A modified QuEChERS method for determination of organophosphate esters in milk by GC-MS.

Organophosphate esters (OPEs) are substances that have been detected in several matrices due to their use as flame retardants and plasticizers. Human exposure to OPEs can cause endocrine disruption, neurotoxicity, and reproductive disturbance. Ingestion of contaminated food can be a significant route of exposure to OPEs. Food can be contaminated by OPEs in the food chain, during cultivation, and by contact with plasticizers during the production chain of processed foods. In this study, a method for the determination of 10 OPEs in commercial bovine milk was developed. The procedure was based on QuEChERS extraction and gas chromatography coupled to mass spectrometry (GC-MS) analysis. QuEChERS modification included a freezing-out step after the extraction followed by the concentration of the entire acetonitrile phase before the clean-up step. Calibration linearity, matrix effects, recovery, and precision were evaluated. Significant matrix effects were observed, which were compensated by matrix-matched calibration curves. Recoveries ranged from 75 to 105%, with a relative standard deviation ranging from 3 to 38%. The method detection limits (MDLs) were in the range of 0.43-4.5 ng mL-1, while the method quantification limits (MQLs) were within the range from 0.98 to 15 ng mL-1. The proposed method was successfully validated and applied to determine the concentrations of OPEs in bovine milk. The 2-ethylhexyl diphenyl phosphate (EHDPHP) was detected in the analyzed milk samples but at levels below the MQL.

Trends of legacy and emerging organic contaminants in a sediment core from Cienfuegos Bay, Cuba, from 1990 to 2015.

Legacy and emerging organic pollutants pose an ever-expanding challenge for the marine environment. This study analysed a dated sediment core from Cienfuegos Bay, Cuba, to assess the occurrence of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), alternative halogenated flame retardants (aHFRs), organophosphate esters (OPEs), and phthalates (PAEs) from 1990 to 2015. The results evidence the continuing presence of historical regulated contaminants (PCBs, OCPs, and PBDEs) in the southern basin of Cienfuegos Bay. PCB contamination declined since 2007, likely in response to the gradual global phasing out of PCB containing materials. There have been relatively consistent low accumulation rates for OCPs and PBDEs at this location (in 2015 approximately 1.9 and 0.26ng/cm2/year, respectively, with 2.8ng/cm2/year for Σ6PCBs), with indications of recent local DDT use in response to public health emergencies. In contrast, sharp increases are observed between 2012 and 2015 for the contaminants of emerging concern (PAEs, OPEs, and aHFRs), and in the case of two PAEs (DEHP and DnBP) the concentrations were above the established environmental effect limits for sediment dwelling organisms. These increasing trends reflect the growing global usage of both alternative flame retardants and plasticizer additives. Local drivers for these trends include nearby industrial sources such as a plastic recycling plant, multiple urban waste outfalls, and a cement factory. The limited capacity for solid waste management may also contribute to the high concentrations of emerging contaminants, especially plastic additives. For the most recent year (2015), the accumulation rates for Σ17aHFRs, Σ19PAEs, and Σ17OPEs into sediment at this location were estimated to be 10, 46 000, and 750ng/cm2/year, respectively. This data provides an initial survey of emerging organic contaminants within this understudied region of the world. The increasing temporal trends observed for aHFRs, OPEs, and PAEs highlights the need for further research concerning the rapid influx of these emerging contaminants.

Consumption of fruits and vegetables contaminated with pesticide residues in Brazil: A systematic review with health risk assessment.

