Estimating the risks and benefits of pesticides: considering the agroecosystem and integrated pest management in the use of EBDC fungicides on apples

Calculating the risks and benefits of agricultural pesticides determines whether a pesticide will be registered for use on commodities. Historically, the US Environmental Protection Agency (EPA) has used very conservative estimates of health risks, particularly in the absence of data regarding actual use patterns of the pesticide and actual pesticide residue at the point of food purchase. However, when grower groups and manufacturers were faced with the problem of losing the ethylene bisdithiocarbamate (EBDC) fungicides, they approached EPA offering to provide hard data in place of estimates. Plant pathologists familiar with apple agroecosystems pointed out that different fungicides have highly specific uses in integrated pest management (IPM) programs, and that banning EBDC use on apples would probably raise total pesticide use in apples by compromising the pesticide reductions obtained under existing IPM programs. In addition, an early study showed that use-patterns could significantly reduce the amount of EBDC residue on apples. This approach led to a more realistic appraisal of both risks and benefits of the fungicides, lowering risks and raising benefits. The process ended with a registration prescribing use-patterns which result in minimal residue at harvest, thus providing valuable tools for use in IPM programs.     

Toxicity of commercial fungicides in relation to the larvae of Drosophila melanogaster Meigen (Diptera, Drosophilidae) and effect on the sex ratio

Bouillie bordelaise, Benlate, Euparène and Dithane M45 had no effects on Drosophila eggs. However, a post-hatching mortality was observed and, in all cases, a "dose effect" was established. There was a quick effect with Bouillie bordelaise, a slow and continued one with Benlate and Euparène, and the effect was delayed until the pupal stage with Dithane. Bouillie bordelaise, Benlate and Euparène slowed down the larval development and the emergence period was longer, according to the doses. Bouillie bordelaise was always the most toxic fungicide and Dithane the least one. The sex-ratio was not disturbed with Bouillie bordelaise. With Benlate and Euparène, the females were more sensitive than the males, while Dithane was more toxic towards males. Considering a same fungicide, a difference was exhibited according to the chosen criterion: Benlate caused an effect on larval mortality which was more important than its effect on the developing-time. Moreover, both carbamates, Benlate and Dithane, acted differently whatever their toxicity level.     

Residues behavior of some fungicides applied on two greenhouse tomato varieties different in shape and weight

The degradation of 12 fungicides (azoxystrobin, cymoxanil, cyproconazole, cyprodinil, fenarimol, fludioxonil, iprovalicarb, mepanipyrim, penconazole, pyrimethanil, tolclofos-methyl, triadimenol), commonly used in pest management strategies on Sardinian greenhouse tomato crops was studied. A different residue behaviour was observed between the studied cultivar. On the smaller, a "cherry" type tomato, field data showed an initial residue mostly higher than the "beefsteak" tomato. In any case, except for penconazole, all pesticide residues were below their maximum residue levels (MRLs) reaching the pre-harvest interval (PHI). On both cultivar, triadimenol and cymoxanil residues completely disappeared reaching their PHI, while iprovalicarb, fenarimol, and fludioxonil disappeared in a time of 17 to 24 days. On the contrary, azoxystrobin, cyproconazole, cyprodinil, penconazole, tolclofos-methyl, mepanipyrim, and pyrimethanil showed a long persistence on both tested cultivar and may have residual problems due to an accumulation effect if repeated field treatments will be performed. The first group of molecules according to their rapid degradation could be used in low pesticide-input management in order to obtain tomatoes with low or no detectable residues.     

Residues behavior of some fungicides applied on two greenhouse tomato varieties different in shape and weight

The degradation of 12 fungicides (azoxystrobin, cymoxanil, cyproconazole, cyprodinil, fenarimol, fludioxonil, iprovalicarb, mepanipyrim, penconazole, pyrimethanil, tolclofos-methyl, triadimenol), commonly used in pest management strategies on Sardinian greenhouse tomato crops was studied. A different residue behaviour was observed between the studied cultivar. On the smaller, a “cherry” type tomato, field data showed an initial residue mostly higher than the “beefsteak” tomato. In any case, except for penconazole, all pesticide residues were below their maximum residue levels (MRLs) reaching the pre-harvest interval (PHI). On both cultivar, triadimenol and cymoxanil residues completely disappeared reaching their PHI, while iprovalicarb, fenarimol, and fludioxonil disappeared in a time of 17 to 24 days. On the contrary, azoxystrobin, cyproconazole, cyprodinil, penconazole, tolclofos-methyl, mepanipyrim, and pyrimethanil showed a long persistence on both tested cultivar and may have residual problems due to an accumulation effect if repeated field treatments will be performed. The first group of molecules according to their rapid degradation could be used in low pesticide-input management in order to obtain tomatoes with low or no detectable residues.     

