Determination of total Aflatoxins and Carbamate Pesticide Residues in Some Bee Honey Samples Using QuEChERS Method and High Performance Liquid Chromatography (original) (raw)
Pesticides contamination in Egyptian honey samples
Journal of Consumer Protection and Food Safety, 2017
Honey is a natural food and widely used for its nutritional and therapeutic properties. The occurrence of pesticides in honeybees causes a potential risk for consumers. In the current study, LC-MS/MS and GC/MS methods were optimized for analysis of 46 multiclass pesticides residues in honey samples. The effect of different extraction solvents and dispersive solid phase extraction (DSPE) purification on the analytical methods performance were investigated. Acetonitrile performed better than ethyl acetate in terms of method efficiency and decreasing of matrix effects, while DSPE was effective in reducing matrix effect. The analytical methods were validated according to European Commission guidelines, in terms of accuracy, repeatability, reproducibility, linearity, LOD and LOQ. The methods were applied to 52 honey samples collected from northern and southern governorates of Egypt. Detectable levels of penconazole, difenoconazole, metalaxyl and carbofuran residues were found, in the range of 3-30 lg/kg, in 14 % of the samples. These results indicate that the tested honey samples are safe for human consumption, taking into account the effect of environmental conditions of the honey's production region on the pesticides contamination levels.
Study of aflatoxin B 1 production by Aspergillus parasiticus in bee pollen of Greek
Mycotoxin Research, 2010
Aflatoxin B 1 (AFB 1 ) is a carcinogenic metabolite produced by certain Aspergillus species such as A. parasiticus and A. flavus. The beneficial properties of bee pollen have transformed this commodity into an increasingly frequent component of the human diet. As bee pollen is a substrate on which aflatoxigenic fungi can grow, AFB 1 production is likely. In the present study, we describe a method for aflatoxin B 1 determination in bee pollen utilising high pressure liquid chromatography (HPLC) with a fluorescence detector (FD). The recovery factor of the method was found to be 111% (RSD% 1.61), while the detection limit (LOD) was 0.08 ng AFB 1 /g. An additional aim of this study was to investigate the growth of A. parasiticus and AFB 1 production in bee pollen. Results indicated that no mycelial growth was observed and no AFB 1 was detected in bee pollen samples containing natural microbiota throughout the entire observation period (20 days). In contrast, AFB 1 production in treated bee pollen samples (15 g pollen/flask) inoculated with A. parasiticus was significantly higher (p≤0.05) compared to control samples (treated but not inoculated) throughout the entire incubation period, while no mycelial growth was apparent. Maximum production was observed on the 12th day (79.29 ng AFB 1 /flask and 32.44 ng AFB 1 /flask for inoculated and non-inoculated bee pollen, respectively). As a result, AFB 1 production in bee pollen is likely even following a minor contamination, which could occur randomly.
Annals of Agricultural Sciences, 2010
Serial concentrations of three unprocessed honey (mountain; nuwara clover and citrus) samples from Egypt, were evaluated for their ability to act as antimicrobial activity against fifteen fungal species including toxigenic strains of Aspergillus flavus and A. parasiticus and four Gram positive and five Gram negative pathogenic bacterial isolates. Also, investigation of inhibitory action of aflatoxins production by A. flavus and A. parasiticus was studied. 90% and 100% concentrations of three honeys used, exhibited high ability to inhibit the growth of most of fungal and bacterial isolates. Mountain honey was the best honey. It showed antimicrobial activity followed by citrus then nuwara clover honey. However, 80% concentration from only mountain honey showed antimicrobial activity while all other honey concentrations prepared did not show any ability to reduce the growth of all fungal and bacterial isolates tested. As well as, no aflatoxins were produced at 100% concentration of three honeys used, while great reduction of aflatoxins production was detected after treatment with 90% concentration of all honeys. Moderated effect on toxins production was reported by 80% concentration and little inhibition was obtained at 70% honey concentration. Other honey concentrations (10% to 60%) showed opposite effect on aflatoxins production, where the amounts of toxins were increased. Mountain honey was the best, which showed ability to inhibit the production of aflatoxins by both of A. flavus and A. parasiticus followed by nuwara clover then citrus honey.
