Pesticides In Eggs Research Articles

Application of a multiclass screening method for veterinary drugs and pesticides using HPLC-QTOF-MS in egg samples

A multi-class screening method for the determination of veterinary drugs and pesticides in eggs was developed by high performance liquid chromatography quadrupole-time-of-flight mass spectrometry (HPLC-QTOF-MS). A single-injection workflow was developed for qualitative analysis, and method validation was conducted in terms of retention time deviation (ΔRt), exact mass error (Δm), selectivity, specificity, precision and trueness. The characteristic fragment ions in information dependent acquisition (IDA) mode were summarized for retrospective and non-target screening. Five of 70 samples were found positive with sulfachloropyridazine, sulfamonomethoxine and fipronil sulfone. Compared with triple-quadrupole (QqQ) MS method, the obtained results showed that QTOF-MS gave comparable results to QqQ-MS with residue concentrations higher than 10 μg·kg−1, whereas QqQ-MS was more powerful at lower concentrations (<1 μg·kg−1). Moreover, the amount of fragment ions acquired by HPLC-QTOF-MS decreased substantially at trace levels, which may be a potential cause of reduced reliability of identification.

Determination of 60 pesticides in hen eggs using the QuEChERS procedure followed by LC-MS/MS and GC-MS/MS

An analytical method involving QuEChERS (quick, easy, cheap, effective, rugged, and safe) sample preparation, followed by LC-MS/MS and GC-MS/MS was developed and validated for the determination of 60 pesticides in eggs. Recoveries of 70–120% were achieved for selected pesticides and relative standard deviations <20% were obtained for most analytes at three concentrations. The limit of quantification was <10 µg kg−1 for 83% of the total pesticides. This method was used to analyze 58 egg samples and the residues of seven pesticides (disulfoton, fipronil sulfone, cyromazine, o,p-DDT, p,p-DDD, p,p-DDT, and permethrin) were quantified in 16 egg samples at levels of 5–10 µg kg−1, which was below the corresponding the maximum residue levels, as established by Korean Ministry of Food and Drug Safety. We demonstrated that LC-MS/MS and GC-MS/MS in combination with QuEChERS can be used to routinely monitor multiple pesticide residues in egg samples.

Plasma Cholinesterase Activity in Female Green Turtles Chelonia mydas Nesting in Laguna de Terminos, Mexico Related to Organochlorine Pesticides in Their Eggs.

The inhibition of cholinesterase (ChE) activity has been used as a biomarker of exposure to organophosphate and carbamate insecticides. ChE of nesting female green turtles (Chelonia mydas) were biochemically characterized using two substrates, acetylthiocholine iodide and butyrylthiocholine iodide, and three ChE inhibitors (eserine sulfate, BW284C51 and iso-OMPA). The results indicated that BChE is the predominant plasma ChE in female C. mydas, but with atypical properties that differ from those found in human BChE. Eggs from green turtles nesting at two sites in Laguna de Terminos contained µgg-1 (wet weight) quantities of organochlorine (OC) pesticides. Drins (aldrin, dieldrin, endrin, endrin ketone, endrin aldehyde) were found at the highest concentrations with no significant differences in the concentrations in eggs collected at the two sampling sites. A negative relationship was found between levels of OC pesticides in eggs and BChE activity in the plasma of female turtles laying the eggs. Since OC pesticides are not cholinesterase inhibitors, we hypothesized that this inverse relationship may be related to an antagonistic effect between OCs and organophosphate pesticides and mobilization of OCs from the fatty tissues of the female turtles into their eggs. However, further study is required to verify the hypothesis. It is also possible that other contaminants, such as petroleum hydrocarbons are responsible for the modulation of cholinesterase activity in female turtles.

Development and verification for analysis of pesticides in eggs and egg products using QuEChERS and LC–MS/MS

QuEChERS method was applied and validated for the multi-residue analysis of pesticides in eggs and egg products. The method includes extraction with buffered acetonitrile and clean-up with dispersive sorbents, followed by LC–MS/MS analysis. The validation parameters were used based on the guideline of SANCO/12495/2011. Recoveries were within the range of 71–108%, and the relative standard deviations were 2–13% at the 3 different concentrations evaluated for eggs and egg products. The limits of quantification for the target compounds ranged from 0.3 to 6ng/g. Monitoring of 100 domestic eggs and 50 imported egg products were performed to verify the adaptability in real samples. No samples contained residues exceeding the maximum residue limit (MRL). Carbendazim, dimethoate, and pirimicarb were each found in egg yolks at the level of 2ng/g, in the same sample, well below their MRLs of 50–100ng/g.

