC(0)) increased 2- to 10-fold on reduction. Five soils showed higher P(i) sorption capacities in the anoxic than in the oxic state at higher P(sol) concentrations. Solubility calculations indicated that precipitation of vivianite or similar Fe(II) phosphates may have caused the higher sorption capacities. Use of maximum sorption capacity (S(max)) is therefore misleading as a measure of P(i) sorption at low P(sol) concentrations. The results demonstrate that none of the strongly anoxic soils, irrespective of the initial Fe(III) oxide content, the P saturation, and the degree of Fe(III) oxide reduction, could retain P(i) at natural P(sol) concentrations in agricultural drainage water.


Assuntos
Compostos Férricos/química , Fosfatos/análise , Solo/análise , Adsorção , Oxirredução , Fosfatos/química , Termodinâmica
20.
J Environ Qual ; 38(5): 1942-55, 2009.
Artigo em Inglês | MEDLINE | ID: mdl-19704138

RESUMO

Ground water and surface water interactions are of fundamental importance for the biogeochemical processes governing phosphorus (P) dynamics in riparian buffers. The four most important conceptual hydrological pathways for P losses from and P retention in riparian buffers are reviewed in this paper: (i) The diffuse flow path with ground water flow through the riparian aquifer, (ii) the overland flow path across the riparian buffer with water coming from adjacent agricultural fields, (iii) irrigation of the riparian buffer with tile drainage water from agricultural fields where disconnected tile drains irrigate the riparian buffer, and (iv) inundation of the riparian buffer (floodplain) with river water during short or longer periods. We have examined how the different flow paths in the riparian buffer influence P retention mechanisms theoretically and from empirical evidence. The different hydrological flow paths determine where and how water-borne P compounds meet and interact with iron and aluminum oxides or other minerals in the geochemical cycling of P in the complex and dynamic environment that constitutes a riparian buffer. The main physical process in the riparian buffer-sedimentation-is active along several flow paths and may account for P retention rates of up to 128 kg P ha(-1) yr(-1), while plant uptake may temporarily immobilize up to 15 kg P ha(-1) yr(-1). Retention of dissolved P in riparian buffers is not as pronounced as retention of particulate P and is often below 0.5 kg P ha(-1) yr(-1). Several studies show significant release of dissolved P (i.e., up to 8 kg P ha(-1) yr(-1)).


Assuntos
Fósforo/análise , Rios/química , Biotransformação , Conservação dos Recursos Naturais , Monitoramento Ambiental , Inundações , Movimentos da Água , Áreas Alagadas
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