Deactivation of mycotoxins. I. An in vitro study of zearalenone adsorption on new polymeric adsorbents.

This study describes the elimination of zearalenone concentrations in vitro using two new polymeric forms of cross-linked polyvinylpyrrolidone (cryogels of cross-linked PVP). Adsorption of zearalenone was studied under isothermal conditions and simulating pH of intestinal environment. A Freundlich isotherm was used to describe the adsorption data obtained. The results showed significant decrease of zearalenone concentrations, ranging from 33.5-66.2% per 25 mg of polymer. Adsorption capacity (k) was estimated to be higher than that of previously tested adsorbents, including crospovidone. The data indicate the need to investigate structure peculiarities in order to improve mycotoxin deactivation procedures using PVP derivatives.     

The effect of acute administration of the mycotoxin zearalenone to female pigs∗

Abstract

Crystalline zearalenone was administered to young female pigs at dose levels of 0, 3.5, 7.5 and 11.5 mg zearalenone/kg body weight. All animals receiving the mycotoxin exhibited vulva vag‐initis and had enlarged reproductive tracts, 1 week after dosing. Free zearalenone was found in the blood, feces and urine of dosed animals. The highest zearalenone level detected was 2.61 ng/ml from a pig that received the 7.5 mg/kg dose. After 24 hours, feces collected contained on average up to 308 ng zearalenone per g of dried feces. Zearalenone levels of up to 59 ng/ml, and a ‐zearalenol levels of up to 155 ng/ml urine were found. ß ‐zearalenol was also detected in the urine.     

Sorptive interactions and binding of δ‐endotoxin protein from bacillus thuringiensis subsp. kurstaki inforest soils

Abstract

The adsorption, desorption and binding of the insecticidal protein from Bacillus thuringiensis subsp. kurstaki (Btk toxin) onto autoclaved sandy and clay loam forest soils were studied at 23°C in a buffer medium (pH 10.2) using the precipitated protein mixture (active + inactive) obtained from a commercial Btk formulation. The active protein in the buffer solution was quantified by ELISA technique. Maximum adsorption of the toxin onto the sandy (301 μg/g) and clay (474 μg/g) loam soils was found to occur after 3 and 4 hours of agitation, respectively. Adsorption of the toxin was higher in the clay loam soil than in sandy loam. Adsorption parameters were calculated using the Freundlich and linear isotherm equations. The K_F and 1/n values for the soils were 1.12 and 1.48 (sandy), and 20.42 and 0.874 (clay), respectively, indicating stronger affinity of the toxin for the clay compared to the sandy loam soil. The linear model showed deviations at higher concentrations, nevertheless using the best fit, K_D and K_OC values were computed for the two soils. For sandy loam, the K_D and K_OC values were 9.38 and 391, respectively; the corresponding values for clay loam were 13.19 and 425, confirming the higher sorption affinity of the toxin for clay loam. The adsorption data did not fit the Langmuir equation because of heterogeneity of the soil surface. Desorption studies showed that more than half of the adsorbed toxic protein remained firmly attached to sandy (162.6 μg/g or 54.5%) and clay (314.0 μg/g or 67.4%) loam soils after six 0.5‐h washes (total 3.0 h wash time). Although the toxin appears to be a non‐leacher, its lateral mobility, soil persistence and biological consequences, including bioavailability of the bound residues, are poorly understood and require further investigation.     

A high pressure liquid chromatographic method for the analysis of zearalenone in chicken blood

Abstract

A high pressure liquid chromatographic (HPLC) method is described to determine zearalenone in chicken blood. Samples are extracted with acetonitrile, followed by a hexane cleanup procedure and extracted further with ethyl acetate. The analysis of zearalenone is by HPLC using a reverse phase radial compression separation system, an ultraviolet absorbance detector and a mobile phase of acetonitrile‐water 60:40 (v/v). Recoveries of zearalenone in blood at levels of 50–200 ng/ml are in the range of 66.8–72.6%.     