Study of aflatoxin B1 production by Aspergillus parasiticus in bee pollen of Greek origin
Mycotoxin Research, 2010
Aflatoxin B 1 (AFB 1 ) is a carcinogenic metabolite produced by certain Aspergillus species such as A. parasiticus and A. flavus. The beneficial properties of bee pollen have transformed this commodity into an increasingly frequent component of the human diet. As bee pollen is a substrate on which aflatoxigenic fungi can grow, AFB 1 production is likely. In the present study, we describe a method for aflatoxin B 1 determination in bee pollen utilising high pressure liquid chromatography (HPLC) with a fluorescence detector (FD). The recovery factor of the method was found to be 111% (RSD% 1.61), while the detection limit (LOD) was 0.08 ng AFB 1 /g. An additional aim of this study was to investigate the growth of A. parasiticus and AFB 1 production in bee pollen. Results indicated that no mycelial growth was observed and no AFB 1 was detected in bee pollen samples containing natural microbiota throughout the entire observation period (20 days). In contrast, AFB 1 production in treated bee pollen samples (15 g pollen/flask) inoculated with A. parasiticus was significantly higher (p≤0.05) compared to control samples (treated but not inoculated) throughout the entire incubation period, while no mycelial growth was apparent. Maximum production was observed on the 12th day (79.29 ng AFB 1 /flask and 32.44 ng AFB 1 /flask for inoculated and non-inoculated bee pollen, respectively). As a result, AFB 1 production in bee pollen is likely even following a minor contamination, which could occur randomly.
Detection of Carbamates in Honeybees and Bee-products of Karnataka State
Honeybee species like A. cerana, A. dorsata and A. florea are well distributed in Karnataka state. Monitoring of pesticides by honeybees and their products as biological indicators is of great importance because of their toxicity to human beings and potential hazard. The monitoring of pesticide residues in honey helps to assess the potential risk to consumers’ health, providing information on the pesticides used in the field crops. The indiscriminate use of pesticides in the agro ecosystems is the major environmental health concern. In the present investigation, 253 samples of honeybees, honey, pollen, brood and wax were collected in different zones of Karnataka during 2010-2013. The concentration of three pesticides like carbaryl carbofuran and methomyl belonging to carbamate group was determined through HPLC. Twenty samples were contaminated of which carbofuran and methomyl were detected in 16 and four samples respectively. Carbamates have one of the highest acute toxicities to humans among pesticides widely used on agri-horticultural crops due to its activity as a cholinesterase inhibitor and neurotoxicity. The study revealed that the agro and forest ecosystems of Karnataka has not been contaminated with high degree of pesticide residues as indicated by the bees and bee products except very low concentration in few areas of the state. There is an urgent need to monitor bee pollinator health as they are indispensible organism in the ecosystem and contributing for increased crop production and food security.
Saudi Journal of Biological Sciences, 2020
Honey is a complex foodstuff found in nature which is used without any processing. Honey has been in use in medicine as well as raw food since ancient times. Essentially, it is a blend of sugars especially fructose and glucose. The objectives of the study were to determine major sugar composition as well as pesticides contamination in honey samples. Further, Hydroxy-methyl-furfuraldehyde (HMF) level was also determined to ascertain the freshness of honey samples. A total of 14 samples were collected from local market and tested for fructose, glucose, sucrose, HMF and organochlorine pesticides using HPLC and GC-MS techniques respectively. The total sugars in the 14 honey samples were found ranging between 50.26 and 74.74 g/100 g of honey. The chromatographic results showed the presence of the sugars like fructose and glucose in all honey samples. The honey sample SH-11 was found to contain the highest amount of fructose (40.63%). On the other hand, the lowest amount of fructose with 29.08% was observed in SH-7. The HPLC analysis also revealed the presence of sucrose in two samples but under the permissible limit. The average ratio of fructose to glucose in these honey samples was 1.3. None of the sample has ratio below 1.0 indicating lesser chances for honey to crystallize on storage. Out of 14 honey samples, 13 samples were found negative for the presence of any of the 63 pesticides tested. Only sample No. 13, was found to contain 15.95 ppb hexachlorobenzene per kilogram of honey. The HMF was not detected in four samples but in remaining samples it was well below the maximum permissible limit. No pesticide and sugar adulteration was observed in any of the honey samples. The honeys collected from Saudi Arabian markets were found to confirm the standards set by the regional and international standardization organization, the GSO and Codex Alimentarius Commission respectively.
