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1.
Environ Res ; 221: 115339, 2023 03 15.
Artigo em Inglês | MEDLINE | ID: mdl-36682445

RESUMO

The changes of physicochemical and biochemical parameters of a silty loam (S1) and sandy loam (S2) vineyard soils added with spent mushroom substrate (SMS) or SMS composted with ophite (OF) as rock dust (SMS + OF) were studied. Two doses of SMS or SMS + OF (25 and 100 Mg ha-1) were applied for two consecutive years (2020-2021) and changes of soil physicochemical parameters, and dehydrogenase activity (DHA), respiration (RES), microbial biomass (BIO), and the phospholipid fatty acids (PLFAs) profile were assayed on a temporal basis. The results showed an increase in soil organic carbon (OC) content, total and mineralised N, P, and K, especially when the highest SMS dose was applied to soils. Repeated application caused OC content over time up to 2.3 times higher than initial content in the silty loam soil. This increase was not observed in sandy soil, possibly due to a higher bioavailability of OC, as indicated by the evolution of extractable humic acid/fulvic acid pools. In both soils, all biochemical parameters increased after amendment, being favoured both by the OC and by the presence of OF. Significant positive correlations were found between DHA, RES and BIO, and OC content especially in the first part and then levelled off after the second dose application. Total bacterial or fungal PLFAs patterns reflected the variation of BIO by SMS application. The higher growth of fungi vs. bacterial community in amended soils was recorded after the first SMS application, although the opposite effect occurred after the second application, with similar results in both soils. The findings indicate that the application of SMS or SMS + OF in vineyard soils could be an appropriate agronomic management practice for maintaining soil sustainability, although doses and application times of these amendments should first be evaluated depending on soil texture.


Assuntos
Agaricales , Poluentes do Solo , Solo/química , Fazendas , Agaricales/química , Carbono , Poluentes do Solo/análise , Areia
2.
Environ Res ; 195: 110871, 2021 04.
Artigo em Inglês | MEDLINE | ID: mdl-33581091

RESUMO

S-metolachlor is a widely used herbicide that may contaminate groundwater when applied to irrigated crops, especially when the soil has a low organic carbon (OC) content. The objective here was to assess the capacity of two organic wastes, namely, green compost (GC) and pelletised organo-mineral manure fertilizer (PM), applied to two soils (S) with different textures at a rate of 10% dry weight to modify the fate of S-metolachlor. The herbicide's Freundlich adsorption coefficient (Kf) increased within a range of 3.2-8.2 times in S + GC and 3.8-6.8 times in S + PM. A positive correlation between adsorption and OC and the coefficient of variation of the OC normalised adsorption coefficients (Kfoc) higher than 20% indicated the evident influence on this process of soil OC content and its nature. The increase in adsorption did not prevent the dissipation of S-metolachlor in the amended soils, although the degradation rate decreased up to ~2 times or was not significantly modified across the different soil types. The S-metolachlor metabolites, metolachlor ethane sulfonic acid and metolachlor oxanilic acid, were detected in the herbicide's dissipation in the unamended soils, but they were not detected in the amended soils. The mobility experiments indicated leached amounts of S-metolachlor higher than 50% in unamended soil. The amounts decreased 1.1-1.7 times and 1.7-1.8 times in the S + GC and S + PM when a saturated flow was applied. Moreover, breakthrough curves indicated a slow leaching kinetics of herbicide in amended soils, with low concentrations continuously detected in the leachates together with a decrease in the maximum peak concentration. The results show the effect of the application of organic wastes especially in sandy soils to promote the immobilisation and/or degradation of S-metolachlor, avoiding its transfer to other environmental compartments.


