Honey as a bioindicator of environmental organochlorine insecticides contamination / Mel como bioindicador de contaminação ambiental de inseticidas organoclorados

Abstract Honey is a suitable matrix for the evaluation of environmental contaminants including organochlorine insecticides. The present study was conducted to evaluate residues of fifteen organochlorine insecticides in honey samples of unifloral and multifloral origins from Dir, Pakistan. Honey samples (5 g each) were extracted with GC grade organic solvents and then subjected to Rotary Evaporator till dryness. The extracts were then mixed with n-Hexane (5 ml) and purified through Column Chromatography. Purified extracts (1μl each) were processed through Gas Chromatograph coupled with Electron Capture Detector (GC-ECD) for identification and quantification of the insecticides. Of the 15 insecticides tested, 46.7% were detected while 53.3% were not detected in the honey samples. Heptachlor was the most prevalent insecticide with a mean level of 0.0018 mg/kg detected in 80% of the samples followed by β-HCH with a mean level of 0.0016 mg/kg detected in 71.4% of the honey samples. Honey samples from Acacia modesta Wall. were 100% positive for Heptachlor with a mean level of 0.0048 mg/kg followed by β-HCH with a mean level of 0.003 mg/kg and frequency of 83.3%. Minimum levels of the tested insecticides were detected in the unifloral honey from Ziziphus jujuba Mill. Methoxychlor, Endosulfan, Endrin and metabolites of DDT were not detected in the studied honey samples. Some of the tested insecticides are banned in Pakistan but are still detected in honey samples indicating their use in the study area. The detected levels of all insecticides were below the Maximum Residue Levels (MRLs) and safe for consumers. However, the levels detected can cause mortality in insect fauna. The use of banned insecticides is one of the main factors responsible for the declining populations of important insect pollinators including honeybees.

Resumo O mel é uma matriz adequada para a avaliação de contaminantes ambientais, incluindo inseticidas organoclorados. O presente estudo foi conduzido para avaliar resíduos de 15 inseticidas organoclorados em amostras de mel de origem unifloral e multifloral de Dir, Paquistão. Amostras de mel (5 g cada) foram extraídas com solventes orgânicos de grau GC e, em seguida, submetidas ao evaporador rotativo até a secura. Os extratos foram então misturados com n-hexano (5 ml) e purificados por cromatografia em coluna. Os extratos purificados (1μl cada) foram processados através de cromatógrafo gasoso acoplado a detector de captura de elétrons (GC-ECD) para identificação e quantificação dos inseticidas. Dos 15 inseticidas testados, 46,7% foram detectados enquanto 53,3% não foram detectados nas amostras de mel. O heptacloro foi o inseticida mais prevalente com um nível médio de 0,0018 mg / kg detectado em 80% das amostras, seguido por β-HCH com um nível médio de 0,0016 mg / kg detectado em 71,4% das amostras de mel. Amostras de mel da parede de Acacia modesta foram 100% positivos para heptacloro com um nível médio de 0,0048 mg / kg seguido por β-HCH com um nível médio de 0,003 mg / kg e frequência de 83,3%. Níveis mínimos dos inseticidas testados foram detectados no mel unifloral de Ziziphus jujuba da usina. Metoxicloro, Endosulfan, Endrin e metabólitos do DDT não foram detectados nas amostras de mel estudadas. Alguns dos inseticidas testados são proibidos no Paquistão, mas ainda são detectados em amostras de mel, indicando seu uso na área de estudo. Os níveis detectados de todos os inseticidas estavam abaixo dos Níveis Máximos de Resíduos (MRLs) e seguros para os consumidores. No entanto, os níveis detectados podem causar mortalidade na fauna de insetos. O uso de inseticidas proibidos é um dos principais fatores responsáveis pelo declínio das populações de importantes insetos polinizadores, incluindo as abelhas.

