Uptake of (14)C-atropine and/or its transformation products from soil by wheat (Triticum aestivum var Kronjet) and their translocation to shoots.

Plant uptake of toxins and their translocation to edible plant parts are important processes in the transfer of contaminants into the food chain. Atropine, a highly toxic muscarine receptor antagonist produced by Solanacea species, is found in all plant tissues and can enter the soil and hence be available for uptake by crops. The absorption of atropine and/or its transformation products from soil by wheat (Triticum aestivum var Kronjet) and its distribution to shoots was investigated by growing wheat in soil spiked with unlabeled or (14)C-labeled atropine. Radioactivity attributable to (14)C-atropine and its transformation products was measurable in plants sampled at 15 d after sowing (DAS) and thereafter until the end of experiment. The highest accumulation of (14)C-atropine and/or its transformation products by plants was detected in leaves (between 73 and 90% of the total accumulated) with lower amounts in stems, roots, and seeds (approximately 14%, 9%, and 3%, respectively). (14)C-Atropine and/or its transformation products were detected in soil leachate at 30, 60, and 90 DAS and were strongly adsorbed to soil, with 60% of the applied dose adsorbed at 30 DAS, plateauing at 70% from 60 DAS. Unlabeled atropine was detected in shoots 30 DAS at a concentration of 3.9 ± 0.1 µg kg(-1) (mean ± SD). The observed bioconcentration factor was 2.3 ± 0.04. The results suggest a potential risk of atropine toxicity to consumers.

Comment on Sinkovic et al. Isotope Fingerprints of Common and Tartary Buckwheat Grains and Milling Fractions: A Preliminary Study. Foods 2022, 11, 1414.

We read with interest the publication by Sinkovic et al. [...].

Assessment of geographical origin of virgin coconut oil using inductively coupled plasma mass spectrometry along with multivariate chemometrics.

Recently, Virgin coconut oil (VCO) has emerged as one of the most favorable edible oils because of its application in cooking, frying as well as additive used in food, pharmaceuticals, and cosmetic goods. These qualities have established VCO in high consumer demand and there is a great need of establishing a reliable method for the identification of its geographical origin. Through this present study, for the first time, it has been established that Inductively Coupled Plasma-Mass-Spectrometry (ICP-MS) combined with multivariate chemometrics can be used for the identification of the geographical origin of the VCO samples of various provinces. Principal Component Analysis (PCA), and Linear Discriminant Analysis (LDA) were able to differentiate and classify the VCO samples of different geographical origins. Further, calibration models (Principal Component Regression and Partial Least Square Regression) were developed on the calibration dataset of the elemental concentration obtained from the ICP-MS analysis. An external dataset was used to develop the prediction model to predict the geographical origin of an unknown sample. Both PCR and PLS-R models were successfully able to predict the geographical origin with a high R2 value (0.999) and low RMSEP value 0.074 and 0.075% v/v of prediction respectively. In conclusion, ICP-MS combined with regression modelling can be used as an excellent tool for the identification of the geographical origin of the VCO samples of various provinces. This whole technique is the most suitable as it has high sensitivity as well as provides easy multi-metal analysis for a single sample of edible oil.

The use of multispectral imaging for the discrimination of Arabica and Robusta coffee beans.

Arabica coffee beans are sold at twice the price, or more, compared to Robusta beans and consequently are susceptible to economically motivated adulteration by substitution. There is a need for rapid, non-destructive, and efficient analytical techniques for monitoring the authenticity of Arabica coffee beans in the supply chain. In this study, multispectral imaging (MSI) was applied to discriminate roasted Arabica and Robusta coffee beans and perform quantitative prediction of Arabica coffee bean adulteration with Robusta. The Orthogonal Partial Least Squares Discriminant Analysis (OPLS-DA) model, built using selected spectral and morphological features from individual coffee beans, achieved 100% correct classification of the two coffee species in the test dataset. The OPLS regression model was able to successfully predict the level of adulteration of Arabica with Robusta. MSI analysis has potential as a rapid screening tool for the detection of fraud issues related to the authenticity of Arabica coffee beans.