Adsorption behavior of RH‐5992 insecticide onto sandy and clay loam forest soils

Abstract

Adsorption‐desorption behavior of RH‐5992 [Mimic®, N'‐t‐butyl‐N'‐(3,5‐dimethylbenzoyl)‐N‐(4‐ethylbenzoyl) hydrazine] in sandy and clay loam forest soils was studied using the batch equilibrium method. Adsorption was higher in the clay loam soil than in the sandy loam, and increased linearly with RH‐5992 concentration, but decreased with increasing pH and temperature. The adsorption data fit better to the Freundlich, than to the Langmuir equation. The K_D (linear adsorption constant) and K_F (Freundlich constant) were similar for each soil at 5, 15 and 25°C and decreased with increase of temperature, indicating that the enthalpy of adsorption was negative. The exponent of the Freundlich equation was close to unity for both soils at all three temperatures. The low E_a (energy of activation) indicated a diffusion‐controlled process during the initial stages of adsorption. The desorption isotherm differed from that of adsorption, and the linear desorption constant, K_D(d), was ca 25 times higher than the K_D, indicating that adsorption of RH‐5992 was not readily reversible. Evaluation of thermo‐dynamic parameters confirmed the presence of strong bonds between the solute and soil. These findings suggest that RH‐5992 has a limited potential for downward mobility leading to groundwater contamination.     

Behavior of Two Phenyl Urea Herbicides in Clayey Soils and Effect of Alternating Dry-Wet Conditions on their Availability

Adsorption and mobility of linuron (3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea) and diuron (3-(3,4-dichlorophenyl)-1, 1-dimethylurea) were studied in clayey soils from the Gharb area (Morocco). Soils A and B were planted with sun flower (Helianthus annuus) while soil C was planted with sugar cane (Saccharum offcinarum). Adsorption was studied for linuron in soils A and B, while mobility was studied only in soil B. Adsorption data were found to fit the Freundlich equation with correlation coefficients r² > 0.9. Freundlich coefficients (K_f, n_f) were in agreement with L and S isotherm types for soils A and B, respectively. Values of K_oc (195 and 102) indicate moderate adsorption. Desorption isotherms for linuron showed hysteresis for both soils. The pesticide would be more bound to soil A (H = 8.44) than to soil B (H = 4.01). The effect of alternating wet and dry conditions was tested for soils A and B. Results showed that retention would increase in soil subject to an additional wet and dry cycle. In the case of diuron isotherm was of type L in soil C. Desorption was noticeable at high concentrations and tended to decrease when concentrations diminished. Mobility of linuron was tested in polyvinyle chloride (PVC) columns, which received different treatments before their percolation. The pesticide was more mobile in a previously saturated column. In columns subject to a drying step after saturation with water, linuron mobility was greatly reduced.     

Evaluation of a Daphnia magna renewal life‐cycle test method with diazinon

Abstract

Acute and chronic toxicity tests with diazinon (diethyl 2‐isopropyl‐6‐methyl‐4‐pyrimidinyl phosphorothionate) were conducted on Daphnia magna. The 24‐hr static LC50 was 0.86 μL.L^‐1. The sublethal effects of 0.05, 0.1, 0.5, 0.75 and 1.0 ngL^‐1 of diazinon concentrations on the survival, reproduction and growth of D. magna were monitored for 21 days. The algae Nannochloris oculata (5 x 10⁵ cellsmL^‐1) was used to feed the daphnids. The parameters used to determined the effect of the pesticide on D. magna were: mean total young per female; mean brood size; days to first brood; intrinsic rate of natural increase (r); growth; and survival. Reproduction as well as survival was significantly reduced at diazinon concentrations of 0.10 ngL^‐1 and higher. The intrinsic rate of natural increase (r) decreased with increasing concentrations of diazinon. Growth, as measured by body length, was depressed significantly at 0.05 ngL^‐1 of diazinon and higher concentrations. The maximum acceptable toxicant concentration (MATC) was calculated. The chronic data was used to formulate an acute/chronic ratio.     