Detection of enteropathogens and research of pesticide residues in Lactuca sativa from traditional and agroecological fairs / Detecção de enteropatógenos e pesquisa de resíduos de agrotóxicos em Lactuca sativa de feiras tradicionais e agroecológicas

Agroecological production represents a new reality in vegetable farming. Thus, the study aimed to search for the presence of pesticides in agroecological samples and microbiological and parasitological contamination in Lactuca sativa L. of agroecological and conventional fairs in Alagoas. Thirty-two samples were collected, a hygienicsanitary checklist was performed, along with coliform, Salmonella spp., Staphylococcus aureus research and Gas Chromatography with Mass Spectrometer (GC-MS) for pesticide research; using two methodologies for parasitological studies. Thirty-two samples were analyzed, with a sanitary adequacy level at 45% and 38% for fairs (agroecological and conventional) respectively, with three samples (9.4%) in total, being adequate to the microbiological pattern according to RDC no. 12/2001. Among the 23 samples which were tested positive for parasites, 69.5% originated from samples extracted at conventional fairs, and 53% of every positive samples presented Entamoeba coli as the main contaminant. All together, no traces of deltamethrin were detected, but in two of the samples a peak retention for diphenoconazole was detected. In conclusion, the fairs represent an adequate environment for human pathogens and indicators. Therefore greater hygiene training of vegetable traders and consumers in the state of Alagoas is required, especially in conventional fairs, which presented more critical microbiological and parasitological indexes comparing to fairs with agroecological products; however, the presence of difenoconazole in two samples of agricultural fairs suggests accidental contamination or indiscriminate use of this chemical in the production of Lactuca sativa, however, products with agroecological origin represents a better choice for the consumers.

A produção agroecológica representa uma nova realidade no cultivo das hortaliças. Assim, o estudo teve como objetivo verificar a presença de agrotóxicos em amostras agroecológicas e analisar a contaminação microbiológico e parasitológico em Lactuca sativa L. de feiras agroecológicas e convencionais de Alagoas. Foram coletadas 32 amostras, realizando checklist higiênico-sanitário, análises de coliformes, Salmonella spp., Staphylococcus aureus e Cromatografia Gasosa com Espectrômetro de Massas (GC-MS) para pesquisa de agrotóxicos; utilizando-se duas metodologias para estudos parasitológicos. Foram analisadas 32 amostras, com nível de adequação sanitária de 45% e 38% para feiras (agroecológicas e convencionais) respectivamente, sendo três amostras no total (9,4%) adequadas a padrão microbiológico segundo RDC n° 12//2001; Dentre as 23 amostras positivas para parasitos, 69,5% teve origem em amostras de feiras convencionais, e 53% de todas as amostras positivas apresentaram Entamoeba coli como principal contaminante, juntamente, não foi detectado traços de deltametrina, porem foi visualizado em duas amostras, pico de retenção para padrão de difenoconazol. Concluindo-se que as feiras representam um ambiente adequado para patógenos humanos e indicadores, necessitando de uma maior higienização e treinamento dos comerciantes e consumidores de hortaliças do estado de Alagoas, principalmente em feiras convencionais, que apresentaram índices microbiológicos e parasitológicos mais críticos em relação a feiras com produtos agroecológicos; mas, a presença de difenoconazole em duas amostras de feiras agroecológicas sugerem contaminação acidental ou uso indiscriminado deste químico em produção da Lactuca sativa L., todavia os produtos de origem agroecológica representam uma melhor escolha para o consumidor.

Research progress on pesticide residues of Lonicera Japonica Flos / 中国中药杂志

Lonicera Japonica Flos is the dried bud or nascent flower of Lonicera japonica(Caprifoliaceae). The plant suffers from various diseases and pests in the growth period and thus pesticides are often used. As a result, the resultant pesticide residues in Lonicera Japonica Flos have aroused great concern. This review summarized the investigation, detection methods, content analysis, and risk assessment of pesticide residues in Lonicera Japonica Flos since 1996, and compared the maximum residue limits among different countries and regions. The results showed that the pesticide residues were detected in Lonicera Japonica Flos from different production areas, and only some exceeded the limits. The residual pesticides have changed from organochlorines to new types such as tebuconazole and nitenpyram. The detection method has upgraded from chromatography to chromatography-mass spectrometry. Most pesticide residues will not cause health risks, except carbofuran. Pesticide residues limit the development of Lonicera Japonica Flos industry in China. In practice, we should improve the drug registration of Lonicera Japonica Flos, promote ecological prevention and control technology, and formulate and promote pesticide residue limit standard of Lonicera Japonica Flos.

