The technical feasibility, mechanisms, and performance of degradation of aqueous imidacloprid have been studied at pilot scale in two well-defined photocatalytic systems of special interest because natural UV light can be used: heterogeneous photocatalysis with titanium dioxide and homogeneous photocatalysis by photo-Fenton. Equivalent pilot-scale and field conditions used for both allowed adequate comparison of the degree of mineralization and toxicity achieved as well as the transformation products generated in route to mineralization by both systems. Ninety-five percent of mineralization (<2.0 mg/L) was reached after 250 min of photocatalytic treatment with Fenton and 450 min with TiO2, meaning that TOC disappears 2.4 times faster with photo-Fenton photocatalytic treatment than with TiO2. The Daphnia Magna test for final residual TOC does not reveal anytoxic behavior. Transformation products evaluated by GC-MS/AED after two SPE procedures and LC-IC were the same in both cases. The main differences between the two processes are in the amount of transformation products (TPs) generated, not in the TPs detected which were always the same. At the end of both processes low concentration (<0.1 mg/L) of 2 pyrrolidinone (transformation product) remains in the dissolution and around 1 mg/L of formate in the case of photo-Fenton.
The technical feasibility, mechanisms, and performance of degradation of aqueous diuron (22 mg/L) have been studied at pilot scale in two well-defined photocatalytic systems of special interest because natural UV light can be used: heterogeneous photocatalysis with titanium dioxide and homogeneous photocatalysis by photo-Fenton. Equivalent pilot-scale (made up of Compound Parabolic Collectors (CPCs) specially designed for solar photocatalytic applications) and field conditions used for both allowed adequate comparison of the degree of mineralization and toxicity achieved as well as the transformation products generated en route to mineralization by both systems. Total disappearance of diuron is attained by both phototreatments in 45 min. 100% of chlorine was recovered as chloride, but total recovery of nitrogen as inorganic ions was not attained. 90% of mineralization was reached after 200 min of photocatalytic treatment, but toxicity measured by two different bioassays (Daphnia magna and a Microalga) was reduced to below the threshold (EC50%) in a shorter time. Transformation products evaluated by LC-IT-MS by direct injection of the samples were the same in both cases. The main differences between the two processes were in the amount of transformation products (DPs) generated, not in the DPs detected, which were always the same.
Antifouling biocides used in boat paints were analyzed with a battery of toxicity bioassays to evaluate the toxic effects of these compounds on Vibrio fischeri, Daphnia magna and Selenastrum capricornotum. The antifoulants tested were Irgarol 1051, Kathon 5287, chlorothalonil, diuron, dichlofluanid, 2-thiocyanomethylthiobenzothiazole (TCMTB) and tributyltin (TBT). In most cases, the sensitivity of the organisms towards the toxicants followed the order: S. capricornotum > D. magna > V. fischeri. Toxicity by concentration level had the following order:, the toxicity order of compounds was TBT > Kathon 5287 > chlorothalonil > TCMTB > dichlofluanid > Irgarol 1051 > diuron. For V. fischeri (30 min test), the compound toxicity had the following order: Kathon 5287 > TBT > TCMTB > dichlofluanid > Irgarol 1051 > chlorothalonil.Degradation products of Irgarol 1051 and diuron were also tested. Degradation product of Irgarol 1051 was found to be less toxic to the crustacean and the microalga but more toxic to the bacterium. Degradation products of diuron were less toxic to the microalga in comparison with the bacterium. For mixtures of compound, toxicities were additive in only 33% of the cases and 21% of mixtures were less toxic than expected based on the sum of concentrations of toxicants (antagonistic effect). Synergistic enhancements of toxicity were observed for a majority (46%) of the mixtures.The average reproducibility of the EC 50 and LOEC measurements was 27, 24 and 28%, respectively, in the V. fischeri, S. capricornotum and D. magna bioassays. For single compound, the reproducibility of EC 50 was better than ±20% for a vast majority of the measurements with the V. fischeri system, thus agreeing closely with the reported reproducibility values for this relatively well-known assay.
Liquid chromatography tandem mass spectrometry (LC-MS/MS) and liquid chromatography time-of-flight mass spectrometry (LC-TOFMS) are powerful and complementary techniques that can independently cover the majority of the challenges related with pesticide residue food control. The sequential combination of both systems benefits from their complementary advantages and assists to increase the performance and to simplify routine large scale pesticide multiresidue methods. The proposed approach consists of three stages: (1) automated pesticide screening by LC-TOFMS; (2) identification by LC-TOFMS accurate mass measurements; and (3) confirmation and quantitation by LC-MS/MS. We have developed a fast comprehensive (identification/confirmation + quantitation) automated screening method for 100 target pesticides in crops. In the first stage, a set of data including m/z accurate mass windows (within 20 mDa width) and retention time is obtained (using a standard solution containing all the targeted pesticides) in order to build the automated screening procedure, which is created automatically by assigning retention time and the m/z mass window for each target pesticide. Samples are then analyzed, and the method enables the screening and preliminary identification of the species first by retention time and m/z mass window, followed by subsequent identification (only if positive results) by LC-TOFMS accurate mass measurements. After that, final confirmation of the positive findings using two MRM transitions and accurate quantitation is performed by LC-MS/MS using a hybrid triple quadrupole linear ion trap (QqLIT) mass spectrometer. In addition, the use of this QqLIT instrument also offers additional advantageous scanning modes (enhanced product ion and MS3 modes) for confirmatory purposes in compounds with poor fragmentation. Examples of applications to real samples show the potential of the proposed approach, including the detection of nonselected "a priori" compounds as a typical case of retrospective evaluation of banned or misused substances.
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