Adulteration Detection of Edible Bird's Nests Using Rapid Spectroscopic Techniques Coupled with Multi-Class Discriminant Analysis.

Edible bird's nests (EBNs) are vulnerable to adulteration due to their huge demand for traditional medicine and high market price. Presently, there are pressing needs to explore field-deployable rapid screening techniques to detect adulteration of EBNs. The objective of this study is to explore the feasibility of using a handheld near-infrared (VIS/SW-NIR) spectroscopic device for the determination of EBN authenticity against the benchmark performance of a benchtop mid-infrared (MIR) spectrometer. Forty-nine authentic EBNs from the different states in Malaysia and 13 different adulterants (five types) were obtained and used to simulate the adulteration of EBNs at 1, 5 and 10% adulteration by mass (a total of 15 adulterated samples). The VIS/SW-NIR and MIR spectra collated were subsequently processed, modelled and classified using multi-class discriminant analysis. The VIS/SW-NIR results showed 100% correct classification for the collagen and nutrient agar classes in authenticity classification, while for the other classes, the lowest correct classification rate was 96.3%. For MIR analysis, only the karaya gum class had 100% correct classification whilst for the other four classes, the lowest rate of correct classification was at 94.4%. In conclusion, the combination of spectroscopic analysis with chemometrics can be a powerful screening tool to detect EBN adulteration.

Detecting adulteration of stingless bee honey using untargeted 1H NMR metabolomics with chemometrics.

As stingless bee honey (SBH) is gaining in popularity in the Malaysian market, it is now prone to adulteration. The higher price of SBH compared to floral honey has led to the use of unusual adulterants such as vinegar and even floral honey to mimic the unique taste and appearance of SBH. Since the current AOAC 998.12 method fails to detect these adulterants as their δ13C values are in the range for C3 plants, untargeted 1H NMR metabolomics was proposed. Principal component analysis of SBH 1H NMR fingerprints was able to distinguish authentic SBHs from adulterated ones down to 1% adulteration level for selected adulterants. Discriminant analysis showed promising results in distinguishing the preliminary datasets of authentic SBHs from the adulterated ones, including discriminating SBHs adulterated with different adulterants derived from C3 and C4 plants. Hence, to assure any emerging adulterant can be detected, all 1H NMR regions should be considered.

Detection of exogenous sugars in pineapple juice using compound-specific stable hydrogen isotope analysis.

An improved procedure for determining 2H/1H isotope ratios, using gas chromatography-isotope ratio mass spectrometry, has been used to detect the addition of exogenous C4-plant-derived sugars to pineapple juice. Isotopic techniques are commonly used to identify the addition of low-cost sugars to fruit juices and are difficult to subvert as it is not economically viable to change the isotopic ratios of the sugars. However, the addition of cane sugar to pineapple juice has presented a significant challenge that is only detected by site-specific 13C analysis of the methyl and methylene positions of ethanol derived from pineapple sugars, measured by nuclear magnetic resonance. This new GC-IRMS-based procedure utilises the trifluoroacetate derivative of sucrose to allow direct measurement of the carbon-bound non-exchangeable hydrogen. This provides advantages over alternative isotopic methods in terms of analysis time and sensitivity. This feasibility study has demonstrated the potential to reliably differentiate between authentic pineapple juices and those adulterated with commercial beet and cane sucrose.

Rapid and non-destructive approach for the detection of fried mustard oil adulteration in pure mustard oil via ATR-FTIR spectroscopy-chemometrics.

Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy integrated with chemometrics was effectively applied for the rapid detection and accurate quantification of fried mustard oil (FMO) adulteration in pure mustard oil (PMO). PMO was adulterated with FMO in the range of 0.5-50% v/v. Principal component analysis (PCA) elucidated the studied adulteration using two components with an explained variance of 97%. The linear discriminant analysis (LDA) was adopted to classify the adulterated PMO samples with FMO. LDA model showed 100% accuracy initially, as well as when cross-validated. To enhance the overall quality of models, characteristic spectral regions were optimized, and principal component regression (PCR) and partial least square regression (PLS-R) models were constructed with high accuracy and precision. PLS-R model for the 2nd derivative of the optimized spectral region 1260-1080 cm-1 showed best results for prediction sample sets in terms of high R2 and residual predictive deviation (RPD) value of 0.999 and 31.91 with low root mean square error (RMSE) and relative prediction error (RE %) of 0.53% v/v and 3.37% respectively. Thus, the suggested method can detect up to 0.5% v/v of adulterated FMO in PMO in a short time interval.

Geographical Differentiation of Hom Mali Rice Cultivated in Different Regions of Thailand Using FTIR-ATR and NIR Spectroscopy.

Although Hom Mali rice is considered the highest quality rice in Thailand, it is susceptible to adulteration and substitution. There is a need for rapid, low-cost and efficient analytical techniques for monitoring the authenticity and geographical origin of Thai Hom Mali rice. In this study, two infrared spectroscopy techniques, Fourier-transform infrared spectroscopy with attenuated total reflection (FTIR-ATR) and near-infrared (NIR) spectroscopy, were applied and compared for the differentiation of Thai Hom Mali rice from two geographical regions over two production years. The Orthogonal Projections to Latent Structures Discriminant Analysis (OPLS-DA) model, built using spectral data from the benchtop FTIR-ATR, achieved 96.97% and 100% correct classification of the test dataset for each of the production years, respectively. The OPLS-DA model, built using spectral data from the portable handheld NIR, achieved 84.85% and 86.96% correct classification of the test dataset for each of the production years, respectively. Direct NIR analysis of the polished rice grains (i.e., no sample preparation) was determined as reliable for analysis of ground rice samples. FTIR-ATR and NIR spectroscopic analysis both have significant potential as screening tools for the rapid detection of fraud issues related to the geographical origin of Thai Hom Mali rice.

Evidence of natural occurrence of the banned antibiotic chloramphenicol in herbs and grass.

Chloramphenicol (CAP), a broad-spectrum antibiotic, was detected in several herb and grass samples from different geographic origins. Due to its suspected carcinogenicity and linkages with the development of aplastic anemia in humans, CAP is banned for use in food-producing animals in the European Union (EU) and many other countries. However, products of animal origin originating from Asian countries entering the European market are still found noncompliant (containing CAP) on a regular basis, even when there is no history of chloramphenicol use in these countries. A possible explanation for the continued detection of these residues is the natural occurrence of CAP in plant material which is used as animal feed, with the consequent transfer of the substance to the animal tissues. Approximately 110 samples were analyzed using liquid chromatography coupled with mass spectrometric detection. In 26 samples, the presence of CAP was confirmed using the criteria for banned substances defined by the EU. Among other plant materials, samples of the Artemisia family retrieved from Mongolia and from Utah, USA, and a therapeutic herb mixture obtained from local stores in the Netherlands proved to contain CAP at levels ranging from 0.1 to 450 microg/kg. These findings may have a major impact in relation to international trade and safety to the consumer. The results of this study demonstrate that noncompliant findings in animal-derived food products may in part be due to the natural occurrence of chloramphenicol in plant material. This has implications for the application of current EU, USA, and other legislation and the interpretation of analytical results with respect to the consideration of CAP as a xenobiotic veterinary drug residue and the regulatory actions taken upon its detection in food.

Stable isotope analysis of non-exchangeable hydrogen in carbohydrates derivatised with N-methyl-bis-trifluoroacetamide by gas chromatography - Chromium silver reduction/High temperature Conversion-isotope ratio mass spectrometry (GC-CrAg/HTC-IRMS).