Research progress on pesticide residues of Panax notoginseng / 中国中药杂志

Panax notoginseng is a perennial Chinese medicinal plant, which has serious continuous cropping obstacles and is prone to a variety of diseases and insect pests during the growth process. At present, the prevention and control of pests and diseases is mainly carried out through chemical pesticides, and the consequent pesticide residues of P. notoginseng have attracted much attention. This study reviewed the types and detection methods of pesticide residues in P. notoginseng from 1981 to 2021, and compared the limits of pesticide residues in P. notoginseng in China and abroad to provide a reference for rational application of pesticides in P. notoginseng and quality control of medicinal materials, thereby promoting the sustainable development of the P. notoginseng industry in China. Currently, there are only 40 published papers on pesticide residues of P. notoginseng, which is indicative of a serious problem of insufficient research. At present, hundreds of pesticide residues in P. notoginseng can be detected simultaneously by using chromatography-tandem mass spectrometry. The pesticides detected have gradually changed from early prohibited ones, such as dichlorodiphenyl trichloroethane(DDT), benzene hexachloride(BHC), and parathion, to low toxic ones(e.g., dimethomorph, procymidone, propicona-zole, and difenoconazole). The dietary risk from pesticide residues in P. notoginseng is low, which would not cause harm to consu-mers. This study concluded that in the future, the development of the quality standard for pesticide residues of P. notoginseng should be actively carried out. To increase the pesticides used in actual production in the quality standard based on the existing ones and to guide farmers to use pesticides scientifically will be the focus of future work.

Research progress on pesticide residues of Panacis Quinquefolii Radix / 中国中药杂志

Panacis Quinquefolii Radix is the dry root of Panax quinquefolium, which is a perennial plant of Araliaceae. The plant has a long growth cycle and serious growth barrier problem, which leads to the use of pesticides. As a result, the pesticide residues in Panacis Quinquefolii Radix are arousing great concern. This paper reviews the research findings on the investigation, detection methods, content analysis and risk assessment of pesticide residues in Panacis Quinquefolii Radix since 1993, and compares the pesticide residue limit standards of different countries and regions. The pesticide residues in Panacis Quinquefolii Radix have been changing from organochlorines with high toxicity to triazines and triazoles with low toxicity. The pesticide residues are generally low, while the pollution of pentachloronitrobenzene and other pesticides still exist. The detection method has evolved from chromatography to chromatography-mass spectrometry. There are no reports of health risks caused by pesticide residues of Panacis Quinquefolii Radix. Pesticide residue is a major factor restricting the sound development of Panacis Quinquefolii Radix industry in China. Therefore, we suggest to improve the registration of pesticides applied to the plant, popularize mature ecological planting mode and supporting technology, and strengthen the research on the risk assessment and limit standard of pesticide residue in Panacis Quinquefolii Radix.

Research progress on pesticide residues of Panax ginseng / 中国中药杂志

Panax ginseng, a perennial herb, is prone to diseases and insect pests in the growth process, which are primarily prevented and treated by pesticides. However, due to the lack of standardization in the types, frequencies, and doses of pesticides, pesticide residues have become the main exogenous pollutants of P. ginseng. To explore the risk of pesticide residues in P. ginseng, this paper summarized and analyzed the common pesticide residues in P. ginseng, detection techniques, and pesticide residue limit stan-dards based on the published literature in recent years. The results revealed that the main pesticide residues in P. ginseng were organochlorine pesticides, such as tetrachloronitrobenzene, pentachloronitrobenzene, and hexachlorobenzene, and the detection techniques were dominated by gas chromatography(GC), liquid chromatography(LC), or those combined with mass spectrometry(MS). Because of the long half-life and difficulty in degradation, organochlorine pesticides have become the main factor affecting the export of P. ginseng. It is worth mentioning that P. ginseng has been classified as food in Japan, South Korea, the European Union, and other countries, and the standards of pesticide residues and limits are stricter than those in China. The quality and safety of P. ginseng are prerequisites for the efficacy of Chinese medicine and the development of traditional Chinese medicine. The formulation of scientific and effective standards for pesticide application and limits would promote the high-quality development of the P. ginseng industry.