Evaluation of Beta‐naphthoxyacetic Acid for Mutagenic Activity in the Salmonella/mammalian Microsome Assay

1,3‐β‐d‐Glucan derived from baker's yeast was chemically modified in two steps yielding crosslinked carboxymethyl glucan as the sodium salt (2). After cation exchange with hexadecyltrimethylammonium chloride, a hydrophobic adsorbent (3) was obtained which showed an excellent binding of the estrogenic mycotoxin zearalenone with a maximum adsorption of up to 183 mg/g. Compound 3 additionally showed a relatively high adsorption capacity for the trichothecene T‐2 toxin of at least 10 mg/g. Starting from 2, various derivatives were prepared by cation exchange using quaternary ammonium salts bearing substituents besides methyl from four to 18 carbon atoms. The adsorption of T‐2 toxin on these derivatives were compared with compound 3 leading to the conclusion that 3 is the best adsorbent of all investigated tetraalkylammonium‐modified derivatives of 2.     

Effect of tracer dyes on initial deposits and persistence of bacillus thuringiensis subsp. kurstaki toxin after application of two commercial formulations onto spruce trees

Abstract

The effect of two tracer dyes [Erio Acid Red (EAR) and Acid Black 48 (AB‐48)] on initial deposits and persistence of Bacillus thuringiensis subsp. kurstaki (Btk) toxin (delta‐endotoxin) was studied after spraying two commercial formulations, Foray® 48B and Foray® 76B, over potted white spruce [Picea glauca (Moench) Voss] seedlings, at a dosage rate of 30 billion international units (BIU) per ha. Spray was applied using a spinning disc atomizer calibrated to deliver droplet sizes similar to those utilized in ultra‐low‐volume (ULV) treatments in operational insect control programs. The sprayed seedlings were left outdoors at the Sault Ste. Marie laboratory for 18 days under natural conditions of sunlight, wind and rainfall. Initial deposits and persistence of delta‐endotoxin protein in spruce foliage were determined by immunoassay [enzyme linked immunosorbent assay (ELISA)] quantification of the delta‐endotoxin. The total protein (inactive plus active) and delta‐endotoxin (active protein) concentrations in the two formulations were determined by a gravimetric procedure and by ELISA respectively.

The initial deposit levels of the toxin on foliage were not markedly affected by the addition of either of the two tracer dyes, and showed only a narrow range of 1521 to 1625 ng/g foliage (fresh weight) for Foray 48B, and 1789 to 2056 ng/g for Foray 76B. However, the persistence of the toxin was significantly influenced by the presence of the dyes. The toxin persisted in foliage only for 7 d post‐spray When the EAR dye was added to Foray 48B, compared to 10 d when no dye was added. The average half‐life (DT₅₀) of disappearance was 17.4 h for Foray 48B with EAR, and 20.9 h when no dye was present. In contrast, the situation was reversed in Foray 76B, since the duration of persistence was 10 d when EAR was added to Foray 76B, compared to 7 d when no dye was added. The average DT₅₀ was 27.9 h for Foray 76B with EAR, and 22.2 h without the dye. Persistence was the longest (14 d) when the AB‐48 dye was added to Foray 76B, and the DT₅₀ was 44.9 h.     

Effects of lindane on Daphnia magna during chronic exposure

Abstract

Acute and chronic toxicity tests with lindane were conducted on Daphnia magna. The 24‐hr static LC50 was 1.64 mgL^‐1. The sublethal effects of 0.16, 0.25, 0.32, 0.60 and 0.80 mgL^‐1 lindane on the survival, reproduction and growth of D. magna were monitored for 21 days. The algae Nannochloris oculata (5 × 10⁵ cellsmL^‐1) was used to feed the daphnids. The parameters used to determined the effect of the pesticide on D. magna were:mean total young per female, mean brood size, days to first brood, intrinsic rate of natural increase (r), growth, and survival. Reproduction as well as survival was significantly reduced at lindane concentrations of 0.25 mgL^‐1 and higher. The intrinsic rate of natural increase (r) decreased with increasing concentrations of lindane. Growth, as measured by body length, was depressed significantly at 0.25 mgL^‐1 lindane and higher. The chronic data was used to formulate an acute/chronic ratio.     