Assuntos
Herbicidas , Poluentes do Solo , Acetamidas , Adsorção , Herbicidas/análise , Solo , Poluentes do Solo/análise
3.
J Sep Sci ; 37(16): 2215-24, 2014 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-24910322

RESUMO

A procedure for multiresidue analysis was developed for the extraction and determination of 17 pesticides, including herbicides, fungicides, and insecticides, as well as certain degradation products, in vineyard soils from La Rioja region (Spain). Different solvents and mixtures were tested in spiked pesticide-free soils, and pesticides were comparatively evaluated by gas chromatography with mass spectrometry and liquid chromatography with mass spectrometry. Recoveries >70%, with relative standard deviations <9%, were obtained when a mixture of methanol/acetone or a mixture of methanol/CaCl2 0.01 M for the most polar compounds was selected as the extraction solvent. Method validation was accomplished with acceptable linearity (r(2) ≥ 0.987) within the concentration range of 0.005-1 µg/mL corresponding to 1.667-333.4 µg/kg and 0.835-167.1 µg/kg for liquid chromatography with mass spectrometry and gas chromatography with mass spectrometry, respectively, and detection limits <0.4 µg/kg for the compounds were studied. The extraction method was applied to 17 real vineyard soil samples, and terbuthylazine and its metabolite desethylterbuthylazine were the most ubiquitous compounds, as they were detected in the 100% of the soils analyzed. The presence of fungicides was also high, and the presence of insecticides was lower than other pesticides. The results confirm the usefulness of the optimized procedure for monitoring residues in vineyard soils.


Assuntos
Monitoramento Ambiental/métodos , Resíduos de Praguicidas/análise , Praguicidas/química , Solo/química , Cromatografia Gasosa , Cromatografia Líquida , Espectrometria de Massas , Metanol/química , Reprodutibilidade dos Testes , Espanha , Triazinas/análise , Triazinas/química
4.
J Sep Sci ; 35(24): 3492-500, 2012 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-23225715

RESUMO

A reliable multiresidue method based on solid phase extraction was developed using GC-MS to determine and quantify 34 pesticides, including herbicides, fungicides, insecticides, and some of their degradation products, in groundwater in a vineyard region of La Rioja (northern Spain). Different parameters were optimized and good recoveries (65-108% range) and precisions (12-19% range) were achieved with spiked water samples for a concentration of 0.1 µg/L. The experimental results showed an excellent linearity (r(2) > 0.99) over the 0.1-1.5 µg/L range. The detection limits of the proposed method were 1-37 ng/L for most of the compounds studied. The methodology has been successfully applied to the analysis of groundwater samples from vineyard areas in La Rioja and the presence of pesticides, especially fungicides and herbicides, at several concentration levels was revealed. Terbuthylazine, its metabolite desethyl-terbuthylazine, and fluometuron were the pesticides most frequently detected in higher concentrations. Overall and taking into consideration the European Union maximum residue limit of pesticides in groundwater, 16 of the 34 compounds included in this study were detected in concentrations over that limit in at least one of the samples analyzed.


Assuntos
Cromatografia Gasosa-Espectrometria de Massas/métodos , Água Subterrânea/química , Resíduos de Praguicidas/análise , Vitis , Poluentes Químicos da Água/análise , Limite de Detecção , Extração em Fase Sólida
5.
Environ Monit Assess ; 184(5): 3359-71, 2012 May.
Artigo em Inglês | MEDLINE | ID: mdl-21713466

RESUMO

The long-term variability of total Cu content from fungicides applied in a certified wine region of Spain (La Rioja) and of other metals (Cd, Cr, Ni, Pb, and Zn) was evaluated in three young vineyard soils and subsoils unamended and amended with spent mushroom substrates (SMS) over a 3-year period (2006-2008). SMS is a promising agricultural residue as an amendment to increase the soil organic matter content but may modify the behaviour of metals from pesticide utilisation in vineyards. Fresh and composted SMS was applied each year at a rate of 25 t ha(-1) (dry-weight). Copper concentrations in the three unamended soils were 21.2-88.5, 25.5-77.1, and 29.4-78.4 mg kg(-1). They exceeded natural Cu concentrations of the region and reference sub-lethal hazardous concentration for soil organism. The concentrations of Cd, Ni, Pb, and Zn were largely below the sub-lethal limits. Thus, although Cu levels were lower than those of established vineyards, vine performance, and productivity might be affected. The variation in behaviour between different amendments for each soil was high, so a generic conclusion could not be drawn. The amendment practice seemed to have caused temporarily Cu mobilization respect to untreated soils. Total zinc concentrations fall within the range of the natural soil of La Rioja and were significantly affected (p < 0.05) especially by fresh state SMS addition, with increasing up to 75% respect to untreated specimen. The results indicated a build-up of fresh sites for metal retention at both surface and subsurface level, although no accumulation of metals was observed in the short-term period. However, the benefit for soils and the negative effects need to be monitored in the long run.