Pesticide residues in Chinese medicinal materials and suggestions for safety / 中国中药杂志

The present study counted the frequency of detection technologies and monitoring frequency of pesticide species by frequency analysis based on the 28 258 pieces of data on pesticide content of Chinese medicinal materials in CNKI, calculated the detection rate and exceeding rate of different types of pesticides, and systematically analyzed the pesticide residue pollution of Chinese medicinal materials. The results showed that there were 40 types of pesticides with detection rates higher than 10%, where new pesticides such as organochlorines and nicotine accounted for 55%, and organic phosphorus, pyrethroids, and carbamates accounted for 17.5%, 15.0%, and 12.5%, respectively. Seventeen types of pesticides exceeded the standard to varying degrees, including 12 types(70.59%) with exceeding rates not higher than 5%, four types(23.53%) with exceeding rates in the range of 5%-10%, and one type(5.88%) with an exceeding rate higher than 10%. As revealed by the analysis results of the past five years, the pesticide residue pollution of Chinese medicinal materials showed a downward trend. Compared with the conditions at worst, organochlorines decreased by about 2/3 in detection rate and 47.23% in exceeding rate, carbamates by about 1/2 in detection rate and 10.78% in exceeding rate, organic phosphorus by 3/4 in detection rate and 7.22% in exceeding rate, pyrethroids by 1/2 in detection rate and 11.05% in exceeding rate, and other types by about 1/2 in detection rate but not exceeded the standard. In general, pesticide residues in Chinese medicinal materials and safety have been significantly improved. However, pesticide residues are still important factors affecting the quality and safety of Chinese medicinal materials. It is suggested to further improve the control standards of pesticide residues in Chinese medicinal materials, strengthen the monitoring of pesticides used in practical production, and promote the ecological planting mode to facilitate the high-quality development of the Chinese medicinal material industry.

Research progress of pesticide residues in Chrysanthemum / 中国中药杂志

Chrysanthemum is widely used as a type of edible flower and also considered as the important materials of many beverages in China. Due to the occurrence of diseases and pests, and the lack of regulations for species, frequency, dose of pesticides in Chrysanthemum, pesticides have become one of the main pollutants in Chrysanthemum. The pesticide residues in Chrysanthemum were detected frequently and worth noting. This paper focused on the types of pesticides, pesticide residue detection techniques, and risk assessment methods for Chrysanthemums on the basis of relevant literatures. The pesticide residues of traditional Chinese medicine are mainly organochlorines, organophosphorus and pyrethroids, and the detection techniques include gas chromatography(GC), liquid chromatography(LC) or both combined with mass spectrometry(MS). With the increasing use of traditional Chinese medicine, Chrysanthemum is widely circulated in the market. Therefore, it is important to understand the current situation of pesticide residues in different varieties of Chrysanthemum, so as to provide theoretical reference for the control of quality and safety of Chrysanthemum and the formulation of the maximum residue limit.

Recent advances in surface-enhanced Raman scattering technique for pollutant detection in Chinese medicinal material / 中国中药杂志

Chinese medicinal material is the foundation of traditional Chinese medicine(TCM) industry. Its quality is not only closely related to the health of residents but also the key to the development of the TCM industry. Pesticide residues, heavy metals and mycotoxins are the major pollutants of Chinese medicinal materials. In recent years, quite a number of rapid detection methods for pollutants have been constructed. Among them, surface-enhanced Raman scattering(SERS), which has been widely used in food chemistry, environmental analysis, and other fields because of its speediness and non-destructiveness, shows its great potential in the pollutant detection in Chinese medicinal material. This paper firstly reviews the application of SERS for the detection of common pollutants in Chinese medicinal material. We then discussed the characteristics and advantages of SERS technique for pesticide detection, including the principle, SERS substrate design, specific recognition, etc. Finally, simultaneous detection of multiple pesticide residues in Chinese medicinal material was explored.

Desafios e avanços no controle de resíduos de agrotóxicos no Brasil: 15 anos do Programa de Análise de Resíduos de Agrotóxicos em Alimentos / Challenges and strides in the control of pesticide residues in Brazil: 15 years of the Program for Analysis of Pesticide Residues in Food Products / Desafíos y avances en el control de residuos de pesticidas en Brasil: 15 años del Programa de Análisis de Residuos de Pesticidas en Alimentos