Sulphur-containing metabolites of the fungicides pentachloronitrobenzene (PCNB) and hexachlorobenzene (HCB) I. Syntheses

Syntheses of sulphur-containing metabolites of the fungicides pentachloronitrobenzene and hexachlorobenzene are described.     

Sulphur-containing metabolites of the fungicides pentachloronitrobenzene (PCNB) and hexachlorobenzene (HCB) II. Mass spectra

Mass spectrometric data of synthesized sulphur-containing derivatives of the fungicides pentachloronitrobenzene (PCNB) and hexachlorobenzene (HCB), such as thiophenols, thioanisoles, disulphides, pentachlorophenylmethylsulphoxide, pentachlorophenylmethylsulphone, and acetylcysteine-conjugates, as well as non sulphur-containing derivatives, such as phenols, pentachloroanisole, and chlorinated benzenes are reported.     

Detection of fullerenes (C60 and C70) in commercial cosmetics

Detection methods are necessary to quantify fullerenes in commercial applications to provide potential exposure levels for future risk assessments of fullerene technologies. The fullerene concentrations of five cosmetic products were evaluated using liquid chromatography with mass spectrometry to separate and specifically detect C₆₀ and C₇₀ from interfering cosmetic substances (e.g., castor oil). A cosmetic formulation was characterized with transmission electron microscopy, which confirmed that polyvinylpyrrolidone encapsulated C₆₀. Liquid-liquid extraction of fullerenes from control samples approached 100% while solid-phase and sonication in toluene extractions yielded recoveries of 27-42%. C₆₀ was detected in four commercial cosmetics ranging from 0.04 to 1.1 μg/g, and C₇₀ was qualitatively detected in two samples. A single-use quantity of cosmetic (0.5 g) may contain up to 0.6 μg of C₆₀, demonstrating a pathway for human exposure. Steady-state modeling of fullerene adsorption to biosolids is used to discuss potential environmental releases from wastewater treatment systems.     

Impact of three different fungicides on fungal epi- and endophytic communities of common bean (Phaseolus vulgaris) and broad bean (Vicia faba)

In this study, the impacts of three different fungicides to fungal phyllosphere communities on broad bean (Vicia faba, Fabaceae) and common bean (Phaseolus vulgaris, Fabaceae) were analyzed. The fungicides included copper, sulfur, and azoxystrobin. The plants were sowed, grown, and treated under conditions occurring in conventional and organic farming. A culture-based approach was used to identify changes in the phyllosphere fungal community after the treatment. Different effects on species richness and growth index of the epiphytic and endophytic communities for common bean and broad bean could be shown. Treatments with sulfur showed the weakest effect, followed by those based on copper and the systemic azoxystrobin, which showed the strongest effect especially on endophytic communities. The epiphytic fungal community took five weeks to recover after treatment with azoxystrobin. However, the effect of azoxystrobin on the endophytic community lasted more than five weeks. Finally, the data suggest that the surface structure of the host leaves have a huge impact on the mode of action that the fungicides exert.     

Identification and estrogenic characterization of impurities in commercial bisphenol A diglycidyl ether (BADGE)

A sample of commercial BADGE was fractioned by HPLC and eight impurities including novel propyl derivatives (2), (5) and (6) were identified by NMR spectrometry, FAB-MS and GC-MS. The estrogenicity, both agonist and antagonist, of fractions containing these impurities was measured with a yeast two-hybrid assay incorporating the human (hER alpha) and a competitive binding assay for hER alpha (ELISA). In the yeast two-hybrid assay, estrogenic antagonist activity was found in two fractions, while estrogenic agonist activity was not found in any. In the ELISA method, the binding affinity to hER alpha was found in three fractions. It is probable that a comprehensive assessment of the estrogenic properties of commercial BADGE, and their implications for human health, will require examination of all its components as described here.     