Brazil is the third largest exporter of fruits and vegetables in the world and, consequently, uses large amounts of pesticides. Food contamination with pesticide residues (PRs) is a serious concern, especially in developing countries. Several research reports revealed that some Brazilian farmers spray pesticides on fruits and vegetables in large quantities, generating PRs after harvest. Thus, ingestion of food contaminated with PRs can cause adverse health effects. Based on information obtained through a systematic review of essential information from 33 articles, we studied the assessment of potential health risks associated with fruit and vegetable consumption in children and adults from Brazilian states. This study identified 111 PRs belonging to different chemical groups, mainly organophosphates and organochlorines, in 26 fruit and vegetable samples consumed and exported by Brazil. Sixteen of these PRs were above the Maximum Residue Limit (MRL) established by local and international legislation. We did not identify severe acute and chronic dietary risks, but the highest risk values were observed in São Paulo and Santa Catarina, associated with the consumption of tomatoes and sweet peppers due to the high concentrations of organophosphates. A high long-term health risk is associated with the consumption of oranges in São Paulo and grapes in Bahia due to chlorothalonil and procymidone. We also identified that 26 PRs are considered carcinogenic by the United States Environmental Protection Agency (US EPA), and the carcinogenic risk analysis revealed no severe risk in any Brazilian state investigated due to the cumulative hazard index (HI) < 1. However, the highest HI values were in São Paulo due to acephate and carbaryl in sweet pepper and in Bahia due to dichlorvos. This information can help regulatory authorities define new guidelines for pesticide residue limits in fruits and vegetables commonly consumed and exported from Brazil and monitor the quality of commercial formulations.

A comparison of pesticide residues in soils from two highly technified agricultural valleys in northwestern Mexico.

A pesticide characterization is presented for two highly technified valleys in northwest Mexico: Culiacan Valley (CV) in Sinaloa and Yaqui Valley (YV) in Sonora. Approximately 250,000 kg of active ingredients are used every year, half of which are considered highly hazardous pesticides. Legacy pesticides are still present in the soils of these valleys. The aim of the present study was to identify and quantify a wide variety of pesticides in soils and correlate their concentrations with historical and current use. Agricultural soils from both valleys were sampled and analyzed using accelerated solvent extraction and subsequent quantification by gas chromatography with selective detectors. The most frequently detected pesticides (mean, µg g-1) in CV were organochlorines (0.1967), organophosphates (0.0928), synthetic pyrethroids (0.2565), organonitrogen (0.0552), and miscellaneous pesticides (0.1851). In YV, the most frequently detected pesticides were organochlorines (0.8607), organophosphates (0.0001), synthetic pyrethroids (0.0124), and miscellaneous pesticides (0.0009). The pesticides were more diverse in CV compared to those of YV, which was based on the types of crops produced. Both locations presented highly hazardous pesticides, including concentrations above the action levels established by the Canadian Soil Quality Guide. A follow-up risk assessment is recommended to assess potential effects.

Distribution of organochlorine, organophosphates, carbamate, thiocarbamate, pyrethroids, and strobilurins in surface sediments of the Rio de Ondas watershed by GC-MS.

The determination of some pesticides in surface sediments can provide important information about their distribution in the water column. This work aimed to determine the distribution of the classes of pesticides along the Ondas River's hydrographic basin (ORHB), in eighteen different points, during the dry and rainy periods. The pesticides were extracted from the sediment samples by solid-liquid extraction and then analyzed using a gas chromatograph coupled to mass spectrometry. After the development and validation of the method, nineteen pesticides from the group of organochlorine, organophosphates, carbamate and thiocarbamate, pyrethroids, and strobilurins were quantified in at least one point in the two collection periods, with accuracy varying between 86 and 126%. The average concentrations were 0.020 ng g-1 (carbofuran) to 249.123 ng g-1 (dimethoate) and 0.029 ng g-1 (carbofuran and sulfotep) to 533.522 ng g-1 in the dry and rainy periods, respectively. The results showed a wide distribution of pesticide residues in the ORHB, with higher levels for dimethoate, phenitrothion, and malathion, which may be related to their agricultural use in the region. In Brazil, it does not have specific legislation for maximum permitted values of pesticides in sediment, allowing for inappropriate or prohibited use and, consequently, affecting water quality.

Determination of organochlorine and organophosphorus residues in surface waters from the coffee zone in Quindío, Colombia.