Absorption of current use pesticides by snapping turtle ( Chelydra serpentina) eggs in treated soil

Reptiles often breed within agricultural and urban environments that receive frequent pesticide use. Consequently, their eggs and thus developing embryos may be exposed to pesticides. Our objectives were to determine (i) if turtle eggs are capable of absorbing pesticides from treated soil, and (ii) if pesticide absorption rates can be predicted by their chemical and physical properties. Snapping turtle ( Chelydra serpentina) eggs were incubated in soil that was treated with 10 pesticides (atrazine, simazine, metolachlor, azinphos-methyl, dimethoate, chlorpyrifos, carbaryl, endosulfan (I and II), captan, and chlorothalonil). There were two treatments, consisting of pesticides applied at application rate equivalents of 1.92 or 19.2 kg a.i/ha. Eggs were removed after one and eight days of exposure and analyzed for pesticides using gas chromatography coupled with a mass selective detector (GC–MSD) or high performance liquid chromatography (HPLC). Absorption of pesticides in eggs from soil increased with both magnitude and duration of exposure. Of the 10 pesticides, atrazine and metolachlor generally had the greatest absorption, while azinphos-methyl had the lowest. Chlorothalonil was below detection limits at both exposure rates. Our preliminary model suggests that pesticides having the highest absorption into eggs tended to have both low sorption to organic carbon or lipids, and high water solubility. For pesticides with high water solubility, high vapor pressure may also increase absorption. As our model is preliminary, confirmatory studies are needed to elucidate pesticide absorption in turtle eggs and the potential risk they may pose to embryonic development.

Snapping Turtles (Chelydra serpentina) as Bioindicators in Canadian Areas of Concern in the Great Lakes Basin. 1. Polybrominated Diphenyl Ethers, Polychlorinated Biphenyls, and Organochlorine Pesticides in Eggs

We examined the concentrations and spatial patterns of congeners of PBDEs, PCBs, and organochlorine pesticides in snapping turtle (Chelydra serpentina) eggs from Areas of Concern (AOCs) on the Canadian shores of Lake Ontario, St. Lawrence River, and connecting channels. Eggs from Lyons Creek (Niagara River AOC) reflected a local PCB source over a range of 7.5 km (3.2-10.8) from the Welland Canal. PCB contamination in eggs declined with increasing distance from the Welland Canal, whereas the relative contribution of congeners associated with Aroclor 1248/1254 increased with sigma PCB concentrations. Compared to turtle eggs from other sites in Lake Erie and Lake Ontario, eggs from Lyons Creek and Snye Marsh had PCB congener patterns that reflected a strong contribution from Aroclor 1254. PCBs in the eggs were associated with industrial sources and reflected the composition of different Aroclor technical mixtures. Organochlorine pesticides in eggs tended to be highest at Hamilton Harbour and Bay of Quinte AOCs, and were dominated by DDE, sigma chlordane, and mirex. In contrast, PBDE congener patterns in turtle eggs resembled PentaBDE technical formulations regardless of absolute concentrations or location, and were largely associated with urban environments.

An Assessment of PCBs and OC Pesticides in Eggs of Double-crested (Phalacrocorax auritus) and Pelagic (P. pelagicus) Cormorants from the West Coast of Canada, 1970 to 2002