Resumo: No Brasil, desde 2001, o monitoramento da presença de agrotóxicos nos alimentos ocorre por meio do Programa de Análise de Resíduos de Agrotóxicos em Alimentos (PARA). O objetivo foi analisar os desafios e avanços no controle de resíduos de agrotóxicos nos alimentos, no Brasil, com base nos resultados do PARA, entre os anos 2001 e 2015. Foi realizada pesquisa descritivo-analítica documental, que utilizou dados provenientes dos relatórios do PARA, disponíveis no sítio eletrônico da Agência Nacional de Vigilância Sanitária. Entre os principais desafios apresentados pelo PARA estão a grande variabilidade no número de amostras e ingredientes ativos analisados, bem como no formato dos relatórios apresentados. Existe a necessidade do aprofundamento das discussões a respeito dos critérios usados para a classificação e autorização dos ingredientes ativos no Brasil, bem como da transparência destas informações para a sociedade. No total, foram analisados 25 tipos de alimentos e mais de 30 mil amostras ao longo da vigência do PARA, porém, o máximo de ingredientes ativos analisados foi 228. A presença de ingredientes ativos não autorizados para a cultura e não autorizados no país foi a principal causa de irregularidades diagnosticadas nos alimentos. Embora ainda existam diversos desafios apresentados no PARA, ele contribui para disparar a reflexão sobre o tema junto à sociedade. Haja vista a atual conjuntura do governo, de maior flexibilização na liberação de ingredientes ativos no país, é necessário que o PARA seja fortalecido.

Abstract: In Brazil, since 2001, pesticides in food products have been monitored by the Program for Analysis of Pesticide Residues in Food Products (PARA, in Portuguese). The study aimed to analyze the challenges and strides in the control of pesticide residues in food products in Brazil based on the program's results from 2001 to 2015. A descriptive-analytical document review was conducted that used data from reports by the PARA, available at the website of the Brazilian Health Regulatory Agency. The program's main challenges feature the wide variation in the number of samples and active ingredients analyzed, as well as the reports' format. There is a need for more in-depth discussions of the criteria used for classification and authorization of active ingredients in Brazil, as well as the information's transparency to society. A total of 25 types of foods were analyzed, with more than 30,000 samples, since the PARA has been in force, but the maximum number of active ingredients analyzed was 228. The presence of active ingredients unauthorized for crops and unauthorized in the country was the principal cause of irregularities diagnosed in the foods. Although the program still faces various challenges, it helps spawn debate on the issue in society. Given the current government context of greater flexibility in the authorization of active ingredients in Brazil, it is necessary to strengthen the PARA.

Resumen: En Brasil, desde 2001, la supervisión de la presencia de pesticidas en los alimentos se produce mediante el Programa de Análisis de Residuos de Pesticidas en Alimentos (PARA). El objetivo fue analizar los desafíos y avances en el control de residuos de pesticidas en los alimentos, en Brasil, a partir de los resultados del PARA, entre los años 2001 y 2015. Investigación descriptivo-analítica documental, que utilizó datos provenientes de los informes del PARA, disponibles en la página web de la Agencia Nacional de Vigilancia Sanitaria. Entre los principales desafíos presentados por el PARA, están la gran variabilidad en el número de muestras e ingredientes activos analizados, así como en el formato de los informes presentados. Existe la necesidad de profundizar en las discusiones, respecto a los criterios utilizados para la clasificación y autorización de los ingredientes activos en Brasil, así como la transparencia de esta información para la sociedad. En total, se analizaron 25 tipos de alimentos y más de 30 mil muestras, a lo largo de la vigencia del PARA, no obstante, el máximo de ingredientes activos analizados fue 228. La presencia de ingredientes activos no autorizados para el cultivo y no autorizados en el país fue la principal causa de irregularidades diagnosticadas en los alimentos. A pesar de que todavía existan diversos desafíos presentados en el PARA, contribuye a activar la reflexión sobre este tema junto a la sociedad. Ante la actual coyuntura de gobierno, con una mayor flexibilización en la autorización de ingredientes activos en el país, es necesario que el PARA sea fortalecido.