A novel procedure for the rapid isotope analysis of the carbon-bound non-exchangeable (CBNE) hydrogen in mono and disaccharides has been developed to demonstrate the feasibility of detecting undeclared addition of exogenous sugar products in foods and beverages susceptible to economically motivated adulteration. The procedure utilizes a simple one-step reaction, with the derivatising agent N-methyl-bis-trifluoroacetamide, to substitute the exchangeable hydroxyl-hydrogens with trifluoroacetate derivatives that are sufficiently volatile to be separated and measured by a gas chromatograph coupled to an isotope ratio mass spectrometer. The conversion of the derivatised sugars into the measuring gas is achieved using a high temperature chromium-silver reactor that retains carbon, oxygen and fluorine whilst releasing hydrogen gas for stable isotope measurement. The new procedure has advantages over existing methods in terms of ease of use, analysis time and compound-specific information. Sugars from fruit juice and honey have been measured to demonstrate the feasibility of using this technique.

Rapid detection and quantification of sucrose adulteration in cow milk using Attenuated total reflectance-Fourier transform infrared spectroscopy coupled with multivariate analysis.

Adulteration of milk to gain economic benefit has become a common practice in recent years. Sucrose is illegally added in milk to reconstitute its compositional requirement by improving the total solid contents. The present study is aimed to use FTIR spectroscopy in combination with multivariate chemometric modelling for the differentiation and quantification of sucrose in cow milk. Pure milk and adulterated milk spectra (0.5-7.5% w/v) were observed in the spectral region 4000-400 cm-1. Principal component analysis (PCA) was used for the discrimination of pure milk and adulterated milk. Soft independent modelling of class analogy (SIMCA) was able to classify test samples with a classification efficiency of 100%. Partial least square regression (PLS-R) and principle component regression (PCR) models were established for normal spectra, 1st derivative and 2nd derivative for the quantification of sucrose in milk. PLS-R model (normal spectra) in the combined wavenumber range of 1070-980 cm-1 showed the best prediction based on parameters like coefficient of determination (R2) (Cal: 0.996; Val: 0.993), RMSE (Cal: 0.15% w/v; Val: 0.20% w/v), RE% (Cal: 4.9% w/v; Val: 5.1% w/v) and RPD (13.40). This method has a detection level of 0.5% w/v sucrose adulteration.

Development of an FTIR based chemometric model for the qualitative and quantitative evaluation of cane sugar as an added sugar adulterant in apple fruit juices.

A Fourier Transform Infrared Spectroscopy based chemometric model was evaluated for the rapid identification and estimation of cane sugar as an added sugar adulterant in apple fruit juices. For all the ninety samples, spectra were acquired in the mid-infrared range (4000 cm-1-400 cm-1). The spectral analysis provided information regarding the distinctive variable region, which lies in the range of 1200cm-1 to 900cm-1, designated as fingerprint region for the carbohydrates. A specific peak in the fingerprint region was observed at 997cm-1 in all the adulterated samples and was undetectable in pure samples. Based on different levels of cane sugar adulteration (5, 10, 15, and 20%), principal component analysis showed the clustering of samples and further helped us in compression of data by selecting wavenumbers with maximum variability based on the loading line plot. Supervised classification methods (SIMCA and LDA) were evaluated based on their classification efficiencies for a test set. Though SIMCA showed 100% classification efficiency (Raw data set), LDA was able to classify the test set with an accuracy of only 96.67% (Raw as well as Transformed data set) between pure and 5% adulterated samples. For the quantitative estimation, calibration models were developed using partial least square regression (PLS-R) and principal component regression method (PCR) methods. PLS-1st derivative showed a maximum coefficient of determination (R2) with a value of 0.991 for calibration and 0.992 for prediction. The RMSECV, RMSEP, LOD and LOQ observed for PLS-1st derivative model were 0.75% w/v, 0.61% w/v, 1.28%w/v and 3.88%w/v, respectively. The coefficient of variation as a measure of precision (repeatability) was also determined for all models, and it ranged from 0.23% to 1.83% (interday), and 0.25% to 1.43% (intraday).