Residues of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides in organically-farmed vegetables

The residues of polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in soils from organic farms and their uptake by four varieties of organic-produced potatoes and three varieties of organic carrots from England were investigated. Samples of the soils, crop peels and cores were all Soxhlet-extracted in triplicate, cleaned up by open-column chromatography and analysed by a multi-residue analytical method using gas chromatography with mass selective detection. The concentrations of PAHs, PCBs and OCPs in soils from organic farms ranged from 590+/-43 to 2301+/-146 microg/kg, 3.56+/-0.73 to 9.61+/-1.98 microg/kg and 52.2+/-4.9 to 478+/-111 microg/kg, respectively. Uptake by different crop varieties were 8.42+/-0.93 to 40.1+/-4.9 microg/kg sigmaPAHs, 0.83+/-0.19 to 2.68+/-0.94 microg/kg sigmaPCBs and 8.09+/-0.83 to 133+/-27 microg/kg sigmaOCPs. Residue uptake from soils depended on plant variety; Desiree potato and Nairobi carrot varieties were more susceptible to PAH contamination. Likewise, uptake of PCBs and OCPs depended on potato variety. There were significant positive correlations between the PCB and OCP concentrations (P<0.05) in soils and carrots but no significant correlation was found between the concentrations of any contaminants in soils and potatoes. Peeling carrots and potatoes was found to remove 52-100% of the contaminant residues depending on crop variety and the properties of the contaminants. Soil-crop bioconcentration factors (BCFs) decreased with increasing logK(ow) for PAHs up to about 4.5 and for PCBs up to about 6.5, above which no changes were discernible for either class of contaminants. No relationship was observed between soil-crop BCFs and logK(ow) for OCPs, most likely because their concentrations were low and variable.     

Influence of several fungicides on the antioxidant activity of red wines (var. Monastrell)

The antioxidant activity of wines obtained from grapes treated with six fungicides (famoxadone, fenhexamid, fluquinconazole, kresoxim-methyl, quinoxyfen and trifloxystrobin) was investigated. Two field trials in triplicate were carried out for each formulation of the fungicide at the recommended dose of the manufacturer. The first trial was carried out under good agricultural practices (GAP), following the recommended pre-harvest interval, and the second one under critical agricultural practices (CAP) that involves treating the same field just before the harvest. The residue levels were determined by gas and liquid chromatography coupled to mass detectors (GC-MS and LC-MS). The antioxidant activity was determined in the wines obtained from the thirteen trials including one control, six from treated grapes obeying the pre-harvest interval, and six from grapes treated at the day of harvest or at most unfavorable conditions. Elimination of 40–100% of the initial fungicide residues present in grapes was observed during the wine-making process. It can be inferred from the results that the use of these fungicides did not produce any decrease of the antioxidant activity in the wines (7.19 ± 0.22 mmol Trolox/L for the blank wine versus a range of 6.45 ± 0.82 mmol Trolox/L to 10.06 ± 0.59 mmol Trolox/L for the treated wines) at the pre-harvest interval and most unfavorable conditions. Nevertheless, the presence of famoxadone, kresoxim-methyl and quinoxyfen increased the antioxidant activity and this was directly related to their residue levels in the grapes. Also, the wine phenolic composition was altered in variable intensity by the presence of the fungicide residues.     

Persistent Organochlorine Residues in Livers of Six Species of Ciconiiformes (Aves) from Spain

Liver samples of 42 birds belonging to 6 species of Ciconiiformes (grey heron (n = 17), little egret (n = 12), cattle egret (n = 1), glossy ibis (n = 1), little bittern (n = 1), and white stork (n = 10)), collected from two different zones of Spain (Ebro Delta and Madrid) in 1992–1997, were analyzed for organochlorine pesticides and PCBs. ΣPCBs (sum of concentrations of individual congeners), p,p′-DDE, HCB, γ-HCH, and heptachlor epoxide were the most prevalent residues detected in all samples (occurrence > 95%). There were no statistically significant differences in organochlorine levels between grey herons and little egrets, while levels of ΣPCBs, p,p′-DDE, HCB, γ-HCH, and heptachlor were significantly lower for white storks. These results could be explained by the different habitat of these species, aquatic in the Ebro Delta (grey herons, little egrets) and dry in Madrid (white stork), and their diverse feeding habits.     