Chromatographic-based methods for pesticide determination in honey: An overview
Talanta, 2007
Nowadays the control of pesticides in honey is an issue of primary health importance as consequence of the increasing content of these chemicals in the aforementioned matrix. This poisoning has led to the worldwide increasing loss of bees since 1995. From Europe to Canada, scientist, beekeepers and chemical companies disagree about the reasons that have led to colony losses higher than 50% in some areas. This problem has become a public health issue due to the high honey worldwide consumption. The presence of pesticides in honey has been directly related to bees' mortality by some researchers through pesticide presence in (1) pollen, (2) honeycomb walls, (3) own bees and (4) honey. In this work we describe the actual state-of-the-art for pesticides determination in honey along with a review in this subject focused on sample treatments and instrumentation. Finally, future trends are also commented.
Mycotoxin Profile of Honey and Dry-Cured Meat (Kilishi) for Export in Abuja, Nigeria
Food Science and Engineering
Animal products are not immune to contaminants and could render them not safe for local consumption or unacceptable for export. This study aimed to ascertain the prevalence and profile of Aflatoxins (AFs), Ochratoxins (OTs) and Fumonisins (FBs) contamination in honey and dry-cured meat (kilishi) intended for export in the Federal Capital Territory (FCT) of Nigeria. Ninety (90) samples of each animal product were collected and analyzed. Mycotoxins were determined using High-Performance Liquid Chromatography (HPLC) quantitative techniques. According to the investigation, none of the honey samples for export from the FCT Abuja was positive for Aflatoxin B1 (AFB1) and Aflatoxin B2 (AFB2) contaminants. The occurrence of Ochratoxin A (OTA) was most prevalent in the samples of honey from Abuja East, but with the greatest average concentration (62.87 μg/Kg) in the samples from Abuja South. In samples from the Abuja South zone, the prevalence of AFB1 and AFB2 in the kilishi was relatively hi...
Determination of Pesticide Residues in Honey Samples
Bulletin of Environmental Contamination and Toxicology, 2009
Protocol for the determination of pesticides residues in honey samples have been standardized using a simple technique of liquid-liquid extraction. The method is sensitive to detect low levels of pesticides in honey. Honey sample was fortified with pesticides, namely, cypermethrin, fenvalerate, alphamethrin, lamba-cyhalothrin, endosulfan (a, b and sulfate) and chlorpyrifos. The method of extraction and clean up was optimized and validated in the laboratory. The method was applied to screen six samples of honey locally available for pesticides residues. Recoveries ranged from 60% to 90.6% with RSDs from 2% to 10%. Low recoveries were recorded for a and b-endosulfan in the range of 60%-71%. The LOQs, varied from 0.05 to 1.0 mg kg-1 .
Environmental Monitoring and Assessment , 2024
Pesticides are of immense importance in agriculture, but they might contaminate bees’ products. In this study, samples of honey, pollen, and beeswax were collected, seasonally, from apiaries in Toshka (Aswan), El-Noubariya (El-Beheira), and Ismailia (Ismailia) cities in Egypt. The pesticide residues were analyzed using the GC-MS after being extracted and cleaned using the QuEChERS method. Results showed that samples from El-Noubariya had great content of residues followed by Ismailia, and finally Toshka. Samples collected during fall and winter had the highest pesticide residue contents. Specifically, the phenylconazole fungicide group was repeatedly detected in all the examined samples along with organophosphate insecticides. Beeswax samples had the greatest amounts of pesticide residues followed by pollen and then honey samples. Chlorpyrifos (0.07–39.16 ng/g) and profenofos (1.94–17.00 ng/g) were detected in honey samples and their products. Pyriproxyfen (57.12 ng/g) and chlorpyrifos-methyl (39.16 ng/g) were detected in great amounts in beeswax samples from Ismailia and El-Noubariya, respectively. Yet, according to health hazard and quotient studies, the amounts of pesticides detected in honey do not pose any health threats to humans.