Sorption of 14C-carbofuran in Austrian soils: evaluation of fate and transport of carbofuran in temperate regions.

Carbofuran is an anticholinesterase carbamate commonly used as an insecticide, nematicide and acaricide in agricultural practice throughout the world. However, data on its sorption in temperate soils from Europe is limited. Laboratory studies were conducted to determine the adsorption of carbofuran on three distinct Austrian soils using batch experiments and radiometric techniques. Carbofuran adsorption capacity of the soils was found to be low in the three soils tested and showed to be related to the soils clay and organic carbon contents. The pesticide presented linear adsorption isotherms in all of the three soils. Due to the low sorption of carbofuran in the soils tested and to its high water solubility, there is a risk of migration to water bodies through run off and consequent negative effects on aquatic organisms and soil biota.

Validation of an Analytical Method for the Determination of Pesticide Residues in Vine Leaves by GC-MS/MS.

A modified and miniaturized SweEt/QuEChERS method for pesticide residue analysis applied to vine leaves is presented. The deep-frozen plant material was cryogenically processed. A 2 g analytical portion was hydrated for 30 min and extracted with acidified ethyl acetate after buffering with NaHCO3 and adding Na2SO4. A dispersive solid-phase (d-SPE) cleanup step with primary-secondary amine (PSA) was performed. The pesticide residues were determined using GC-MS/MS. The whole procedure was validated for 54-59 pesticides at 0.01, 0.02, 0.1, and 0.2 mg/kg in fresh vine leaves ( Vitis vinifera). The key method performance parameters investigated were specificity, linearity, trueness, within laboratory repeatability and reproducibility, limit of detection, limit of quantitation, and matrix effects. Recoveries for the 59 pesticides tested ranged from 60 to 110%, and the RSDs were lower than 20% for the majority of the pesticides studied.

Multi-class determination of anthelmintics in soil and water by LC-MS/MS.

The translocation of antiparasitic drugs from animal excrement through soil and water to crops and forages and their recycling to food-producing animals is a potential concern with respect to the contamination of the food chain. To facilitate the investigation of this problem, an LC-MS/MS method for selected anthelmintics in soil and water was developed. The soil sample preparation involved a simple solvent extraction and dispersive clean-up technique. The method was validated at 10, 20 and 40 µg kg(-1) for levamisole, fenbendazole, fenbendazole sulphoxide and fenbendazole sulphone and at 20, 40 and 80 µg kg(-1) for eprinomectin. LOQs were 10 µg kg(-1) for the first four compounds and 20 µg kg(-1) for eprinomectin. The overall mean recoveries ranged from 76.1% to 89% for loamy soils and from 79.9% to 96.9% for sandy soils. Analysis of water samples was performed by extraction/concentration on an Oasis-HLB (Aschaffenburg, Germany) cartridge. Validation was performed at 0.25, 0.5 and 1.0 µg l(-1). The LOQ for all compounds was 0.25 µg l(-1). Method recovery (and RSD) varied between 35.4% (28) for eprinomectin and 125.1% (16) for fenbendazole sulphone. The validated methods were applied to soil and water samples in a study on the behaviour of anthelmintic drugs in a soil-plant-water system (manuscript on "transport investigation of antiparasitic drugs based on a lysimeter experiment" in preparation).

Anopheles arabiensis egg treatment with dieldrin for sex separation leaves residues in male adult mosquitoes that can bioaccumulate in goldfish (Carassius auratus auratus).