Estimation of chronic dietary intake of pesticide residues / Estimativa de ingestão crônica de resíduos de agrotóxicos por meio da dieta

ABSTRACT OBJECTIVE To estimate the maximum theoretical daily intake of pesticides potentially consumed, chronically, by the Brazilian population. METHOD By using data from the food consumption section of the 2008-2009 Household Budget Survey to characterize the population diet, a database was built to group the foods based on the NOVA classification. Considering the maximum residue limit values of each pesticide authorized in the country until 2016, the limits of all consumed foods were added and multiplied by the amount consumed, resulting in the maximum theoretical intake index, which was compared with the acceptable daily intake. RESULTS The results show that, of the 283 pesticides considered in the database, 71 (25%) compounds had estimates of zero intake, 144 compounds (50.8%) reached acceptable daily intake values and 68 compounds (24%) showed median intake that exceeded the acceptable daily value. The pesticide intake estimation according to the different regions of the country showed a variation in the amount of compounds that exceeded the acceptable daily intake (48 to 69 substances) due to the different consumption patterns. The categories of products that most exceeded the limits were the insecticides, herbicides and fungicides. CONCLUSION The application of this methodology is valid for the first step in risk assessment, but the resulting values may be different from the actual exposure since they do not include other factors, such as the combined use of pesticides or unauthorized products. The importance of developing research on specific national food consumption data in a systematic way is emphasized, which generates data and analyses that allow a detailed risk assessment.

RESUMO OBJETIVO Estimar a ingestão diária máxima teórica dos agrotóxicos potencialmente consumidos, de forma crônica, pela população brasileira. MÉTODO Utilizando os dados do bloco de consumo alimentar da Pesquisa de Orçamentos Familiares de 2008-2009 para caracterização da dieta da população, foi construído um banco de dados agrupando os alimentos com base na classificação NOVA. Considerando os valores de limite máximo de resíduos de cada agrotóxico autorizado no país até o ano de 2016, foram somados os limites de todos os alimentos consumidos, multiplicados pela quantidade consumida, gerando o índice de ingestão teórica máxima, que foi comparado com a ingestão diária aceitável. RESULTADOS Os resultados mostram que dos 283 agrotóxicos considerados no banco de dados, 71 compostos tiveram estimativas de ingestão zero (25%), 144 compostos (50,8%) atingiram aos valores de ingestão diária aceitável e 68 compostos (24%) apresentaram mediana de ingestão que excedeu o valor diário aceitável. Quando realizada a estimativa de ingestão de agrotóxicos discriminando as distintas regiões do país, houve variação (entre 48 e 69 substâncias) na quantidade de compostos que excederam a ingestão diária aceitável devido aos diferentes padrões de consumo da população. As categorias dos produtos que mais excederam as estimativas são inseticidas, herbicidas e fungicidas. CONCLUSÃO A aplicação dessa metodologia é válida para o primeiro passo na avaliação de risco, porém os valores resultantes podem ser diferentes da exposição real por não englobar outros fatores, como o uso combinado de agrotóxicos ou de produtos de uso não autorizado. É ressaltada a importância do desenvolvimento de pesquisas de dados específicos de consumo de alimentos nacionais de forma sistemática, gerando dados e análises que viabilizem uma avaliação pormenorizada sobre riscos.

Health risk assessment of exogenous harmful pollutants in Chinese medicine: a review / 中国中药杂志

In recent years, the quality and safety problems have been limiting the internationalization of Chinese medicine. The pollutants in Chinese medicine, particularly the exogenous harmful pollutants mainly including mycotoxins, pesticide residues, heavy metals, harmful elements, and sulfur dioxide, are of high risks for people. Therefore, the World Health Organization(WHO) and relevant national organizations have clearly defined the maximum residue limits(MRLs) of such pollutants. Chinese Pharmacopoeia(2020 edition, volume Ⅳ) also demonstrates the detection methods, MRLs and preliminary risk assessment methods for four typical exogenous harmful pollutants in Chinese medicine. Therefore, continuous optimization of the health risk assessment system can further help further raise the quality and safety of Chinese medicine. This paper reviews the research on the health risk assessment of four typical exogenous harmful pollutants in Chinese medicine and discusses the problems of and challenges for the assessment system, which is expected to lay a scientific basis for the establishment of the risk warning mode and response measures suitable for specific types of Chinese medicine.