Eggs of double-crested and pelagic cormorants were collected between 1970 and 2002 from colonies in the Strait of Georgia, BC, Canada, and assayed for concentrations of organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs). Double-crested cormorant eggs from the early 1970's contained up to 4.1 mg kg-1 p,p'-DDE and 12.5 mg kg-1 sigmaPCBs. Corresponding values for pelagic cormorant eggs were 1.5 mg kg-1 p,p'-DDE and 3.9 mg kg-1 sigmaPCBs. Egg tissue concentrations of the dominant OC pesticides and sigmaPCBs dropped mainly during the 1970's, with minor declines thereafter. The data suggest that contaminant levels in cormorants have now stabilized at low levels throughout the resident population. Small but significant latitudinal gradients in several OC pesticides and PCBs indicated that areas of the southern strait were more contaminated than areas of the less populated northern strait. Interspecific differences in contamination may indicate that pelagic cormorants have a reduced capacity to metabolize chlordanes, DDT and PCBs compared to double-crested cormorants. Alternatively, the two species may have more divergent prey bases than previously thought. During the 1980's, TCDD toxic equivalents, largely contributed by polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), were correlated with physiological and biochemical alterations. Also, from 1989 to 1990, four deformed cormorant chicks (two of each species) were found during nest visits; none were found between 1991 and 1995. The relative rates of deformed chicks were 6 per 10,000 for double-crested and 16 per 10,000 for pelagic cormorants. The findings of deformed chicks were coincident with the period of highest PCDD and PCDF contamination; however, the sample sizes were too low to derive a substantive connection. Colony-wide productivity of double-crested cormorants was poorer in the southern colonies where PCBs in particular were elevated. While of concern, these lines of evidence are insufficient to conclude that chlorinated hydrocarbon contamination was a dominant contributor to population declines. It seems more probable that ecological variables, particularly changing prey and predator dynamics, drove the reductions in population size.

Residues of Organochlorinated Pesticides in Eggs of Water Birds from Tai Lake in China

The levels of organochlorine compounds in eggs of water birds from the colony on Tai Lake in China were studied. The eggs were collected in 2000 and belonged to the following species: 65 samples of black-crowned night heron (Nycticorax nycticorax), 36 samples of little egret (Egretta garzetta), 26 samples of cattle egret (Bubulcus ibis) from 13 clutches and 43 samples of Chinese pond heron (Ardeola bacchus) from 17 clutches. Dichlorodiphenyltrichloroethane (DDT) and its derivates (DDE and DDD), hexachlorocyclohexane (HCH) and its isomers (alpha-HCH, beta-HCH, gamma-HCH, delta-HCH), heptachlor, heptachlor epoxide, aldrin, dieldrin, endrin, endrin aldehyde, alpha-endosulfan, beta-endosulfan, and endosulfan sulfate were determined in the laboratory by gas chromatography. The data showed that DDE had the highest levels in all the samples, followed by beta-HCH. The mean levels of DDE among the water bird species were in the order as follows: black-crowned night heron (5464.26 ng/g, dry weight) > Chinese pond heron (2791.12 ng/g, dry weight) > little egret (1979.97 ng/g, dry weight) > cattle egret (660.11 ng/g, dry weight). DDT and its metabolites accounted for 90% of the total organochlorines, except that it was only 73% for cattle egret. The differences of the residue among the bird species were statistically significant and could be attributed to their variations in prey and habitat. Although the DDE burdens in Tai Lake were much lower than 8 microg/g (wet weight) which are thought to have significant adverse effects on black-crowned night herons, they would be expected to increase the risk of adverse effects on survival of chicks of herons and egrets, particularly black-crowned night heron, based on the critical value of 1 microg/g (wet weight) DDE. The burdens of HCHs in this study were higher and the cyclodienes were lower than those found elsewhere.

Organochlorine Pesticides in Eggs of Birds of Prey from the Stavropol Region, Russia

Organochlorine Pesticides in Eggs of Birds of Prey from the Stavropol Region, Russia

Using chorioallantoic membranes for non-lethal assessment of persistent organic pollutant exposure and effect in oviparous wildlife.

David Peakall and co-workers pioneered innovative approaches that utilized extra-embryonic membranes to assess accumulation of organochlorine pesticides in eggs. This technique provided the foundation for an entire line of research to improve non-lethal methods for assessing contaminant exposure in oviparous wildlife. Currently, analysis of chorioallantoic membranes (CAMs) provides predictable estimates of chlorinated contaminant presence in eggs and in maternal tissues. Field studies have been conducted with herons, stilts, alligators, crocodiles, and sea turtles. Controlled dose-response studies have been completed in chickens. The following manuscript presents the foundations for the CAM approach and a review of research findings involving this technique.