Detailed PCB congener patterns in incinerator flue gas and commercial PCB formulations (Kanechlor)

In this study, we determined the detailed PCB congener patterns in flue gases from eight incinerators and four commercial PCB formulations (Kanechlors). About 160 PCB peaks were identified in samples using a DB-5 column and HRGC/HRMS. The concentration of incinerator stack emission gas ranged from 0.02 to 44 ngWHO-TEQ/Nm3. The ratios of dioxin-like PCBs in the total PCB concentration were from 3.4% to 25.7% and from 0.63% to 9.1% in stack emission gases and Kanechlor samples, respectively. The PCB congener profiles of Kanechlor samples were similar to those of previous studies. To determine characteristic congeners in flue gas and Kanechlor samples, principal component analysis (PCA) of the data was conducted using STATISTICA for Windows 5.0J (StatSoft, Inc.). As a result, we obtained four principal components (PCs) and accounted for 74% of the total variance. PC 1 was interpreted combustion, PC 2 and PC 3 were interpreted the difference in the number of substituted chlorines and, PC 4 could not be determined. Moreover, we obtained three groups according to the PCB congeners pattern among samples by PCA. These specific congeners that represent characteristics of each class were identified. These data will be useful for the source analysis of PCBs in the environment.     

The toxicology of the three commercial polybrominated diphenyl oxide (ether) flame retardants

Three commercial polybrominated diphenyl oxide flame retardants (PBDPO, PBDE) are manufactured: decabromodiphenyl oxide (DBDPO), octabromodiphenyl oxide (OBDPO) and pentabromodiphenyl oxide (PeBDPO). The composition, production volumes, uses and toxicology of the three products differ. In 1999, DBDPO accounted for approximately 82% of the global PBDPO usage. DBDPO has been extensively tested. DBDPO was not acutely toxic, was not irritating to the skin or eye, and did not induce skin sensitization. No evidence of genotoxic effects was detected in the Ames Salmonella, chromosome aberration, mouse lymphoma, or sister chromatid exchange tests. No cytogenic changes were observed in the bone marrow of rats (parents and offspring) undergoing a one-generation reproduction test. DBDPO did not adversely affect development or reproduction in rats. DBDPO's no-adverse-effect-level (NOAEL) in repeated dose studies was > or = 1000 mg/kg body weight. No, equivocal, or some evidence of carcinogenicity, dependent on genus and sex, was found in mice and rats at 2.5% and 5% of the diet administered for 2 years. DBPDO was poorly absorbed from the gastrointestinal tract (< 0.3-2% oral dose), had a short half-life (< 24 h) compared to PCB 153 (only 2% of an oral dose eliminated by rats in 21 days), and was rapidly eliminated via the feces (> 99% in 72 h). In contrast, components of the PeBDPO product were well absorbed and slowly eliminated, OBDPO's effect level in a 90-day study was approximately 100 mg/kg, PeBDPO's no-effect-level (NOEL) in a 30-day study was 1 mg/kg, and OBDPO induced developmental toxicity in the rat. In aquatic species, neither DBDPO nor OBDPO were toxic to aquatic organisms or bioconcentrating. Components of the PeBDPO product bioconcentrated in fish but produced little evidence of adverse effects.     

Herbicide residues in grapes and wine

The persistence of several common herbicides from grapes to wine has been studied. Shiraz, Tarrango and Doradillo grapes were separately sprayed with either norflurazon, oxyfluorfen, oxadiazon or trifluralin-persistent herbicides commonly used for weed control in vineyards. The dissipation of the herbicides from the grapes was followed for 28 days following treatment. Results showed that norflurazon was the most persist herbicide although there were detectable residues of all the herbicides on both red and white grapes at the end of the study period. The penetration of herbicides into the flesh of the grapes was found to be significantly greater for white grapes than for red grapes. Small-lot winemaking experiments showed that norflurazon persisted at levels close to the initial concentration through vinification and into the finished wine. The other herbicides degraded, essentially via first-order kinetics, within the period of "first fermentation" and had largely disappeared after 28 days. The use of charcoal together with filter pads, or with diatomaceous earth was shown to be very effective in removing herbicide residues from the wine. A 5% charcoal filter removed more than 96% of the norflurazon persisting in the treated wine.     