Assuntos
Fungicidas Industriais/análise , Metais/análise , Poluentes do Solo/análise , Agricultura , Monitoramento Ambiental , Poluição Ambiental/estatística & dados numéricos , Recuperação e Remediação Ambiental/métodos , Espanha , Vitis , Vinho
6.
Ecotoxicol Environ Saf ; 74(6): 1480-8, 2011 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-21543118

RESUMO

The persistence, mobility and degradation of tebuconazole were assessed under field conditions in a sandy clay loam soil amended with spent mushroom substrate (SMS) at two rates. The aim was to evaluate the environmental impact of the simultaneous application of SMS and fungicide in a vineyard soil. SMS is the pasteurized and composted organic material remaining after a crop of mushroom is produced. SMS is generated in increasing amounts in La Rioja region (Spain), and could be used as soil amendment in vineyard soils, where fungicides are also applied in large amounts. The study was carried out in 18 experimental plots (6 treatments and 3 replicates per treatment) over one year. Laboratory experiments were also conducted to verify the changes over time in the adsorption of fungicide by soils and in soil dehydrogenase activity caused by the fungicide and/or SMS. Tebuconazole dissipation followed biphasic kinetics with a rapid dissipation phase, followed by a slow dissipation phase. Half-life (DT50) values ranged from 8.2 to 12.4 days, with lower DT50 for amended soils when compared to the non-amended controls. The distribution of tebuconazole through the soil profile (0-50 cm) determined at 124, 209 and 355 days after its application indicated the higher mobility of fungicide to deeper soil layers in amended soils revealing the influence of solid and dissolved organic matter from SMS in this process. Tebuconazole might be available for biodegradation although over time only chemical or photochemical degradation was evident in surface soils. The results obtained highlight the interest of field and laboratory data to design rational applications of SMS and fungicide when they are jointly applied to prevent the possible risk of water contamination.


Assuntos
Agaricales/metabolismo , Recuperação e Remediação Ambiental/métodos , Fungicidas Industriais/metabolismo , Poluentes do Solo/metabolismo , Triazóis/metabolismo , Adsorção , Fungicidas Industriais/análise , Meia-Vida , Cinética , Oxirredutases/metabolismo , Medição de Risco , Solo/química , Microbiologia do Solo , Poluentes do Solo/análise , Espanha , Triazóis/análise
7.
Int J Mol Sci ; 12(5): 3322-39, 2011.
Artigo em Inglês | MEDLINE | ID: mdl-21686187

RESUMO

A molecularly imprinted polymer (MIP), obtained by precipitation polymerisation with 4-vinylpyridine as the functional monomer, ethylene glycol dimethacrylate as cross-linker, and bisphenol-A (BPA) as template, was prepared. The binding site configuration of the BPA-MIP was examined using Scatchard analysis. Moreover, the behaviour of the BPA-MIP for the extraction of several phenolic compounds (bisphenol-A, bisphenol-F, 4-nitrophenol, 3-methyl-4-nitrophenol) and phenoxyacid herbicides such as 2,4-D, 2,4,5-T and 2,4,5-TP has been studied in organic and aqueous media in the presence of other pesticides in common use. It was possible to carry out the selective preconcentration of the target analytes from the organic medium with recoveries of higher than 70%. In an aqueous medium, hydrophobic interactions were found to exert a remarkably non-specific contribution to the overall binding process. Several parameters affecting the extraction efficiency of the BPA-MIP were evaluated to achieve the selective preconcentration of phenols and phenoxyacids from aqueous samples. The possibility of using the BPA-MIP as a selective sorbent to preconcentrate these compounds from other samples such as urine and river water was also explored.