Reproductive success and chlorinated hydrocarbon contamination of resident great blue herons ( Ardea herodias) from coastal British Columbia, Canada, 1977 to 2000

Over the period 1977–2000, eggs of Pacific great blue heron ( Ardea herodias fannini) were collected from 23 colonies along the southern coast of British Columbia, Canada, and analyzed for persistent organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs). Concentrations of OC pesticides in eggs declined sharply in the late 1970s, after which there were minimal changes. The sums of PCB congeners were not reduced appreciably during the 1980s and 1990s, but Aroclor 1260 concentrations suggested a sharp decline in PCB contamination of eggs in the late 1970s, similar to that shown for OC pesticides. Eggs collected along or near the Fraser River delta showed higher levels of most pesticides compared to other monitored colonies. Although the delta lands support a long-standing agricultural economy, the primary factors influencing OC levels in the delta colonies were thought to be driven by estuarine processes. We suggest two possible influencing factors were: 1) a greater rate of bioaccumulation in the estuary due to the deposition of particulates collected over a vast area encompassed by the Fraser River watershed; or 2) a higher rate of biomagnification in the estuary due to species differences at lower trophic levels of the heron food chain. Eggs from urban colonies contained higher levels of PCBs. The congener pattern was not clearly different from that observed in less contaminated eggs from rural and pulp mill-influenced colonies, except that colonies in Vancouver had greater proportions of PCB-66, suggesting a local source of Aroclor 1242. Productivity in the coastal heron colonies was highly variable over the period of study, with 71% of recorded colony-wide reproductive failures occurring in colonies near pulp mills. However, the predominant factors influencing reproductive success were probably disturbance by humans and bald eagles, combined with loss and degradation of nesting habitat, and not sublethal toxicity.

PCDDs/PCDFs, PCBs, and organochlorine pesticides in eggs of Eurasian sparrowhawks (Accipiter nisus), hobbies (Falco subbuteo), and northern goshawks (Accipiter gentilis) collected in the area of Berlin-Brandenburg, Germany.

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and organochlorine (OC) pesticides were measured in unsuccessfully hatched eggs of three different kinds of predatory birds: 3 eggs of sparrowhawks, 7 eggs of hobbies, and 16 eggs of goshawks collected in the German region of Berlin-Brandenburg. Using toxic equivalency factors for birds, eggs of hobbies contained mean concentrations of 478 pg TEQ/g fat and 551 pg TEQ/g fat contributed by PCDD/Fs and coplanar PCBs, respectively. For sparrowhawks the respective TCDD equivalents were 424 and 1278 pg/g fat; those for goshawks were 211 and 935 pg/g fat. The mean value of the summed concentrations of the PCB congeners 28, 52, 101, 138, 153, and 180 amounted to 11 microg/g fat in eggs of hobbies, 9.5 microg/g fat for sparrowhawks, and 16.1 microg/g fat for goshawks. Of the analyzed organochlorine pesticides the concentration of p,p'-DDE was highest (up to 273 microg/g); the concentration of the other OCs, with the exception of methoxychlor in eggs of goshawks (highest level of 10.6 microg/g fat), were negligible. In all cases the calculated toxicity of the coplanar PCBs surpassed the toxicity of the PCDD/Fs, at least by a factor of two. Due to the higher concentration of the coplanar PCB 77 compared to PCB 126 in eggs of hobbies, it is concluded that its metabolic excretion in this species is much lower than in sparrowhawks and goshawks.

Supercritical fluid extraction of organochlorine pesticides in eggs.