Effect of fungicides on plant growth promoting activities of phosphate solubilizing Pseudomonasputida isolated from mustard (Brassica compestris) rhizosphere

This study was navigated to examine the effects of fungicide-stress on the activities of plant-growth-promoting rhizobacterium Pseudomonasputida with inherent phosphate solubilizing activity. The fungicide-tolerant and phosphate solubilizing P.putida strain PS9 was isolated from the mustard rhizosphere and tentatively identified following standard morphological, physiological and biochemical tests. To further consolidate the identity of the strain PS9, the 16S rDNA sequence analysis was performed. Following the BLAST program, the strain PS9 was identified as P.putida. In the presence of the varying concentrations (0-3200 μg mL⁻¹; at a two fold dilution interval) of four fungicides of different chemical families (tebuconazole, hexaconazole, metalaxyl and kitazin) amended in minimal salt agar medium, the P.putida strain PS9 showed a variable tolerance levels (1400-3200 μg mL⁻¹) against the tested fungicides. The strain PS9 produced plant-growth-promoting (PGP) substances in significant amount in the absence of fungicides. In general, fungicides applied at the recommended, two and three times of the recommended rates, decreased the PGP attributes of P.putida the strain PS9 and affected the PGP activities in concentration-dependent manner. Fungicides at the recommended dose had minor reducing effect while the doses higher than the recommended dose significantly reduced the PGP activities (phosphate solubilization, salicylic acid, 2,3-dihydroxy benzoic acid, and indole-3-acetic acid production except exo-polysaccharides, hydrogen cyanate and ammonia production). Of the four fungicides, tebuconazole generally, showed maximum toxicity to the PGP activities of the strain PS9. This study inferred that fungicides must be examined in vitro for their possible adverse effects on soil micro flora before their application in agricultural fields. Moreover, the results also suggested the prerequisite of application of fungicide-tolerant PGPR strains as bioinoculants so that their PGP activities may not be suppressed under fungicide stress.     

Residues of dioxins (PCDD/Fs) and PCBs in eggs, fat and livers of laying hens following consumption of contaminated feed

Laying hens were fed with feed from the Belgian dioxin incident diluted ten-fold with non-contaminated feed, resulting in concentrations of 61 ngTEQkg(-1) PCDD/Fs, 23 ngTEQkg(-1) non-ortho PCBs, 116 ngTEQkg(-1) mono-ortho PCBs and 3.2 mgkg(-1) of the seven indicator PCBs. Following exposure for seven days, feed was replaced by non-contaminated feed for a period up to six weeks. Concentrations of PCDD/Fs in eggs showed a maximum of 214 pgTEQg(-1) fat after nine days and decreased to 44 pgTEQg(-1) after seven weeks. Dioxin concentrations in abdominal fat of chickens killed just after the last treatment, or after 1, 3 or 6 weeks on clean feed were 69, 84, 54 and 41 pgTEQg(-1) fat, respectively. Concentrations in livers decreased more rapidly, being 35, 7, 4 and 3 pgTEQg(-1) tissue, respectively. In both eggs and tissues, total TEQ concentrations were 3-4 times higher. Concentrations of the seven indicator PCBs in egg fat showed a stronger decrease with concentrations of 16.5 microgg(-1) at the peak (day 9) and 2.2 microgg(-1) after seven weeks. Corresponding concentrations in abdominal fat were, respectively, 4.6 and 2.6 microgg(-1) fat, and in livers 0.77 and 0.14 microgg(-1) tissue. The ratio of indicator PCBs to PCDD/Fs in feed was 52200. In eggs this ratio was initially higher (85000), but decreased towards 50000 after six weeks on clean feed. In abdominal fat the ratio varied between 49000 and 67000. In livers, the ratio was initially low (22000) but increased to 45000 towards the end of the study. It is concluded that the behaviour of PCDD/Fs and PCBs in laying hens is comparable and that the use of indicator PCBs appears to be a good alternative for PCDD/Fs but only in the case of co-exposure to both PCBs and PCDD/Fs, such as in incidents with PCB oil.     

Ecotoxicological evaluation of fungicides used in viticulture in non-target organisms

Environmental Science and Pollution Research - The effect of fungicides, commonly used in vine cultures, on the health of terrestrial and aquatic ecosystems has been poorly studied. The objective...