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A direct, fast and sensitive LC–MS/MS method was developed to measure biomarkers for mycotoxin exposure in human urine. In total, 32 biomarkers were quantitatively or semi-quantitatively measured in 32 urine samples of Belgian volunteers using two injections. All urine samples contained deoxynivalenol-15-glucuronide, the major detoxification metabolite of deoxynivalenol, in the ng/mL range. Also deoxynivalenol-3-glucuronide and de-epoxy-deoxynivalenol-glucuronide were present in, respectively, 90 and 25 % of the samples, while deoxynivalenol was detected in 60 % of the samples, in lower concentrations. Deoxynivalenol glucuronides were the major biomarkers for deoxynivalenol exposure. Ochratoxin A was detected in 70 % of the samples in pg/mL. Citrinin and/or dihydrocitrinone were detected in 90 % of the samples, also in concentrations of pg/mL. The presence of ochratoxin A and citrinin was confirmed by a second method using sample cleanup by immunoaffinity columns, followed by LC–MS/MS. Our data show that humans are much more exposed to citrinin than realized before and suggest further work on citrinin exposure in relation with ochratoxin A exposure, as both mycotoxins are nephrotoxic.

Two methods of application of pesticides viz. (i) application of the chemical (carbofuran or furathiocarb, a carbofuran precursor) on seeds; and (ii) soil application of encapsulated formulations (Ca2+-, Al3+- and Fe3+ alginate beads) of carbofuran were evaluated for their abilities to cope with practical problems resulting from the accelerated degradation of carbofuran in adapted soils. In previously-untreated soil, the half-life of carbofuran applied as the pure compound, the commercial microgranule formulation and the encapsulated formulation, was 8 weeks or more under standardized conditions (18-22 degrees C; 80% of the soil water retention capacity). The half-life of the carbofuran applied on seeds was only 2 weeks in this soil. In the previously-treated soil, the half-life of the pure active ingredient of carbofuran was 3 weeks with some of the encapsulated formulations such as alginate-Fe3+ beads and alginate-Ca2+ beads co-formulated with the fungicide TMTD. There was some evidence that degradation occurred only after the active ingredient had diffused out of the beads. The persistence of furathiocarb and carbofuran applied on seeds was < 5 days for all the seed treatments tested in the previously-untreated soil. Encapsulated chemicals in alginate beads were more promising than seed treatment in increasing their persistence in soils showing accelerated degradation. It is, however, necessary to check whether these kinds of formulations are still effective with respect to their insecticidal activity. (C) 1997 Elsevier Science Ltd.

Several studies carried out in Europe showed the importance of direct losses to the contamination of surface water by pesticides. These pesticides losses can occur at the farm site when the sprayer equipment is filled with the pesticide formulation (spills, overflowing, leaking) and during the clean-up (rinsing) of the sprayer after the treatment. In Belgium studies are carried out on biofilters to treat in an efficient way effluents containing pesticides. The biofilter substrate is elaborated from a homogenised mixture of local soil, chopped straw and peat or composted material, able to absorb or degrade the active substances. Biofilters consist in systems of 2 or 3 units depending on the spray equipment of the farmer and on the configuration of the farmyard. Each unit is made from a 1 m3 plastic container and the different units are stacked in a vertical pile and connected between them using plastic valves and pipes. Eight pilot systems were installed in March 2002 in seven farms and in one agricultural school, all selected in the loamy region of Belgium specialised in arable crops such as cereals, sugar beets and vegetables. The efficacy (yield) of the systems was determined by measuring the balance of the inputs and outputs of the pesticides. Results were expressed in percent of pesticide retained on the biofilters. The results obtained after two years with 5 tracer pesticides (atrazine, carbofuran, diuron, lenacil and simazine) brought on the biofilter installations are very satisfactory since the percentage of retention is generally higher than 95% of the amount applied. In the beginning of 2004, ten new pilot biofilters were installed in several farms or agricultural technical centres (producing cereals, sugar beets, potatoes, vegetables, fruits or ornamental plants), and in a municipal maintenance service. Some biofilters were installed in duplicate in order to compare the efficacy of different substrates. The efficacy of the biofilters was studied for the 5 classical tracer pesticides but also for other chemical classes of herbicides (sulfonylurea, aryloxyalcanoic acids, chloroacetanilides), insecticides (pyrethroids, carbamates) and fungicides (dicarboximides, phenylamides, triazoles and strobilurines). To monitor these pesticides in elutes and substrates, two analytical methods were developed, optimised and validated : the first one by Gas Chromatography with Mass Spectrometry Detection (GC-MS), and the second one by High Performance Liquid Chromatography with UV Diode Array Detection (HPLC-DAD). The micro-organisms activity in the substrate was also measured in some situations.

Pollution of surface and groundwater by pesticides is an increasing problem that needs to be addressed by the authorities as well as by the farmers themselves. Nowadays, some researchers are considering the numerous small spillages at the farm sites as a relevant entry route to be taken into account for predicting surface and groundwater pollution. In order to tackle this problem, several solutions exist for limiting the disposal of pesticide wastes into the environment. One such system is biopurification of farm wastes by biobed, biofilter or phytobac. In this study, the results of pesticides retention by biofilters under outdoor conditions are presented. The biofilters were filled with a mixture of a soil + peat constituent (25% by volume for each of them) and the rest (50%) with straw or with composted manure ot with chitin (in this later case at the rate of 5 g chitin per liter of substrate). The soil + peat constituent was made either of a material already challenged by pesticides (= recycled biofilters) or of untreated material (new biofilters). Selected pesticides (atrazine, carbofuran, chloridazon, chlortoluron, cyanazine, isoproturon and lenacil) were applied onto biofilters and the eluates were collected and analyzed. Two successive injections of pesticides into the biofilters were conducted. After the first pesticides application, the recycled biofilters made of soil + peat previously treated with pesticides had better retention and degradation rates than the new biofilters. Adding manure also improved these properties of biofilters. Columns made of unchallenged soil + peat and straw (new biofilters) were the least satisfactory: up to 25% of carbofuran were lost. Biofilters made of unchallenged soil + peat and chitin retained the least lenacil. Atrazine was the most retained by biofilters (either new or recycled) with added chitin. Cyanazine was almost absent in the percolates of all biofilters. After the second application of carbofuran and isoproturon, all biofilters improved to the point where (with the exception the new biofilters made of chitin) they retained the totality of the pesticides.

The objectives of these studies (1) were: (a) to search for experimental evidence that would allow a choice between different models ('egg-box' model of Grant et al. (1973) (2), models of Mackie et al. (1983) (3)); and (b) to find out what the 'cooperativity' in cation-binding by pectates means from a thermodynamic point of view.