Determination of Pesticides Residues in Bee Products: An Overview of the Current Analytical Methods
Insecticides [Working Title], 2022
The presence of undesirable compounds in honey and other bee products may modify their biological attributes. Such molecules may be present because of different human activities (i.e., pollutants, pesticides) or because of veterinary treatments designed to control and prevent diseases that affect bees. The use of pesticides in agricultural crops has been related with negative effects with and acute damages for bees. The widespread agricultural use of neonicotinoids is a common exposure pathway for bees, and it may be an important factor in declining bee health. In 2013, the European Union has forbidden the use of three pesticides belonging to the neonicotinoids: Imidacloprid, Thiamethoxam, and Clothianidin after the analysis of several scientific results of some studies where those pesticides were involved in an increased death of bees.
Assessment of Pesticide Residues in Honey Samples from Portugal and Spain
Journal of Agricultural and Food Chemistry, 2003
Fifty samples of honey collected from local markets of Portugal and Spain during year 2002 were analyzed for 42 organochlorine, carbamate, and organophosphorus pesticide residues. An analytical procedure based on solid-phase extraction with octadecyl sorbent followed by gas chromatographymass spectrometry (GC-MS), for organochlorines, and by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS), for organophosphorus and carbamates, has been developed. Recoveries of spiked samples ranged from 73 to 98%, except for dimethoate (40%), with relative standard deviations from 3 to16% in terms of repeatability, and from 6 to 19% in terms of reproducibility. Limits of quantification were from 0.003 to 0.1 mg kg -1 . Most of the pesticides found in honey were organochlorines. Among them, γ-HCH was the most frequently detected in 50% of the samples, followed by HCB in 32% of the samples and the other isomers of HCH (R-HCH and -HCH) in 28 and 26% of the samples, respectively. Residues of DDT and their metabolites were detected in 20% of the samples. Of the studied carbamates, both methiocarb and carbofuran were detected in 10% of the samples, pirimicarb in 4% and carbaryl in 2%. The only organophosphorus pesticides found were heptenophos in 16%, methidathion in 4%, and parathion methyl in 2% of honey samples. Results indicate that Portuguese honeys were more contaminated than Spanish ones. However, honey consumers of both countries should not be concerned about the amounts of pesticide residues found in honeys available on the market.
Honeybees (Apis mellifera L.) play an important ecological and economic role in the pollination service of crops. Pesticide residues in honey can happen when bees in search nectar and pollen, visit crops that have been treated with various agrochemicals for different reasons. The presence of pollutants in honey can influence honeybee colony performance and devalue its use for human consumption. The aims of this study were to determine pesticide residue levels in honey samples from East Shewa and West Arsi zone and to identify type of pesticides present in honey samples. A total of 24 honey samples were collected from apiaries different localities just after harvesting. Honey samples were analyzed using gas chromatography mass spectrometry. Among different pesticides analyzed in honey samples, Chlorpyrifos was the most frequently detected (16.7%) followed by Endosulfan sulphate (12.5%) and Profenofos (8.3%). The average recoveries of pesticides ranged between 72% and 102.4%, with relative standard deviation less than 20%. All the pesticide residues detected were very low and below their respective maximum residue limits set by the European Union. Hence, pesticide residues in honey samples analyzed do not pose any health risk to consumers. Although the study results showed none significant pesticide residue in the analyzed honey samples, a special precaution should be taken regarding to production of pesticides, their sale, and application in the future.