The aim of this study was to identify organochlorine (OC) and organophosphorus (OP) pesticides levels in water samples collected in secondary water bodies in agricultural area planted with coffee and plantain. A descriptive cross-sectional study was carried out. A validated method for microwave-assisted extraction and gas chromatography with electron microcapture detector (MAE-GC-µECD) was used to analyze pesticide residues in samples. The determinations were based on certified reference material, Organochlorine Pesticide Mix AB #3, Canadian Drinking Organophosphorus Pesticides Mix, and pentachloronitrobenzene (ISTD) Internal Standard Mix 508.1. Pesticide residues were found in 81.3% of the samples, including OCs: 4.4'-DDT (38%), endosulfan II (19.7%), endosulfan sulfate, and endrin (11.7% and 8.8%), and others identified as 4.4'-DDE, Delta-HCB, parathion, chlorpyrifos, endrin aldehyde, heptachlor, heptachlor epoxide, endrin ketone, and methoxychlor. Parathion and/or chlorpyrifos were found in 5.8-8% of samples; the water bodies most heavily affected were those in Filandia and Quimbaya in which 100% of samples were contaminated, followed by those in Calarcá, Córdoba, Pijao, and Génova, with contamination found in over 75% of samples. The results indicated that surface waters from Quindío municipalities are contaminated with pesticide residues hazardous to human health, which are still in use despite being either restricted or prohibited.

Tris(2-chloroethyl) phosphate, a pervasive flame retardant: critical perspective on its emissions into the environment and human toxicity.

Regulations and the voluntary activities of manufacturers have led to a market shift in the use of flame retardants (FRs). Accordingly, organophosphate ester flame retardants (OPFRs) have emerged as a replacement for polybrominated diphenyl ethers (PBDEs). One of the widely used OPFRs is tris(2-chloroethyl) phosphate (TCEP), the considerable usage of which has reached 1.0 Mt globally. High concentrations of TCEP in indoor dust (∼2.0 × 105 ng g-1), its detection in nearly all foodstuffs (max. concentration of ∼30-300 ng g-1 or ng L-1), human body burden, and toxicological properties as revealed by meta-analysis make TCEP hard to distinguish from traditional FRs, and this situation requires researchers to rethink whether or not TCEP is an appropriate choice as a new FR. However, there are many unresolved issues, which may impede global health agencies in framing stringent regulations and manufacturers considering the meticulous use of TCEP. Therefore, the aim of the present review is to highlight the factors that influence TCEP emissions from its sources, its bioaccessibility, threat of trophic transfer, and toxicogenomics in order to provide better insight into its emergence as an FR. Finally, remediation strategies for dealing with TCEP emissions, and future research directions are addressed.

Magnetic restricted-access carbon nanotubes for dispersive solid phase extraction of organophosphates pesticides from bovine milk samples.

Magnetic restricted-access carbon nanotubes (M-RACNTs) were synthesised and used for dispersive solid phase extraction of organophosphates (chlorpyriphos, malathion, disulfoton, pirimiphos) from commercial bovine raw milk samples. Due to their magnetic susceptibility, M-RACNTs were easily separated from the samples/solvents using a neodymium magnet, and the extracted organophosphates were analysed by gas chromatography-mass spectrometry. The protein exclusion capacity was about 100%. Kinetic and isotherm data (for M-RACNTs - malathion interaction) were adequately adjusted to the pseudo-second order and Sips models, respectively, and the maximum adsorption capacity was about 0.55 mg g-1. The method presented linear ranges from 5.0 to 40.0 µg L-1 for all analytes, with determination coefficients from 0.9902 to 0.9963. The intra-assay precisions (as relative standard deviation) and accuracies (as relative error) ranged from 10.47 to 19.85% and from -0.18 to -18.80%, respectively, whereas the inter-assay precisions ranged from 6.48 to 18.76% and from -0.22 to 19.49%, respectively for 5.0, 20.0 and 40.0 µg L-1 organophosphates levels. The organophosphates were not stable at 4 and 24 h (relative errors ranged from -39.30 to 72.07% and -69.64 to 75.95%, respectively). Limits of detection ranged from 0.36 to 0.95 µg L-1, and 5 µg L-1 was defined as the limit of quantification for all the analytes. The proposed method was applied in the determination of organophosphates in five commercial milk samples, and no pesticides were detected.