Utilizing vortex behaviour to minimize drift

Abstract

The ULV spray emitted from a TBM flying in a cross wind was mapped by a scanning lidar system. The fate of the spray cloud for 2 min after release from the aircraft was followed as the material was transported downwind of the flight line. Vertical scans at 6 s intervals with 1 m^‐3 resolution provided detailed insight into the entrainment of the spray into the wing‐tip vortices and ultimate release to drift or deposit. Relative concentration, dosage and deposit profiles are presented for this cross‐wind case. Vortex lifetimes were found to be significantly different for the up‐wind and downwind vortices. The majority of the near field deposit was associated with the up‐wind vortex while the drift was linked to the down‐wind vortex.     

1‐Aminobenzotriazole increases glutathione‐s‐transferase activity of maize

Abstract

Glutathione‐S‐transferase (GST) activity of maize (Zea mays L.) seedlings treated with 1‐aminobenzotriazole (ABT) derivatives and/or EPTC were measured using EPTC‐sulfoxide as substrate. Both safeners and ABT derivatives significantly elevated the GST activity in the concentrations needed for effective safening action. ABT is considered as an inhibitor of plant cytochrome P‐450 monooxygenases (P‐450) and, because of this, used to study herbicide mode of action. Our data indicate that ABT has multiple effects on plants influencing not only P‐450 but GST as well. Thus the role of ABT in herbicide metabolism needs reconsideration.     

Curvularin from Penicillium baradicum baghdadi NRRL 3754, and biological effects

Abstract

Curvularin, a fungal metabolite similar in chemical structure to zearalenone, a potent estrogen, was tested for its estrogenic effects to gilts. No estrogenicity was observed to 60 kg gilts after feeding curvularin per os at a rate of 10 mg per day for 5 days. Curvularin was also nontoxic to mice and chick embryo.     

Effects of sublethal exposure to a pesticide on levels of energetic compounds in Anguilla anguilla.

Abstract

The effect of two sublethal fenitrothion concentrations (0.02 and 0.04 mg/L) on the energy metabolism of the european eel Anguilla anguilla and its recovery from intoxication was investigated. Analysis of various parameters such as glycogen, proteins and total lipids was made on liver and muscle eel tissues after 2, 8, 12, 24, 32, 48, 56, 72 and 96 hr of fenitrothion (0,0‐dimethyl 0–3‐methyl‐4‐nitrophenyl phosphorothioate) exposure. Subsequently, the fish were allowed recovery periods of 8, 12, 24, 48, 72, 96, 144 and 192 hr in clean water, and the same parameters were again evaluated. The results obtained during the exposure to the pesticide as well as during the recovery phase were used to calculate the caloric content in both tissues of A. anguilla. A reduction in energy reserves in the selected tissues was observed after exposure to both fenitrothion concentrations and the caloric content in those animals was lower than in the controls. Most of the metabolic disorders did not persist after allowing recovery in clean water during a week.     

