Title: Effect of methylparaben in Artemia franciscana Comeche A, Martin-Villamil M, Pico Y, Varo I Ref: Comparative Biochemistry & Physiology C Toxicol Pharmacol, 199:98, 2017 : PubMed
In this study, the toxicity of methylparaben (MeP) an emerging contaminant, was analysed in the sexual species Artemia franciscana, due to its presence in coastal areas and marine saltworks in the Mediterranean region. The acute toxicity (24h-LC50) of MeP in nauplii was tested and its chronic effect (9days) evaluated by measuring survival and growth under two sublethal concentrations (0.0085 and 0.017mg/L). Also, the effect on several key enzymes involved in: antioxidant defences (catalase (CAT) and gluthathion-S-transferase (GST)), neural activity (cholinesterase (ChE)) and xenobiotic biotransformation (carboxylesterase (CbE), was assessed after 48h under sublethal exposure. The results of acute exposure indicate that MeP is harmful to A. franciscana (24h-LC50=36.7mg/L). MeP causes a decrease in CAT activity after 48h exposure to both concentration tested, that points out at the oxidative stress effect of MeP in A. franciscana. However, no significant effect on ChE, CbE and GST activities was found. In addition, MeP does not affect survival and growth in chronic exposure at the sublethal concentrations tested. The results of this study indicate that MeP is not a threat for A. franciscana under the experimental conditions used. Additional studies should be done considering long-term exposure and reproduction studies to analyse the potential risk of MeP as emerging contaminant in marine and hypersaline environments.
Daphnia magna individuals were transplanted across 12 sites from three Spanish river basins (Llobregat, Ebro, Jucar) showing different sources of pollution. Gene transcription, feeding and biochemical responses in the field were assessed and compared with those obtained in re-constituted water treatments spiked with organic eluates obtained from water samples collected at the same locations and sampling periods. Up to 166 trace contaminants were detected in water and classified by their mode of action into 45 groups that included metals, pharmaceuticals, pesticides, illicit drugs, and other industrial compounds. Physicochemical water parameters differentiated the three river basins with Llobregat having the highest levels of conductivity, metals and pharmaceuticals, followed by Ebro, whereas the Jucar river had the greatest levels of illicit drugs. D. magna grazing rates and cholinesterase activity responded similarly than the diversity of riparian benthic communities. Transcription patterns of 13 different genes encoding for general stress, metabolism and energy processes, molting and xenobiotic transporters corroborate phenotypic responses differentiated sites within and across river basins. Principal Component Analysis and Partial Least Square Projections to Latent Structures regression analyses indicated that measured in situ responses of most genes and biomarkers and that of benthic macroinvertebrate diversity indexes were affected by distinct environmental factors. Conductivity, suspended solids and fungicides were negatively related with the diversity of macroinvertebrates cholinesterase, and feeding responses. Gene transcripts of heat shock protein and metallothionein were positively related with 11 classes of organic contaminants and 6 metals. Gene transcripts related with signaling paths of molting and reproduction, sugar, protein and xenobiotic metabolism responded similarly in field and lab exposures and were related with high residue concentrations of analgesics, diuretics, psychiatric drugs, beta blockers, illicit drugs, trizoles, bisphenol A, caffeine and pesticides. These results indicate that application of omic technologies in the field is a promising subject in water management.
Fifty samples of honey collected from local markets of Portugal and Spain during year 2002 were analyzed for 42 organochlorine, carbamate, and organophosphorus pesticide residues. An analytical procedure based on solid-phase extraction with octadecyl sorbent followed by gas chromatography-mass spectrometry (GC-MS), for organochlorines, and by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS), for organophosphorus and carbamates, has been developed. Recoveries of spiked samples ranged from 73 to 98%, except for dimethoate (40%), with relative standard deviations from 3 to16% in terms of repeatability, and from 6 to 19% in terms of reproducibility. Limits of quantification were from 0.003 to 0.1 mg kg(-)(1). Most of the pesticides found in honey were organochlorines. Among them, gamma-HCH was the most frequently detected in 50% of the samples, followed by HCB in 32% of the samples and the other isomers of HCH (alpha-HCH and beta-HCH) in 28 and 26% of the samples, respectively. Residues of DDT and their metabolites were detected in 20% of the samples. Of the studied carbamates, both methiocarb and carbofuran were detected in 10% of the samples, pirimicarb in 4% and carbaryl in 2%. The only organophosphorus pesticides found were heptenophos in 16%, methidathion in 4%, and parathion methyl in 2% of honey samples. Results indicate that Portuguese honeys were more contaminated than Spanish ones. However, honey consumers of both countries should not be concerned about the amounts of pesticide residues found in honeys available on the market.