Removal of triazines, triazoles and organophophates in biomixtures and application of a biopurification system for the treatment of laboratory wastewaters.

Biopurification systems (BPS) have been barely explored for removing complex mixtures of pesticides. In this study, the potential of a biomixture to remove simultaneously a mixture of herbicides (triazines), fungicides (triazoles) and insecticides (organophosphates) is presented. Also, a BPS using the same biomixture was used for treating a pesticide testing laboratory wastewater containing a mixture of 38 compounds. Ecotoxicological assays were conducted on the BPS elutriates to investigate the mixture detoxification. A mixture (concentrations of 4-8 mg kg-1) run in small-scale biomixture systems (SSB) for 128 d showed 59.3% removal of triazines, 68.5% of organophosphates and no elimination of triazoles. The treatment of the laboratory wastewater (individual concentrations range: 0.0036-0.25 mg kg-1) in the pilot-scale BPS for 281 d resulted in the elimination pattern of organophosphates (90.0%) > triazoles (73.4%) > carbamates (71.3%) > triazines (54.3%). Complete detoxification towards Daphnia magna and partial detoxification in Lactuca sativa seeds germination occurred in the BPS. Although the pesticide mixture complexity is higher in the BPS, the lower concentrations found in this matrix, could explain removal differences between SSB and BPS and the apparent inhibition in the elimination of carbamates and some triazines observed in the latter. These findings suggest that disposal of pesticide-containing laboratory-wastewater should be done in separate containers, according to chemical groups before their treatment in separate BPS, in order to reduce treatment periods. Monitoring the treatment process in the BPS with a battery of ecotoxicological tests is strongly recommended.

Semi-volatile organic compounds in infant homes: Levels, influence factors, partitioning, and implications for human exposure.

While infants are developing, they are easily affected by toxic chemicals existing in their environments, such as semi-volatile organic compounds (SVOCs): phthalates, polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs), and organophosphate esters (OPEs). However, the specific living environment of infants, including increased plastic products and foam floor mats, may increase the presence of these chemicals. In this study, 68 air, dust, and window film samples were collected from homes, with 3- to 6-month-old infant occupants, to analyze phthalates, PAHs, PBDEs, and OPEs. High detection rates and concentrations suggest that these SVOCs are widespread in infant environments and are associated with cooking methods, smoking habits, the period of time after decoration, and room floors. The partitioning behavior of SVOCs indicates that the logarithms of the dust/gas-phase air partition coefficient (logKD) and the window film/gas-phase air partition coefficient (logKF) in homes are not at an equilibrium state when the logarithm of the octanol/air partition coefficient (logKOA) is less than 8 or greater than 11. Considering the 3 exposure routes, ingestion and dermal absorption have become the main routes of infant exposure to phthalates and OPEs, and ingestion and inhalation have become the dominant routes of exposure to PAHs and PBDEs. The total carcinogenic risk of SVOCs, which have carcinogenic toxicities, via ingestion and dermal absorption for infants in homes exceeds the acceptable value, suggesting that the current levels of these SVOCs in homes might pose a risk to infant health.

Trends and Perspectives in Immunosensors for Determination of Currently-Used Pesticides: The Case of Glyphosate, Organophosphates, and Neonicotinoids.

Pesticides, due to their intensive use and their peculiar chemical features, can persist in the environment and enter the trophic chain, thus representing an environmental risk for the ecosystems and human health. Although there are several robust and reliable standard analytical techniques for their monitoring, the high frequency of contamination caused by pesticides requires methods for massive monitoring campaigns that are capable of rapidly detecting these compounds in many samples of different origin. Immunosensors represent a potential tool for simple, rapid, and sensitive monitoring of pesticides. Antibodies coupled to electrochemical or optical transducers have resulted in effective detection devices. In this review, the new trends in immunosensor development and the application of immunosensors for the detection of pesticides of environmental concern-such as glyphosate, organophosphates, and neonicotinoids-are described.