Assuntos
Compostos Benzidrílicos/química , Fenóis/química , Extração em Fase Sólida/métodos , Sítios de Ligação , Cresóis , Poluentes Ambientais/análise , Poluentes Ambientais/química , Herbicidas , Humanos , Nitrofenóis , Tamanho da Partícula , Polimerização , Polímeros/química , Piridinas , Rios/química , Extração em Fase Sólida/instrumentação , Urina/química
8.
Environ Pollut ; 284: 117463, 2021 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-34090253

RESUMO

Sustainable agriculture practices and integrated pest management for avoiding environmental pollution are necessary to maintain a high yield in vineyard areas. Pesticide residues in groundwater in a vineyard area of La Rioja (Spain) have been evaluated in previous years, and they could now have varied after farmers have adopted the different measures recommended. Accordingly, this research's objectives were (i) to evaluate the occurrence and seasonal distribution (spring, summer, and autumn samplings) of pesticides (36) plus their degradation products (DP) (11) in water and soil samples (23 + 15) in La Rioja (Northern Spain), and (ii) to compare the current water quality (2019) with that determined previously (2011). A multi-residue method based on solid phase extraction (for water samples) or solid liquid extraction (for soil samples) and high-performance liquid chromatography coupled to mass spectrometry (HPLC-MS) was used to determine and quantify pesticides. The results reveal the presence in waters of 30 compounds from those selected (15 fungicides + 2 DP, 7 insecticides + 1 DP, and 3 herbicides +2 DP), with 14 of them at concentrations > 0.1 µg L-1 (water quality threshold for human consumption). The highest number of compounds was detected in summer (waters) and spring (soils). The pesticides most frequently detected in water samples were the fungicides metalaxyl, tebuconazole, and boscalid, with the last one being the compound found in the highest number of soil samples. The comparison of water pollution in 2011 and 2019 indicates a significant decrease in the total concentration of herbicides, fungicides and insecticides in 95-100%, 76-90%, and 42-85% of samples in the three campaigns, respectively. The results indicate that an optimized and sustainable use of pesticides in intensive and high-yield agricultural areas could reduce environmental pollution.


Assuntos
Resíduos de Praguicidas , Praguicidas , Poluentes Químicos da Água , Agricultura , Monitoramento Ambiental , Fazendas , Humanos , Resíduos de Praguicidas/análise , Praguicidas/análise , Solo , Espanha , Poluentes Químicos da Água/análise
9.
J Sep Sci ; 33(15): 2240-9, 2010 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-20589783

RESUMO

This work reports the development of a simple and automated method for the quantitative determination of several contaminants (triazine, phenylurea, and phenoxyacid herbicides; carbamate insecticides and industrial chemicals) and their metabolites in human urine with a simplified sample treatment. The method is based on the online coupling of an extraction column with RP LC separation-UV detection; this coupling enabled fast online cleanup of the urine samples, efficiently eliminating matrix components and providing appropriate selectivity for the determination of such compounds. The variables affecting the automated method were optimized: sorbent type, washing solvent and time, and the sample volume injected. The optimized sample treatment reported here allowed the direct injection of large volumes of urine (1500 microL) into the online system as a way to improve the sensitivity of the method; limits of detection in the 1-10 ng/mL range were achieved for an injected volume of 1500 microL of urine, precision being 10% or better at a concentration level of 20 ng/mL. The online configuration proposed has advantages such as automation (all the steps involved in the analysis - injection of the urine, sample cleanup, analyte enrichment, separation and detection - are carried out automatically) with high precision and sensitivity, reducing manual sample manipulation to freezing and sample filtration.


Assuntos
Poluentes Ambientais/urina , Herbicidas/urina , Inseticidas/urina , Compostos de Fenilureia/urina , Triazinas/urina , Automação , Cromatografia Líquida/instrumentação , Poluentes Ambientais/metabolismo , Herbicidas/metabolismo , Humanos , Inseticidas/metabolismo , Compostos de Fenilureia/metabolismo , Valores de Referência , Triazinas/metabolismo
10.
Environ Pollut ; 264: 114666, 2020 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-32380396