Determination of Selected Pesticides in Honey by LC-MS-It: Effects of Sample Preparation
Safety Engineering, 2012
Honey is well known in human diet and it is considered to be one of the healthiest foods with high nutritional value. Due to the growing presence of anthropogenic contaminants, with extremely long half-life and prevalence in all environments, some of them may be present in honey. Honey samples were spiked with six pesticides which are commonly used at the time of plant's blooming, in order to develop an efficient method for preparing honey samples for LC-MS-IT analysis. Samples of honey, spiked with soultion containing mixture of six pesticides (pirimicarb, atrazine, prometrine, malation, cyprodinil and famoxadone), were treated applying SPE with Florisil and C18 cartriges, as well as liquid-liquid extraction method. Afterwards, samples were injected in the HPLC with ESI ionisation source, and IT (ion trap) mass analyzer. Methanol solution of pesticides in the same concentrations as in spiked samples, were used as blank. In spiked honey samples, after treatment with Florisil pro...
American Journal of Applied Chemistry
This study investigated physicochemical properties and pesticide residue levels of honey from West Shewa Zone, Ethiopia. The results of moisture, electrical conductivity, pH, free acidity, reducing sugar, sucrose, ash, and total solids were found to be 16.61-18.64%, 0.384-0.646 mS/cm, 3.77-4.22, 7.42-13.87 meq/kg, 61.38-72.87%, 6.84-15.94%, 0.030-0.095%, and 81.36-83.28%, respectively. Correlation analysis has shown moderate positive correlation at P < 0.01 between sucrose and ash (r = 0.555), and a strong negative correlation between moisture and total solids (r =-0.9171). Residues of 4,4-DDD, 4,4-DDT, Dieldrin, α-Endosulfan, and β-Endosulfan were detected, among 20 organochlorine pesticides analyzed. Most physicochemical parameters have been found within the acceptable range set by national and international standards except sucrose content from Ejere and Toke Kutaye. The estimated daily intakes (EDIs) of pesticides identified in samples were below acceptable daily intakes (ADIs), that indicate honey ingesting has a negligible influence to toxicological risk.
2012
Honey is an important food widely used by people around the world. It can contain agrochemical residues as a result of the use of these products in agriculture. QuEChERS method was used for the determination of seven pesticide residues (chlorothalonil, heptachlor, captan, α-endosulfan, β-endosulfan, endosulfan sulfate and dieldrin) in 25 Brazilian honey samples from different regions. Extraction was carried out through the use of 1% acetic acid-ethyl acetate solvent with MgSO 4 and CH 3 COONa, followed by dSPE cleanup with PSA sorbent. The analyses were carried out with GC-µECD. The chromatographic signal showed good linearity with correlation coefficient ≥ 0.99 and the LOQs for the pesticides studied varied between 0.007 to 0.05 mg kg -1 . The method was validated using a blank sample of honey spiked at three fortification levels (0.07, 0.2 and 0.4 mg kg -1 ). The recoveries for the seven compounds ranged from 75% to 119%, and relative standard deviations were ≤ 26%. Five of the 25 honey samples analyzed contained pesticide residues, with a maximum concentration of 0.026 mg kg -1 for α-endosulfan. From the five contaminated samples, four were from non-agricultural areas, which indicated environmental contamination at these sites. The QuEChERS approach was successfully employed for the GC-µECD analyses of the seven studied pesticides in honey samples.
Determination of some organochlorine pesticide residues in honeys from Konya, Turkey
Environmental monitoring and assessment, 2010
In this study, 24 organochlorine pesticide residues in 109 different honey samples collected from stores and open markets in Konya, Turkey were analyzed by gas chromatography-electron capture detection. Aldrin, cis-chlordane, trans-chlordane, oxy-chlordane, 2,4′ -DDE, and 4,4′ -DDE were found in all honey samples. The mean value was 0.0540 μg g − 1 for oxy-chlordane. In the 55 samples of 109, levels of organochlorine pesticide residues of oxy-chlordane were determined as higher than those of Turkish Alimentarius Codex maximum residual limits (MRLs). Other organochlorine pesticide residues also exceeded MRLs except for cis-heptachlor epoxide and α-hexachlorocyclohexane. Since all of the honey samples are found contaminated and most of these samples exceeded MRLs, a control of organochlorine pesticide residues in honey is necessary for consumer health.