Occurrence and human exposure to brominated and organophosphorus flame retardants via indoor dust in a Brazilian city.

Indoor dust is considered an important human exposure route to flame retardants (FRs), which has arised concern due the toxic properties of some of these substances. In this study, ten organophosphorus flame retardants (OPFRs), eight polybrominated diphenyl ethers (PBDEs) and four new brominated flame retardants (NBFRs) were determined in indoor dust from different places in Araraquara-SP (Brazil). The sampled places included houses, apartments, offices, primary schools and cars. The analysis of the sample extracts was performed by gas chromatography coupled to mass spectrometry and two ionization techniques were used (electron ionization - EI; electron capture negative ionization - ECNI). OPFRs were the most abundant compounds and tris(2-butoxyethyl) phosphate (TBOEP), tris(phenyl) phosphate (TPHP), tris(1,3-dichloroisopropyl) phosphate (TDCIPP) and tris(2-chloroisopropyl) phosphate (TCIPP) were present at the highest concentrations. Among the brominated FRs, the most ubiquitous compounds were BDE-209, bis(2-ethylhexyl) tetrabromophthalate (BEH-TEBP) and decabromodiphenyl ethane (DBDPE). Statistical analysis revealed that there were differences among dust typologies for TBOEP, TDCIPP, ethylhexyl diphenyl phosphate (EHDPHP), BDE-209, 2-ethylhexyl 2,3,4,5-tetrabromobenzoate (EH-TBB), BEH-TEBP and DBDPE, which were attributed to different construction materials in each particular environment and to the age of the buildings. The highest levels of brominated FRs were observed in offices, TBOEP was at high concentration in primary schools, and TDCIPP was at high concentration in cars. A preliminary risk assessment revealed that toddlers were exposed to TBOEP levels higher than the reference dose when considering the worst case scenario. The results obtained in this study showed for the first time that although Brazil does not regulate the use of FRs, these substances are present in indoor dust at levels similar to the observed in countries that have strict fire safety standards, and that humans are exposed to complex mixtures of these contaminants via indoor dust.

Multiresidue method for simultaneous analysis of aflatoxin M1, avermectins, organophosphate pesticides and milbemycin in milk by ultra-performance liquid chromatography coupled to tandem mass spectrometry.

A method developed for the simultaneous analysis of aflatoxin M1, abamectin, doramectin, eprinomectin, ivermectin, moxidectin, acephate, azinphos-ethyl, azinphos-methyl, diazinon, methamidophos, methidathion, mevinphos, pirimiphos-ethyl and pirimiphos-methyl in whole raw milk, based on the QuEChERS method for extraction and clean-up, with detection and quantification by ultra-performance liquid chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) is described. The method was validated according to parameters of the Analytical Quality Assurance Manual from the Brazilian Ministry of Agriculture and Commission Decision 2002/657/EC, and proved suitable for analysis of these analytes within the proposed working range, with recovery values between 77% and 110%, a standard deviation lower than 20%, limits of detection between 0.05 and 0.99 µg l(-)(1), and limits of quantification between 0.15 and 1.98 µg l(-1). Samples from animals treated with abamectin, doramectin, ivermectin and diazinon were analysed by the validated method. Residues of aflatoxin M1 were also found in field samples at levels below the established maximum residue limit.

The influence of tomato processing on residues of organochlorine and organophosphate insecticides and their associated dietary risk.