Title: Determination of five pesticide residues in oranges by matrix solid- phase dispersion and liquid chromatography to estimate daily intake of consumers Valenzuela AI, Pico Y, Font G Ref: Journal of AOAC International, 84:901, 2001 : PubMed
Residues of benzoylphenylurea insecticides (diflubenzuron, hexaflumuron, and flufenuxuron), carboxamide acaricides (hexythiazox), and carbamate insecticides (benfuracarb) were determined in 150 orange fruit samples from September 1998 to June 1999, to estimate exposure of the Valencian population to oranges contaminated with these newly developed pesticides. The method for monitoring these residues is based on matrix solid-phase dispersion and liquid chromatography with UV or atmospheric pressure chemical ionization/mass spectrometry (APCI/MS) detection. Orange samples representing 11 varieties were collected from an agricultural cooperative and examined for the 5 pesticides. In 74.6% of all analyzed samples, the pesticide residues were below detection limits, which ranged from 0.002 to 0.05 mg/kg. Residues were detected in 25.4% of the samples, with higher incidences of diflubenzuron, flufenuxuron, hexythiazox, and benfuracarb; hexaflumuron residues were detected only occasionally. Two different pesticides exceeded maximum residue limits (MRLs) in 4 (2.7%) of the orange samples. Diflubenzuron surpassed 1 mg/kg MRL in 3 samples and flufenuxuron exceeded the 0.3 mg/kg MRL in 3 samples. The estimated daily intake of the 5 pesticide residues during the period was 0.077 microg/kg body weight per day. This value is much lower than the total admissible daily intake proposed by the Food and Agricultural Organization and the World Health Organization.
Title: Evaluation of organophosphorus pesticide residues in citrus fruits from the Valencian community (Spain) Torres CM, Pico Y, Marin R, Manes J Ref: Journal of AOAC International, 80:1122, 1997 : PubMed
Approximately 200 citrus samples from markets of the Valencian Community (Spain) were analyzed to establish their residue levels in 12 organophosphorus pesticide residues during the 1994-1995 campaign. The organophosphorus pesticides carbophenothion, chlorpyriphos, chlorfenvinphos, diazinon, ethion, fenitrothion, malathion, methidation, methylparathion, phosmet, quinalphos, and tetradifon were simultaneously extracted by matrix solid-phase dispersion and determined by gas chromatography-mass spectrometry using selected ion monitoring mode. A total of 32.25% contained pesticide residues and 6.9% exceeded the European Union Maximum Residue Levels (MRLs). The pesticides found in the samples with residues above MRLs were carbophenothion, ethion, methidathion, and methyl parathion. Lower level residues of these and the other pesticides studied (except diazinon) were frequently found. The estimated daily intake of the 12 organophosphorus pesticide residues during the studied period was 4.87 x 10(-4) mg/kg body weight/day. This value is lower than the provisional tolerances dairy intakes proposed by the Food and Agriculture Organization and the World Health Organization.
Title: Matrix solid-phase dispersion extraction procedure for multiresidue pesticide analysis in oranges Torres CM, Pico Y, Redondo MJ, Manes J Ref: Journal of Chromatography A, 719:95, 1996 : PubMed
A multiresidue extraction method based on matrix solid-phase dispersion (MSPD) is optimized for the extraction and gas chromatographic screening of eighteen insecticides (aldrin, carbophenothion, captafol, chlorpyriphos, chlorfenvinphos, diazinon, dicofol, alpha-endosulfan, beta-endosulfan, ethion, fenitrothion, folpet, methidathion, malathion, methyl-azinphos, methyl-parathion, phosmet, and tetradifon) from oranges. After optimization of different parameters, such as type of solid phase used and the amount of solid phase or eluent, recoveries ranged from 67 to 102% with relative standard deviations ranging from 2 to 10%. The limits of detection, calculated as 3 times the baseline noise ranged from 2 to 171 micrograms/kg. These limits of detection were about 10 times lower than the maximum residue levels established by the European Community. Compared with classical methods, the described procedure is simple, less labour intensive and does not require preparation and maintenance of equipment. Troublesome emulsions, such as those frequently observed in liquid-liquid partitioning did not occur.