Current status of organophosphorus pesticide residues in root and rhizome medicinal materials and research progress of rapid detection methods / 中国中药杂志

The medicinal plants with roots and rhizomes as the medicinal parts account for about 1/3 of Chinese medicinal herbs. Root and rhizome medicinal materials are widely used in clinical practice, whereas their wild resource reserves are insufficient to meet the market demand. With the expansion of planting areas, the formation of large-scale production areas, and the increase in planting years, diseases and insect pests of these medicinal plants, which are diverse and have broad transmission routes, strong concealment, and heavy damage, have become more and more serious. The prevention and control of these diseases and insect pests is characterized by multiple ways of pesticide application, large consumption of pesticides, susceptibility to soil barrier, difficulty in the control, and unstable control efficiency. Organophosphorus pesticides(OPPs) are widely used in the cultivation of Chinese medicinal plants because of their diverse varieties, broad-spectrum, good efficacy, and low residues, and have a positive effect on the yield and quality of Chinese medicinal materials. However, the abuse of OPPs not only increases the planting cost, but also affects the quality and safety of Chinese medicinal plants, the safety of clinical use of Chinese medicine, and the ecological safety of production areas. This paper reviewed the research and development progress of OPPs, the registration status of OPPs used in root and rhizome medicinal materials, residue limit standards, residue status, and rapid detection technology progress of OPPs. This review aims to provide research ideas and references for standardizing the use of OPPs in root and rhizome medicinal materials, reducing OPP residues, and establishing a fast, efficient, accurate, and reliable method for the detection of OPP residues in Chinese herbal medicine.

Avaliação de resíduos de pesticidas na dieta brasileira, período de 2001 a 2010 / Evaluation of pesticide residues in the Brazilian diet, from 2001 to 2010

O consumo, de alimentos seguros, vem aumentando e a prática do uso de agrotóxicos é comum no Brasil. A cesta básica deve ter os alimentos monitorados, para tanto, esforços do governo deveriam garantir a produção de alimentos seguros. O monitoramento de resíduos de agrotóxicos auxilia na garantia da qualidade. Neste estudo, no Laboratório de Resíduos de Pesticidas, analisaram-se amostras de frutas, grãos e hortaliças, no período de 10 anos (2001 a 2010). Método multirresíduos foi utilizado para identificar e quantificar os agrotóxicos. As amostras sem resíduos corresponderam de 60 a 95% do total. As amostras positivas apresentaram principalmente fungicidas e inseticidas. As violações (não permitido para a cultura e acima do limite máximo de resíduos-LMR) corresponderam a 20% do total e, apesar dos valores acima do LMR, a ingestão diária aceitável dos agrotóxicos encontrados nos alimentos não foi ultrapassada. Os resultados, embora não sejam críticos, são importantes para avaliar a qualidade do alimento consumido.(AU)

Nowadays, the safe food products concerning the human and animal health is increasing. Pesticide usage is a common practice in Brazil, therefore, the food basket must be controlled. Pesticide residues analysis conducted by laboratories as Pesticide Residues Laboratory (LRP) and national programs are important to guarantee the food quality. The objective of this work was to evaluate the data from LRP to these from monitoring programs. Samples of fruits, grains and vegetables (10-year period, 2001 to 2010) were analyzed. Multi-residues method was used to identify and quantify the pesticide residues. The total of 60 to 95% were negative samples. About 20% of the samples could be declared as inappropriate for the consumption, considering compounds not permitted for the crops and above the MRL. The ADI parameter was not exceeded. Perhaps such levels could represent a public health concern, the results are not critical, but are useful to evaluate the exposure to the food contaminants.

Contaminação de águas superficiais e de chuva por agrotóxicos em uma região do estado do Mato Grosso / Groundwater and rainwater contamination by pesticides in an agricultural region of Mato Grosso state in central Brazil

O presente trabalho objetivou analisar a contaminação de águas superficiais e de chuvas por agrotóxicos em dois municípios do estado do Mato Grosso, Lucas do Rio Verde e Campo Verde, situados entre os maiores produtores de soja, milho e algodão do estado e do país. A metodologia analítica combinou o uso de técnicas cromatográficas em amostras de água superficial e de chuva com análises ecotoxicológicas do impacto da contaminação por agrotóxicos sobre espécies bioindicadoras. Resultados das análises mostraram a presença de resíduos de diferentes agrotóxicos nas amostras de águas superficiais e de chuva coletadas nos dois municípios. Associados a estes dados, resultados das análises ecotoxicológicas mostraram a presença de anomalias em uma espécie de anfíbio anuro coletado em uma das duas localidades, compatíveis com exposição a agrotóxicos. Os resultados aqui apresentados e discutidos apontam para a degradação da qualidade de recursos hídricos da região, causada pelo uso intensivo de agrotóxicos na agricultura, incluindo fontes de água de consumo humano e de chuvas, amplificando o risco de contaminação para além das áreas de plantio.