RESUMO

Water pollution by pesticides used in agriculture is currently a major concern both in Spain and in Europe as a whole, prompting the need to evaluate water quality and ecological risk in areas of intensive agriculture. This study involved monitoring pesticide residues and certain degradation products in surface and ground waters of the Denomination of Origin (DO) Jumilla vineyard area in Spain. Sixty-nine pesticides were selected and evaluated at twenty-one sampling points using a multi-residue analytical method, based on solid-phase extraction (SPE) and analysis by liquid chromatography coupled with mass spectrometry (LC-MS), providing reliable results. Twenty-six compounds from those selected were detected in the samples analyzed (eleven insecticides including one degradation product, nine herbicides, and six fungicides) and fifteen of them were found in concentrations over 0.1 µg L-1 (upper threshold established by the EU for pesticides detected in waters for human consumption). Indoxacarb was present in more than 70% of the samples, being the most frequently detected compound in water samples. Some pesticides were ubiquitous in all the water samples. Ecotoxicological risk indicators, toxic units (TUs) and risk quotients (RQs), for algae, Daphnia magna and fish were calculated to estimate the environmental risk of the presence of pesticides in waters. The compounds with the highest risk were the herbicides pendimethalin, with RQ values > 1 for the three aquatic organisms, and diflufenican, posing a high risk for algae and fish, and the insecticide chlorpyrifos, with a high risk for Daphnia magna and fish. The ∑TUi determined for water at each sampling point posed only a high risk for the three aquatic organisms in a sample. These results are important for considering the selection of pesticides with less environmental risk in intensive agricultural areas.


Assuntos
Resíduos de Praguicidas/análise , Praguicidas/análise , Poluentes Químicos da Água/análise , Animais , Monitoramento Ambiental , Europa (Continente) , Fazendas , Humanos , Medição de Risco , Espanha
11.
Environ Pollut ; 251: 90-101, 2019 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-31071637

RESUMO

In the last twenty years, pesticide use in Chile has increased more than 160%, generating a greater risk of water resources pollution. The objective of this study was to assess the presence of 22 pesticides and 12 degradation products in surface water samples from the Cachapoal River basin, Central Chile, an area characterized by intense agricultural activity. Pesticide concentrations in the dissolved phase (DP) and particulate phase (PP) in samples collected in the dry season and after precipitation events was assessed. The solid-phase extraction technique was used to preconcentrate the samples and GC/MS and LC/MS were used to detect pesticides. The results present spatio-temporal variations in the proportion and concentration of pesticides and their degradation products in both the DP and PP for each site and sampling period. The most ubiquitous compounds in the dissolved phase were atrazine, atrazine-2-hydroxy (HA), cyprodinil, pyrimethanil, and tebuconazole, while in the particulate phase HA, imidacloprid, diazinon and pyrimidinol were detected. The results presented in this study make up the first record of pesticides in the dissolved and particulate phases in surface water in Chile. They show that the problem of pesticide contamination undoubtedly affects the quality of bodies of water in agricultural areas in Chile and support the need for a proper assessment of the water quality of the Cachapoal River in the future.


Assuntos
Monitoramento Ambiental , Praguicidas/análise , Poluentes Químicos da Água/análise , Agricultura , Atrazina , Chile , Cromatografia Gasosa-Espectrometria de Massas , Neonicotinoides , Nitrocompostos , Rios/química , Estações do Ano , Extração em Fase Sólida , Água/química
12.
Sci Total Environ ; 609: 161-171, 2017 Dec 31.
Artigo em Inglês | MEDLINE | ID: mdl-28750227

RESUMO

Pesticides are needed to maintain high production in the vineyard area of La Rioja (Spain), and monitoring their spatial distribution is a priority for preserving the quality of natural resources. Accordingly, the purpose of this work was to conduct a study to evaluate the presence and seasonal distribution of herbicide and insecticide residues in ground and surface waters in this region. The monitoring network comprised 12 surface waters and 78 groundwaters, covering the three subareas (63,593ha) into which the vineyard region is divided. The quality of natural waters was examined through the analysis of twenty-two herbicides, eight of their main degradation products, and eight insecticides. Pesticides were extracted by solid-phase extraction, and analysed by gas chromatography-mass spectrometry or by liquid-chromatography-mass spectrometry. The results reveal the presence of most of the herbicides and insecticides included in the study in one or more of the samples collected during the four campaigns. The herbicide terbuthylazine and its metabolite desethylterbuthylazine were the compounds more frequently detected (present in >65% of the samples across all the campaigns). Other compounds detected in >50% of the samples in one sampling campaign were the herbicides fluometuron, metolachlor, alachlor and ethofumesate. Insecticides were present in a small number of samples, with only pirimicarb being detected in >25% of the samples in March and June campaigns. The results reveal that the sum of compounds detected (mainly herbicides) was higher than 0.5µgL-1 in >50% of the samples, especially in the campaigns with the highest application of these compounds. A possible recovery of the quality of the waters was detected outside the periods of crop cultivation, although more monitoring programmes are needed to confirm this trend with a view to preventing and/or maintaining the sustainability of natural resources.