Comparative assessment of metribuzin sorption efficiency of biochar,hydrochar and vermicompost

Abstract

In this study, we used two biochars (BC) produced from grapevine pruning residues (BCgv) and red spruce wood (BCrs), two hydrochars (HC) from urban pruning residues (HCup) and the organic fraction of municipal solid wastes (HCuw), and two vermicomposts (VC) obtained vermicomposting digestates from buffalo manure (VCbm) and mixed feedstock (VCmf). Adsorption kinetics and isotherms of metribuzin onto these materials were performed. Sorption kinetics followed preferentially a pseudo-second-order model, thus indicating the occurrence of chemical interactions between the sorbate and the adsorbents. Adsorption constants were calculated using the Freundlich and Langmuir models. Metribuzin sorption data on BCgv and both HC fitted preferentially the Freundlich equation, whereas on the other materials data fitted both isotherms well (r?>?0.95). Metribuzin sorption capacity of the materials followed the trend BC?>?HC?>?VC. Sorption constants of metribuzin normalised per organic carbon content (K_OC) on BCgv, BCrs, HCup, HCuw, VCbm and VCmf were 561, 383, 251, 214, 102 and 84?L kg^?1, respectively. A significant positive correlation (P?=?0.016) was calculated between distribution coefficients (K_d) of all materials and the corresponding organic carbon contents, thus indicating a prominent role of the organic fraction of these materials in the adsorption of metribuzin.     

Effects of the herbicide molinate on the metabolic activities of a degradative Streptomyces griseus strain

Abstract

Cometabolic degradation of the herbicide molinate was tested using two microorganisms, Arthrobacter sp., strain M3 and Streptomyces griseus strain M2; the latter classified on the basis of the presence of the enzymatic cofactor SF‐420. The strains M3 and M2, inoculated in a basic salts medium with glucose as carbon source and added with 100 mg L^‐1 of molinate, degraded respectively 35 and 51% of the herbicide in 36 days.

Increasing concentrations of molinate, ranging from 50 to 200 mg L^‐1 in glucose medium, did not affect the final ATP yield of the strain M2, but decreased the final growth yield and the ATP synthesis rate. Moreover, the onset of coenzyme SF‐420 synthesis was progressively delayed.

In contrast, surprisingly, SF‐420 final yield and production rate were increased by progressive increasing concentrations of molinate in the mineral medium.     

Persistence of Bacillus thuringiensis deposits in a hardwood forest,after aerial application of a commercial formulation at two dosage rates

Abstract

A commercial formulation of Bacillus thuringiensis Berliner var. kurstaki (BTK), Foray® 48B, was sprayed aerially over four blocks B13, B14, B15A and B15B in an oak forest in Wayne County, Pennsylvania during May 1990. B13 and B14 were sprayed at 75 billion international units (BIU) in 5.91 litres/ha and the other two at 50 BIU in 3.94 litres/ha. Oak foliage was collected at different intervals of time after treatment. Three types of bioassays were conducted against fourth instar gypsy moth larvae, viz., direct feeding of sprayed foliage, feeding on diet containing homogenized foliage, and force‐feeding of foliar extracts. Larval mortalities were converted into international units of BTK activity per unit area (IU/cm²) of foliage. Foliar extracts were also subjected to enzyme‐linked immunosorbent assay (ELISA) to determine the concentration of delta‐endotoxin protein. Regardless of the type of bioassay used, bioactivity of BTK persisted in foliage for about a week in all the blocks. The half‐life of inactivation, DT₅₀, ranged from ca 12 to 22 h. The immunoassay data indicated a shorter duration of persistence (i.e., about 2 d) of the delta‐endotoxin protein, with DT₅₀ values ranging from 10 to 15 h. Formulation ingredients present in Foray 48B played a role in the toxicity of BTK to gypsy moth larvae.     

Residues of legacy organochlorine pesticides and DDT metabolites in highly consumed fish from the polluted Guanabara Bay,Brazil: distribution and assessment of human health risk