The efficacy of supercritical fluid extraction (SFE) for the recovery of 16 common organochlorine pesticides (OCPs) from liquid whole eggs was investigated by employing supercritical carbon dioxide (SC-CO(2)) without the use of a solvent modifier to minimize interfering coextractives. The OCPs tested included aldrin; alpha-, beta-, delta-, and gamma-BHCs; p,p'-DDD, -DDE, and -DDT; dieldrin; endosulfans I, II, and sulfate; endrin; endrin aldehyde; heptachlor; and heptachlor epoxide. The SFE conditions were as follows: 10000 psi (680 bar), 40 degrees C, SC-CO(2) flow rate of 3.0 L/min with an extraction time of 40 min for a total of 120 L of CO(2). The OCPs were trapped off-line in an SPE cartridge containing Florisil and then eluted by an acetone/hexane mixture and analyzed by gas chromatography-electron capture detection (GC-ECD). Recovery studies were carried out on homogenized eggs fortified at the 0.05, 0.10, and 0.20 ppm levels. At the lowest level, 0.05 ppm, recoveries ranged from 81.8 to 108.3%, with CVs < 9.8%. All recoveries were significantly higher than those obtained by an AOAC/FDA solvent extraction method. Eggs containing incurred endosulfan I were also effectively extracted by SFE. This study suggests that the application of SFE for the extraction of OCPs from eggs will result in significant savings in analysis time and lower solvent use and disposal costs compared to conventional solvent extraction procedures.

Gel Permeation and Florisil Chromatographic Cleanup and Gas Chromatographic Determination of Organochlorine Pesticides in Eggs

Cleanup of residual organochlorine pesticides (OCPs; alpha-, beta-, gamma-, and delta-BHC; aldrin; dieldrin; p, p'-DDE; o,p'-DDT; p,p'-DDD; and p,p'-DDT) in eggs by gel permeation chromatography (GPC) and Florisil minicolumn chromatography is described. Ten OCPs in purified extract are determined by gas chromatography with electron capture detection. The lipids extracted from whole egg are cleaned up first by GPC with an Envirogel column and an ethyl acetate-cychlohexane (1 + 1, v/v) mobile phase and then by Florisil minicolumn chromatography with 15% (v/v) diethyl ether-hexane eluant. Cleanup is highly efficient. Average recoveries of 10 spiked OCPs (0.0025-0.0125 ppm) ranged from 81 to 101%, with coefficients of variation between 1 and 14%. The detection limit was 0.001 ppm for the 10 OCPs.

Residues of chlorinated pesticides in eggs of the gray heron (Ardea cinerea L.): Contribution of capillary gas chromatography ion‐trap mass detection

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Application of an aldrin and dieldrin ELISA to the detection of pesticides in eggs

This paper details the results obtained when a number of egg samples, collected in Egypt from different races of chicken were analyzed for the presence of the organochlorine insecticides aldrin and dieldrin. A simple ELISA was used for the detection and quantification of aldrin and dieldrin. The test was modified for application in this high protein system. Pesticide was detected in 83–352% (14/17) of the samples at levels ranging from 0.006 to 0.7 ppm (0.006 to 0.7 μg ml‐1). People eating eggs containing these amounts of pesticides which are above the World Health Organisation average daily intake levels would be at increased risk.

Pesticide Residues in Eggs and Chicks From Laying Hens Fed Low Levels of Several Chlorinated Hydrocarbon Pesticides

Eighty-four Single-Comb White Leghorn laying hens housed individually in laying cages were fed rations containing less than 0.1 p.p.m. of dieldrin, DDT, heptachlor and mirex individually or in combination for 7 days and in combination for 15 weeks. DDT residues in egg yolk reached 0.043 p.p.m. by 7 days when fed in combination with the other pesticides. None of the residues were above FDA action level at 7 days and all had declined to below trace levels by 8 weeks after termination of pesticide feeding.Residues in eggs from hens fed all four pesticides for 15 weeks increased steadily for the first few weeks and then reached a plateau or increased only slightly until pesticide feeding was terminated. By the end of the 5th week of pesticide feeding all pesticides except DDT had exceeded FDA action levels for pesticides in eggs. DDT residues reached a level of 0.139 p.p.m. by 8 weeks and did not increase thereafter. Traces of the pesticides were still present 24 weeks after termination of pesticide feeding. The pesticides tested did not affect fertility or hatchability of eggs collected during the 14th and 15th weeks of pesticide feeding. Total carcass fat of chicks hatched from these eggs had 0.024 p.p.m. dieldrin, .049 p.p.m. DDT, .001 p.p.m. heptachlor epoxide and, 0.47 mirex at 1 day of age.

Detection and Estimation of Chlorinated Pesticides in Eggs

Detection and Estimation of Chlorinated Pesticides in Eggs