Assuntos
Monitoramento Ambiental , Herbicidas/análise , Inseticidas/análise , Estações do Ano , Poluentes Químicos da Água/análise , Fazendas , Espanha , Recursos Hídricos
13.
Environ Sci Pollut Res Int ; 23(22): 22924-22936, 2016 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-27578090

RESUMO

The temporal trends of fungicides in surface and ground water in 90 samples, including both surface waters (12) and ground waters (78) from an extensive vineyard area located in La Rioja (Spain), were examined between September 2010 and September 2011. Fungicides are used in increasing amounts on vines in many countries, and they may reach the water resources. However, few data have been published on fungicides in waters, with herbicides being the most frequently monitored compounds. The presence, distribution and year-long evolution of 17 fungicides widely used in the region and a degradation product were evaluated in waters during four sampling campaigns. All the fungicides included in the study were detected at one or more of the points sampled during the four campaigns. Metalaxyl, its metabolite CGA-92370, penconazole and tebuconazole were the fungicides detected in the greatest number of samples, although myclobutanil, CGA-92370 and triadimenol were detected at the highest concentrations. The highest levels of individual fungicides were found in Rioja Alavesa, with concentrations of up to 25.52 µg L-1, and more than 40 % of the samples recorded a total concentration of >0.5 µg L-1. More than six fungicides were positively identified in a third of the ground and surface waters in all the sampling campaigns. There were no significant differences between the results obtained in the four sampling campaigns and corroborated a pattern of diffuse contamination from the use of fungicides. The results confirm that natural waters in the study area are extremely vulnerable to contamination by fungicides and highlight the need to implement strategies to prevent and control water contamination by these compounds.


Assuntos
Fazendas , Fungicidas Industriais/análise , Água Subterrânea/química , Rios/química , Triazóis/análise , Poluentes Químicos da Água/análise , Estações do Ano , Espanha , Vitis/crescimento & desenvolvimento
14.
Sci Total Environ ; 536: 31-38, 2015 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-26188530

RESUMO

The aim of this work was to estimate the dissipation of mesotrione applied at three doses (2, 10 and 50 mg kg(-1) dw) in an unamended agricultural soil, and this same soil amended with two organic residues (green compost (C) and sewage sludge (SS)). The effects of herbicide and organic residue on the abundance and activity of soil microbial communities were also assessed by determining soil microbial parameters such as biomass, dehydrogenase activity (DHA), and respiration. Lower dissipation rates were observed for a higher herbicide dose. The highest half-life (DT50) values were observed in the SS-amended soil for the three herbicide doses applied. Biomass values increased in the amended soils compared to the unamended one in all the cases studied, and increased over the incubation period in the SS-amended soil. DHA mean values significantly decreased in the SS-amended soil, and increased in the C-amended soil compared to the unamended ones, under all conditions. At time 0 days, respiration values were significantly higher in SS-amended soils (untreated and treated with mesotrione) than in the unamended and C-amended soils. The effect of mesotrione on soil biomass, DHA and respiration was different depending on incubation time and soil amendment and herbicide dose applied. The results support the need to consider the possible non-target effects of pesticides and organic amendments simultaneously applied on soil microbial communities to prevent negative impacts on soil quality.


