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.

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.

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.

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.

A comparative study of phosphate sorption in lowland soils under oxic and anoxic conditions.

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.

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.

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.

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.

Mass balance of cadmium in two contrasting oak forest ecosystems.

The mass balance of cadmium in forest ecosystems was parameterized. Soil pH is the main variable controlling retention of Cd in the soil and, hence, determines whether Cd is leached from the system or not. However the extent to which root uptake and biomass accumulation of Cd, or the return of Cd to the soil as internal cycling, influences forest Cd balances is unknown. Also unknown is whether these fluxes might counteract Cd leaching from forest soils. The objective of this study was to compare the Cd mass balance of two contrasting oak forest ecosystems, one grown on an acid sandy soil and one on a near-neutral loamy soil. The oak forest ecosystem grown on the acid sandy soil was a source of Cd with an input flux from deposition of 64 microg Cd m(-2) yr(-1), which was only 30% of the output flux with seepage water (175 microg Cd m(-2) yr(-1)). The oak forest ecosystem on the loamy soil acted as a sink for Cd, with an input flux (92 microg Cd m(-2) yr(-1)) 8.4 times higher than the output flux (11 microg Cd m(-2) yr(-1)). Biomass accumulation was 46% and 74% of root uptake on the sandy and the loamy soil, respectively, indicating that biomass accumulation, if harvested, will reduce the net return to the soil and hence the potential amount of Cd prone for leaching.

Phosphorus retention in riparian buffers: review of their efficiency.

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)).

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.

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.

Degradation kinetics of ptaquiloside in soil and soil solution.

Ptaquiloside (PTA) is a carcinogenic norsesquiterpene glycoside produced in bracken (Pteridium aquilinum (L.) Kuhn), a widespread, aggressive weed. Transfer of PTA to soil and soil solution eventually may contaminate groundwater and surface water. Degradation rates of PTA were quantified in soil and soil solutions in sandy and clayey soils subjected to high natural PTA loads from bracken stands. Degradation kinetics in moist soil could be fitted with the sum of a fast and a slow first-order reaction; the fast reaction contributed 20 to 50% of the total degradation of PTA. The fast reaction was similar in all horizons, with the rate constant k(1F) ranging between 0.23 and 1.5/h. The slow degradation, with the rate constant k(1S) ranging between 0.00067 and 0.029/ h, was more than twice as fast in topsoils compared to subsoils, which is attributable to higher microbial activity in topsoils. Experiments with sterile controls confirmed that nonmicrobial degradation processes constituted more than 90% of the fast degradation and 50% of the slow degradation. The lower nonmicrobial degradation rate observed in the clayey compared with the sandy soil is attributed to a stabilizing effect of PTA by clay silicates. Ptaquiloside appeared to be stable in all soil solutions, in which no degradation was observed within a period of 28 d, in strong contrast to previous studies of hydrolysis rates in artificial aqueous electrolytes. The present study predicts that the risk of PTA leaching is controlled mainly by the residence time of pore water in soil, soil microbial activity, and content of organic matter and clay silicates.

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.

Degradation kinetics of glucosinolates in soil.

Glucosinolates are compounds produced by all cruciferous plants. They can be hydrolyzed to several biologically active compounds and, as such, may serve as naturally produced pesticides. To optimize the pesticidal (biofumigation) effect and to assess the risk of glucosinolate leaching and spread in the environment, the degradation in soil of glucosinolates has been studied. The kinetics of degradation of four glucosinolates, two aliphatic (but-3-enyl and 2-hydroxy-but-3-enyl) and two aromatic (benzyl and phenethyl), in four soils was largely independent of the specific glucosinolate structure. Degradation followed logistic kinetics. Degradation was much faster in a clayey soil (half-life, 3.5-6.8 h) than in a sandy soil (half-life, 9.2-15.5 h). Degradation was much slower or nonexistent in the subsoil (<25 cm soil depth). The glucosinolates are not sorbed in the soil, and the degradation potential is, to a large extent, associated with the clay fraction. Measured activity in the soils of the enzyme myrosinase, which can catalyze the hydrolysis of glucosinolates, correlated well with the glucosinolate degradation kinetics. Autoclaving, but not sodium azide or gamma-irradiation, effectively blocked glucosinolate degradation, indicating that extracellular myrosinase is important for glucosinolate degradation.