Due to the increasing food demand, the use of pesticides in agriculture is increasing. Particularly in low income countries poor training among farmers, combined with the use of obsolete pesticides may result in a high risk for the consumers. In this study six organochlorines and five organophosphates were analyzed in 54 samples of tomatoes from small scale farmers in Bolivia. The analyses were done on unprocessed, stored, washed and peeled tomatoes. The cumulated risk associated with consumption of the tomatoes after different storage times and processing treatments was evaluated using the Hazard Index (HI) for acute risk assessment. All 11 pesticides were detected in the analyses although several of them are obsolete and included in the Stockholm convention ratified by Bolivia. The organochlorines were found in the µg pesticide/kg tomato range and below the HI, while the organophosphates were present in the mg pesticide/kg tomato range and most often above the HI. The low organochlorine concentrations were not significantly affected by time or treatment, but storage significantly decreased the concentrations of organophosphates. Washing decreased the initial concentrations to between 53% (malathion) down to 2% (ethyl parathion), while peeling had a larger effect reducing the initial concentrations to between 33% (malathion) and 0.7% (chlorpyriphos). Both the acute and chronic cumulative risk assessment of organophosphates showed a dietary risk for unprocessed tomatoes three days after harvest. For children, also the consumption of washed tomatoes constituted a dietary risk. To reduce the dietary risk of pesticide residues in Bolivia, there is an urgent need of farmer education and introduction of less hazardous pesticides as well as resources for surveillance and enforcement of legislation in order to ensure public health.

Cutaneous changes in rats induced by chronic skin exposure to ultraviolet radiation and organophosphate pesticide

PURPOSE: To study the possible potentiation of the carcinogenic effects of ultraviolet radiation associated with an organophosphate pesticide. METHODS: Forty Wistar rats were assigned into four groups (n=10 each) randomized according to the procedures: group A received only UVR-B radiation; group B, UVR-B for eight weeks followed by a seven week period of pesticide exposure; group C, UVR-B + pesticide concomitantly: group D, only pesticide application. At the end of the fifth, tenth and fifteenth weeks the animals were photographed. Skin biopsy and histopathological study with Hematoxylin-Eosin were done on the fifteenth week. Statistical analysis with Fisher's and Sign (unilateral) tests, 5% value for significance. RESULTS: Macroscopic lesions in the group A evolved from the erythema to erythema + desquamation. The groups B and C, with the association of two carcinogens, and group D presented evolution to keratosis, with higher incidence in group D. The histology showed a significant increase in the severity of injuries when the UVR-B and the pesticide were applied simultaneously, leading to cellular atypia. CONCLUSIONS: Concurrent association of UVR-B to organophosphate pesticide produced more severe lesions microscopically, although this has not been so apparent macroscopically. In daily practice the clinical evaluation should be complemented with laboratory evaluation. .

Cutaneous changes in rats induced by chronic skin exposure to ultraviolet radiation and organophosphate pesticide

PURPOSE: To study the possible potentiation of the carcinogenic effects of ultraviolet radiation associated with an organophosphate pesticide. METHODS: Forty Wistar rats were assigned into four groups (n=10 each) randomized according to the procedures: group A received only UVR-B radiation; group B, UVR-B for eight weeks followed by a seven week period of pesticide exposure; group C, UVR-B + pesticide concomitantly: group D, only pesticide application. At the end of the fifth, tenth and fifteenth weeks the animals were photographed. Skin biopsy and histopathological study with Hematoxylin-Eosin were done on the fifteenth week. Statistical analysis with Fisher's and Sign (unilateral) tests, 5% value for significance. RESULTS: Macroscopic lesions in the group A evolved from the erythema to erythema + desquamation. The groups B and C, with the association of two carcinogens, and group D presented evolution to keratosis, with higher incidence in group D. The histology showed a significant increase in the severity of injuries when the UVR-B and the pesticide were applied simultaneously, leading to cellular atypia. CONCLUSIONS: Concurrent association of UVR-B to organophosphate pesticide produced more severe lesions microscopically, although this has not been so apparent macroscopically. In daily practice the clinical evaluation should be complemented with laboratory evaluation. .(AU)

Occupational exposure to organophosphate and carbamate pesticides affects sperm chromatin integrity and reproductive hormone levels among Venezuelan farm workers.