Assuntos
Cicloexanonas/análise , Herbicidas/análise , Microbiologia do Solo , Poluentes do Solo/análise , Solo/química , Agricultura , Relação Dose-Resposta a Droga
15.
Sci Total Environ ; 514: 351-8, 2015 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-25679815

RESUMO

Spatial and temporal evaluations of seventeen pesticides and some of their degradation products were carried out in seventeen vineyard soils from La Rioja region (Spain). The soils were sampled in March, June and October 2012, and the pesticides were selected among those previously detected in surface and ground waters from the same area. All pesticides were detected in some of the soils in the three different areas of La Rioja at the different sampling times, with only the metalaxyl metabolite, CGA-62826, not being detected in any of the soils sampled in October. The highest concentrations were determined for the fungicides metalaxyl (11.5 µg kg(-1)) and triadimenol (26.1 µg kg(-1)), the herbicides fluometuron (174.6 µg kg(-1)) and terbuthylazine (403.3 µg kg(-1)), and the insecticide methoxyfenozide (4.61 µg kg(-1)). While the highest total concentration of pesticides was detected in March, the highest number of positive detections was recorded in June (46), as opposed to 26 and 19 in March and October, respectively. Significant differences were detected in the concentrations of herbicides in soils from the three areas in La Rioja, but this was not the case for the fungicides and the insecticides. The study revealed a more intensive use of herbicides in March, while the use of insecticides and fungicides probably depended on the specific needs of crops and/or the onset of diseases. The results are consistent with the residues found in waters in the region, and highlight the need to implement strategies for more efficient application of these compounds to avoid risk of water contamination.


Assuntos
Resíduos de Praguicidas/análise , Poluentes do Solo/análise , Solo/química , Agricultura , Monitoramento Ambiental , Espanha , Vinho
16.
J Chromatogr A ; 950(1-2): 157-66, 2002 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-11990989

RESUMO

A procedure based on solid-phase extraction (SPE) has been developed for the simultaneous preconcentration of three widely used herbicides and seven of their most common degradation products. The compounds studied were atrazine and its metabolites, desethylatrazine, desethyldesisopropylatrazine (DEDIA), 2-hydroxyatrazine, desethyl-2-hydroxyatrazine and desisopropyl-2-hydroxyatrazine (DIHA), terbutryne and its metabolite 2-hydroxyterbutylazine, and chlorotoluron and its metabolite 3-chloro-4-methylphenylurea. A HPLC system with diode array detection was used for the separation, identification and quantification of all these analytes. In the SPE preconcentration step, different types of sorbent were studied: C18 on silica and polymeric sorbents (Oasis and LiChrolut EN), the best results being obtained with the styrene-divinylbenzene cartridge and when the elution was performed with methanol and ethyl acetate. The detection limits obtained were between 0.1 microg l(-1) for DIHA and DEDIA and 0.02 microg l(-1) for the other analytes. The method used permitted the determination of these herbicides in drinking water at the concentration levels demanded by current legislation. The proposed method was used to evaluate the presence and evolution with time of these herbicides and their degradation products in samples of surface and ground waters from agricultural zones of the provinces of Salamanca and Zamora (basins of the Rivers Guarefia and Almar), Spain.


Assuntos
Herbicidas/metabolismo , Poluentes Químicos da Água/análise , Sensibilidade e Especificidade
17.
Rev Esp Salud Publica ; 76(2): 133-47, 2002.
Artigo em Espanhol | MEDLINE | ID: mdl-12025263

RESUMO

The contamination of human milk by xenobiotics is a common problem worldwide which is affected by the geographical, climate-related, cultural and socioeconomic variations in each individual location. Public health policies have dealt with this situation by means of ongoing monitoring and restrictive legislation in order to reduce the damaging effects on the populations and the environment, objectivatable data however being recorded particularly in the developing countries. Overall and individual aspects of waste and contaminating oganochlorines, organophosphorates, antibiotics, polychlorate biphenyls, dioxins and furans, their content values, toxic effects studies and the maximum limits permitted under international legislation are highlighted.