Abstract

Organochlorine (OCP) pesticides were determined in samples of sardine (Sardinella brasiliensis), whitemouth croaker (Micropogonias furnieri), and mullet (Mugil liza) from Guanabara Bay (state of Rio de Janeiro, Brazil). OCP concentrations and fish consumption were linked with acceptable daily intake values in order to assess the human health risk for the Brazilian population. The total concentrations of OCPs (Σ OCP) was 6.6?ng/g f.w., 7.5?ng/g f.w., and 2.8?ng/g f.w. for sardines, corvina, and mullet, respectively. There was a significant difference (P?<?0.05) among the species related to o,p’-DDD and o,p’-DDT concentrations. Both DDT-related compounds were 5 and 76 times more abundant in sardines than in whitemouth croaker and mullet. Newly discovered DDT metabolite, o-Cl-DDMU, was frequently detected in the fish. None of the samples exceeded the maximum limits for acceptable levels of OCP residues. According to the data of average intake of Brazilian population, none of three species exceeded toxicological parameter. The investigated fishes are considered as safe for human consumption in regard to exposure of the studied OCPs. However, fish may be a intake source of OCP metabolites such as o-Cl-DDMU whose toxicity is still unknown.     

Root uptake,translocation, accumulation and dissipation of the botanical insecticide,azadirachtin, in young spruce trees

Abstract

A formulation containing the biopesticide azadirachtin‐A (AZ‐A), extracted from the seeds of neem tree, Azadirachta indica A. Juss, was applied (10 μg/mL) in a nutrient solution (200 mL) to the roots of young spruce trees [Picea glauca (Moench) Voss]. The uptake, translocation, persistence and dissipation of AZ‐A in spruce were studied. The insecticide was taken up by the root system, translocated via xylem vessels and accumulated in the photosynthate sinks (areas of new growth, especially shoots), confirming that AZ‐A is systemic. The peak AZ‐A concentrations (μg/g, fresh weight) in the shoots (5.16 ± 0.73) and needles (2.56 ± 0.31) occurred at 8 and 15 d after treatment, respectively. The AZ‐A concentrations in bark and wood during this period were very low, however they were high in the root samples. The dissipation of AZ‐A from the shoots was rapid compared to other matrices. The initial (0‐d) and final (20‐d) AZ‐A concentrations (μg/mL) in the nutrient solution were 8.99 ± 1.24 and 3.24 + 0.55, respectively. The dissipation of AZ‐A in the nutrient solution followed first‐order kinetics. Dissipation half‐life (DT₅₀) and rate constant (C), calculated from the nonlinear regression equation (Y = 8.400 e^‐00544t), were 12.74 d and 0.0544, respectively. Usefulness of AZ‐A as a systemic insecticide in forest insect control programs is discussed.     

Paraquat Adsorption,Degradation, and Remobilization in Tropical Soils of Thailand

Paraquat adsorption, degradation, and remobilization were investigated in representative tropical soils of Yom River Basin, Thailand. Adsorption of paraquat in eight soil samples using batch equilibration techniques indicated that adsorption depended on soil characteristics, including exchangeable basic cations and iron content. Multiple regression analysis indicated significant contribution of exchangeable calcium percentage (ECP), total iron content (TFe) and exchangeable sodium percentage (ESP) to paraquat sorption (Q). ESP and TFe were significant at all adsorption stages, whereas ESP was significant only at the initial stage of paraquat adsorption. Adsorption studies using two soils representing clay and sandy loam textures showed that paraquat adsorption followed the Freundlich model, exhibiting a nonlinear sorption curve. Paraquat adsorption was higher in the clay soil compared to the sandy loam soil with K _f values of 787 and 18, respectively. Desorption was low with 0.04 to 0.17% and 0.80 to 5.83% desorbed in clay and sandy loam soil, respectively, indicating some hysteresis effect. Time-dependent paraquat adsorption fitted to the Elovich kinetic model indicated that diffusion was a rate-limiting process. Paraquat mobility and degradation studies conducted using both field and laboratory soil column experiments with clay soil showed low mobility of paraquat with accumulation only in the surface 0–5 cm layer under field conditions and in the 0–1 cm layer in a laboratory soil column experiment. Degradation of paraquat in soil was faster under field conditions than at ambient laboratory conditions. The degradation rate followed a first-order kinetic model with the DT₅₀ at 36–46 days and DT₉₀ around 119–152 days.