OBJECTIVES: Several reports suggest that chronic pesticide exposure may affect semen quality and male fertility in humans. The objective of this study was to evaluate the association between occupational exposure to organophosphate (OP) and carbamate (CB) pesticides and semen quality, as well as levels of reproductive and thyroid hormones of Venezuelan farm workers. METHODS: Thirty-five healthy men (unexposed group) and 64 male agricultural workers (exposed group) were recruited for clinical evaluation of fertility status. Fresh semen samples were evaluated for sperm quality and analyzed for DNA fragmentation index (DFI) by flow cytometry. Pesticide exposure was assessed by measuring erythrocyte acetylcholinesterase (AChE) and plasma butyrylcholinesterase (BuChE) with a Test-mate ChE field kit. Serum levels of total testosterone (Tt), follicle-stimulating hormone (FSH), luteinizing hormone (LH), prolactin (PRL), thyroid stimulating hormone (TSH) and free thyroxine (FT4) were analyzed using enzyme immunoassay kits. RESULTS: Evidence of pesticide exposure was found in 87.5% of farmers based on AChE and BuChE inhibition. Significant increments were observed in sperm DFI with significant decreases in some semen parameters. DFI was negatively correlated with BuChE, sperm concentration, morphology and vitality in these workers. The levels of Tt, PRL, FT4 and TSH appeared to be normal; however, there was a tendency for increased LH and FSH levels in exposed workers. CONCLUSIONS: Our results confirm the potential impact of chronic occupational exposure to OP/CB pesticides on male reproductive function, which may cause damage to sperm chromatin, decrease semen quality and produce alterations in reproductive hormones, leading to adverse reproductive health outcomes.

Residuos de plaguicidas en aguas para consumo humano en una comunidad agrícola del estado Mérida, Venezuela / Pesticide residues in drinking water of an agricultural community in the state of Mérida, Venezuela

El objetivo del presente trabajo fue determinar la presencia de plaguicidas en agua potable, provenientes de seis acueductos en una región de intensa actividad agrícola del Estado Mérida, Venezuela. El estudio fue realizado durante cuatro semanas continuas, entre mayo y junio de 2008. Los residuos de plaguicidas fueron analizados mediante extracción en fase sólida y HPLC con detector de arreglo de diodos. El método SPE-HPLC-DAD cumplió con los criterios de validación analítica: linealidad (R²: 0,9840-0,9999), precisión (coeficiente de variabilidad inter-día 1,47-6,25%), exactitud (desviación estándar relativa 0,9-9,20%) y sensibilidad (límite de detección ≤ 0,012 µg/L; límite de cuantificación ≤ 0,030 µg/L, excepto mancozeb con 0,400 µg/L). Siete de los trece plaguicidas seleccionados tienen un porcentaje de recuperación entre 100% y 70%, el resto, entre 61% y 37%. En 72 muestras analizadas, se detectaron diez plaguicidas de los grupos químicos: organofosforados, carbamatos, triazinas y derivados de urea. Los plaguicidas con mayor frecuencia de detección fueron: carbofuran y atrazina (39%), malation (25%), dimetoato y metribuzin (19%). Los plaguicidas que se encontraron en niveles más altos fueron: diazinon (26,31 µg/L), metamidofos (10,99 µg/L), malation (2,03 µg/L) y mancozeb (1,27 µg/L). Los niveles de plaguicidas no superaron los valores máximos permitidos por la Legislación Venezolana, sin embargo, fueron superiores al nivel máximo permitido por la Unión Europea y EPA-USA. Este estudio demuestra la urgente necesidad de hacer un monitoreo sistemático de la calidad del agua para consumo humano en las regiones de alta productividad agrícola.