Assuntos
Resíduos de Drogas/efeitos adversos , Resíduos de Drogas/análise , Poluentes Ambientais/efeitos adversos , Poluentes Ambientais/análise , Leite Humano/química , Feminino , Humanos
18.
Sci Total Environ ; 476-477: 611-21, 2014 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-24496034

RESUMO

Dissipation kinetics of pesticides belonging to three chemical groups (linuron, diazinon and myclobutanil) was studied in an unamended agricultural soil and in this soil amended with three organic residues: sewage sludge (SS), grape marc (GM) and spent mushroom substrate (SMS). The soils were incubated with the residues outdoors for one and 12 months. Mineralized, extracted and non-extractable fractions were also studied for (14)C-linuron and (14)C-diazinon. The dissipation kinetics was fitted to single first-order or first-order multicompartment models. The dissipation rate (k) decreased in the order diazinon>linuron>myclobutanil, and DT50 values decreased for linuron (1.6-4.8 times) or increased for myclobutanil (1.7-2.6 times) and diazinon (1.8-2.3 times) in the amended soils relative to the unamended soil. The lowest DT50 values for the three pesticides were recorded in GM-amended soil, and the highest values in SMS-amended soil. After 12 months of soil incubation, DT50 values decreased in both the unamended and amended soils for linuron, but increased for the unamended and SMS-amended soil for diazinon and myclobutanil. A certain relationship was observed between the sorption of pesticides by the soils and DT50 values, although it was significant only for myclobutanil (p<0.05). Dissipation mechanism recorded the lowest mineralization of (14)C-pesticides in the GM-soil despite the highest dissipation rate in this soil. The extracted (14)C-residues decreased with incubation time, with increased formation of non-extractable residues, higher in amended soils relative to the unamended soil. Soil dehydrogenase activity was, in general, stimulated by the addition of the organic amendments and pesticides to the soil after one month and 12 months of incubation. The results obtained revealed that the simultaneous use of amendments and pesticides in soils requires a previous study in order to check the environmental specific persistence of these compounds and their effectiveness in amended soils.


Assuntos
Modelos Químicos , Praguicidas/química , Poluentes do Solo/química , Solo/química , Agaricales , Agricultura , Diazinon/química , Linurona/química , Nitrilas/química , Esgotos , Triazóis/química
19.
Sci Total Environ ; 454-455: 299-306, 2013 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-23562684

RESUMO

A monitoring program was developed for the environmental analysis of four phenols and three phenoxyacid herbicides in natural surface and ground water samples from the vineyard region of La Rioja (Spain). An analytical method based on molecularly imprinted solid phase extraction was developed for the determination of the impact of these compounds on the quality of environmental water samples. Different parameters were evaluated and optimized to achieve limits of detection in the 20-90 ng L(-1) range for both surface and ground water, with relative standard deviations in the 12-18% range. A comparative study of the behavior of the imprinted polymer compared with traditional sorbents (C18 and Oasis HLB) in the analysis of river water was performed. The results revealed that bisphenol-A is the most ubiquitous compound (present in more than 50% of the samples), with values up to 0.72 µg L(-1). Bisphenol-F was also detected in several samples (33% of the samples), although in concentration lower than Bisphenol-A. The herbicide 2,4-D was frequently detected in water samples (present in 33% of the samples), with concentrations above 0.1 µg L(-1) in two samples.


Assuntos
Monitoramento Ambiental/métodos , Herbicidas/análise , Fenóis/análise , Extração em Fase Sólida/métodos , Poluentes Químicos da Água/análise , Absorção , Cromatografia Líquida de Alta Pressão , Água Doce/análise , Impressão Molecular , Polímeros/química , Espanha
20.
Rev. esp. salud pública ; 76(2): 133-147, mar. 2002.
Artigo em Es | IBECS (Espanha) | ID: ibc-16366

RESUMO

La contaminación de la leche humana por xenobióticos es un problema generalizado a nivel mundial, que se ve afectado por las variaciones geográficas, climáticas, culturales y socioeconómicas de cada lugar. Las políticas de salud pública han enfrentado la situación mediante una vigilancia sostenida y legislaciones restrictivas con el objeto de reducir los efectos perjudiciales sobre las poblaciones y el ambiente, sin embargo se registran datos objetivables, sobre todo en los países en desarrollo. En esta revisión se destacan aspectos generales y particulares de los residuos y contaminantes organoclorados, organofosforados, antibióticos, metales pesados, bifenilos policlorados, dioxinas y furanos, valores de sus contenidos, efectos tóxicos estudiados y los límites máximos permitidos por las legislaciones internacionales (AU)


Assuntos
Feminino , Humanos , Leite Humano , Resíduos de Drogas , Poluentes Ambientais
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