This study sought to analyze groundwater and rainwater contamination by pesticides in two municipalities (Lucas do Rio Verde and Campo Verde) of Mato Grosso state. The area is Brazil's mid-west situated among the major soybean, corn and cotton producers in the state and the country. The analytical methodology combined chromatographic techniques on groundwater and rainwater samples with eco-toxicological analyses of the impacts of contamination by pesticide on bio-indicator species. The results revealed the presence of different pesticide residues in the groundwater and rainwater samples collected in the two municipalities. In conjunction with this data, results of the eco-toxicological tests revealed the presence of anomalies in a bio-indicator species collected in one of the two study sites compatible with exposure to pesticides. The results presented and discussed here highlight the degradation of water resources in the region, caused by the intensive use of pesticides in agriculture, including the contamination of drinking water sources and rain, broadening the risk of contamination beyond the cultivated areas.

Impact of changing over of insecticide from synthetic pyrethroids to DDT for indoor residual spray in a malaria endemic area of Orissa, India.

Background & objectives: Development of insecticide resistance in malaria vectors has been a major problem for achieving effective vector control. Due to limited availability of insecticides, the only option is management of resistance by judiciously using the insecticides and rotating them to maintain their effectiveness. This study was carried out in a malaria endemic area of Sundergarh district in Orissa where synthetic pyrethroids (SP) were in use for the last couple of years. The change-over from SP to DDT was done in one arm of study, and the other two arms remained on SP and insecticide-treated nets (ITN). Entomological and parasitological monitoring was done to assess the impact. Methods: The study design comprised of three arms (i) two rounds of indoor residual spraying (IRS) with DDT 1g/m2 as a change-over insecticide in areas previously under synthetic pyrethroids; (ii) two rounds of IRS with synthetic pyrethroid (alphacypermethrin, ACM) @ 25 mg/m2; and (iii) an unsprayed area under ITN/long lasting insecticide nets (LNs). Indoor residual spraying was undertaken under strict supervision to maintain quality and coverage. Contact bioassays were conducted to know the persistence of insecticide on sprayed surfaces and adult vector density was monitored in fixed and randomly selected houses. Malaria incidence was measured through fortnightly domiciliary surveillance under primary health care system in all the study villages. Results: The insecticide susceptibility tests showed that An.culicifacies was resistant to DDT but susceptible to malathion and ACM. However, An. fluviatilis was susceptible to all the three insecticides. ACM was effective in killing An. culicifacies on mud and wooden sprayed surfaces and maintained effective bioefficacy ranging from 92 to 100 per cent up to five months, whereas DDT failed to achieve effective mortality in An.culicifacies. However, there was significant decline in the density of An.culicifacies in ACM and DDT areas in comparison to ITNs/LNs. There was 61 per cent reduction in the slide positivity rate in ACM area in comparison to 48 and 51 per cent in DDT and ITN/LNs areas, respectively. The adjusted incidence rate of malaria cases per 1000 population in three study areas also showed significant declines within each group. Interpretation & conclusions: The present findings show that the change-over of insecticide from synthetic pyrethroids to DDT brings about the same epidemiological impact as envisaged from continuing SP spray or distributing insecticide treated nets/long-lasting insecticidal nets provided there is a good quality spray and house coverage.

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.

Application of liquid chromatography-high resolution mass spectrometry in toxicological screening / 法医学杂志

Due to the diversity of toxicologically relevant substances, the uncertainty of target compounds and the specificity of samples, toxicological screening techniques have always been valued by the forensic toxicologists. Depending on its powerful separation ability, superhigh resolution and accurate mass measurement, combined with the two levels spectrum database matching and abundance ratio of isotope ion, the liquid chromatography-high resolution mass spectrometry (LC-HRMS) analyzers have increasingly advantage in screening and identification of chemical compound. This review focuses on the applications of LC-HRMS in screening and identification of drug-of-abuse, prescription drugs, pesticide and stimulant. The prospect of LC-HRMS in forensic toxicology analysis is also included.