The aim of this study was to determine the presence of pesticides in drinking water from six aqueducts in a region of intense agricultural activity in the state of Merida, Venezuela. The study was conducted for four continuous weeks, between May and June 2008. Pesticide residues were analyzed by solid phase extraction (SPE) and liquid chromatography (HPLC) with diode array detector (DAD). The method SPE-HPLC-DAD met the criteria of analytical validation, with good linearity (R²: 0.9840 to 0.9999), precision (coefficient of inter-day variability from 1.47 to 6.25%), accuracy (relative standard deviation 0.9 to 9.20%) and sensitivity (LOD ≤ 0.012 µg/L; LOQ ≤ 0.030 µg/L, except mancozeb with 0.400 µg/L). Seven of the thirteen selected pesticides have a recovery rate between 100% and 70%, the rest between 61% and 37%. Ten pesticides of the following chemical groups, were detected in 72 samples analyzed: organophosphates, carbamates, triazines and urea derivatives. The pesticides with the highest frequency of detection were: carbofuran and atrazine (39%), malathion (25%), dimethoate and metribuzin (19%). The pesticides found at high levels were diazinon (26.31 µg/L), methamidophos (10.99 µg/L), malathion (2.03 µg/L) and mancozeb (1.27 µg/L). Pesticide levels did not exceed the maximum allowed by Venezuelan law, however, according to international standards (EU and EPA-USA) values were above the maximum permissible levels. This study demonstrates the urgent need for systematic monitoring of the quality of water for human consumption in regions of high agricultural productivity.

Chemical stability study of vitamins thiamine, riboflavin, pyridoxine and ascorbic acid in parenteral nutrition for neonatal use.

BACKGROUND: The objective of this work was to study the vitamins B1, B2, B6 and C stability in a pediatric formulation containing high amounts of calcium in the presence of organic phosphate, amino acids, glucose, sodium chloride, magnesium sulfate, pediatric vitamins and trace elements under different conditions using developed and validated analytical methods. METHODS: The study was carried out during 72 h with formulations packaged in recommended storage temperature (4°C) and 25°C, with and without photoprotection. RESULTS: The results showed that the methodologies used for assessing the chemical stability of vitamins B1, B2, B6 and C in the formulation were selective, linear, precise and accurate. The vitamins could be considered stable in the formulation during the three days of study if stored at 4°C. When stored at 25°C vitamin C presented instability after 48 h. CONCLUSION: The pediatric formulation containing high amount of calcium in the presence of organic phosphate, amino acids, glucose, sodium chloride, magnesium sulphate, pediatric vitamins and trace elements packaged in bag-type trilaminate presented a shelf life of the 72 h, when maintained under refrigeration, between 2°C and 8°C. This shelf life was measured considering the vitamins studied. Further studies are needed including all the vitamins present in this formulation.

A robust method to quantify low molecular weight contaminants in heparin: detection of tris(2-n-butoxyethyl) phosphate.

Recently, oversulfated chondroitin sulfate (OSCS) was identified in contaminated heparin preparations, which were linked to several adverse clinical events and deaths. Orthogonal analytical techniques, namely nuclear magnetic resonance (NMR) and capillary electrophoresis (CE), have since been applied by several authors for the evaluation of heparin purity and safety. NMR identification and quantification of residual solvents and non-volatile low molecular contaminants with USP acceptance levels of toxicity was achieved 40-fold faster than the traditional GC-headspace technique, which takes ~120 min against ~3 min to obtain a (1)H NMR spectrum with a signal/noise ratio of at least 1000/1. The procedure allowed detection of Class 1 residual solvents at 2 ppm and quantification was possible above 10 ppm. 2D NMR techniques (edited-HSQC (1)H/(13)C) permitted visualization of otherwise masked EDTA signals at 3.68/59.7 ppm and 3.34/53.5 ppm, which may be overlapping mononuclear heparin signals, or those of ethanol and methanol. Detailed NMR and ESI-MS/MS studies revealed a hitherto unknown contaminant, tris(2-n-butoxyethyl) phosphate (TBEP), which has potential health risks.