The sterile insect technique (SIT) is a biological control tactic that is used as a component of area-wide integrated pest management (AW-IPM) programs. The SIT can only be applied against disease-transmitting mosquitoes when only sterile male mosquitoes are released, and the blood-sucking and potentially disease-transmitting females are eliminated from the production line. For Anopheles arabiensis, a potent vector of malaria, a genetic sexing strain was developed whereby females can be eliminated by treating the eggs or larvae with the insecticide dieldrin. To evaluate the presence of dieldrin residues in male mosquitoes designated for SIT releases, a simple, sensitive, and accurate gas chromatography-electron capture detector (GC-ECD) method was developed. In addition, bioaccumulation and food chain transfer of these residues to fish after feeding with treated mosquitoes was demonstrated. The overall recovery from method validation studies was 77.3 ± 2.2% (mean ± relative standard deviation [RSD]) for the mosquitoes, and 99.1 ± 4.4% (mean ± RSD) for the fish. The average dieldrin concentration found in adult male An. arabiensis was 28.1 ± 2.9 µg/kg (mean ± standard deviation [SD]). A range of 23.9 ± 1.1 µg/kg to 73.9 ± 5.2 µg/kg (mean ± SD) of dieldrin was found in the fish samples. These findings indicate the need to reassess the environmental and health implications of control operations with a SIT component against An. arabiensis that involves using persistent organochlorines in the sexing process.

Characterisation of antibodies to chloramphenicol, produced in different species by enzyme-linked immunosorbent assay and biosensor technologies.

Six polyclonal antisera to chloramphenicol (CAP) were successfully raised in camels, donkeys and goats. As a comparison of sensitivity, IC50 values ranged from 0.3 ng mL(-1) to 5.5 ng mL(-1) by enzyme-linked immunosorbent assay (ELISA) and from 0.7 ng mL(-1) to 1.7 ng mL(-1) by biosensor assay. The introduction of bovine milk extract improved the sensitivity of four of the antisera by ELISA and two by biosensor assay; a reduction in sensitivity of the remaining antisera ranged by a factor of 1.1-2.6. Porcine kidney extract reduced the sensitivity of all the antisera by a factor ranging from 1.1 to 7 by ELISA and a factor of 1.5 to 4 by biosensor. A low cross-reactivity with thiamphenicol (TAP) and florfenicol (FF) was displayed by antiserum G2 (1.2% and 18%, respectively) when a homologous ELISA assay format was employed. No cross-reactivity was displayed by any of the antisera when a homologous biosensor assay format was employed. Switching to a heterologous ELISA format prompted three of the antisera to display more significant cross-reactivity with TAP and FF (53% and 82%, respectively, using D1). The heterologous biosensor assay also increased the cross-reactivity of D1 for TAP and FF (56% and 129%, respectively) and of one other antiserum (G1) to a lesser degree. However, unlike the ELISA, the heterologous biosensor assay produced a substantial reduction in sensitivity (by a factor of 6 for D1).

Validation of an efficient method for the determination of pesticide residues in fruits and vegetables using ethyl acetate for extraction.

In this study, a version of the "quick, easy, cheap, effective, rugged, and safe" (QuEChERS) method was modified to use ethyl acetate (EtOAc) rather than acetonitrile (MeCN) for extraction in the determination of multiple pesticide residues in fruits and vegetables. EtOAc is better suited than MeCN for gas chromatographic (GC) analysis with electron capture detection (ECD) and nitrogen-phosphorus detection (NPD). The method entailed extraction of 30 g chopped sample plus 5 g NaHCO(3) and 30 g anhydrous Na(2)SO(4) with 60 mL EtOAc using a probe blender. After a centrifugation step, removal of residual water and cleanup were performed using dispersive solid-phase extraction (dispersive-SPE) with MgSO(4) and primary secondary amine (PSA) sorbent. (14)C-labeled chlorpyrifos with liquid scintillation counting was used to assist in optimizing and characterizing the method, and GC-ECD and GC-NPD were used for analysis of 24 selected pesticides. The method was validated using tomato, apple and frozen green bean matrices spiked at 0.05, 0.5, and 5 mg/kg. For 22 of the analytes, recoveries averaged 93% for all three commodities over the validation range with a relative standard deviation of 10% (n = 1182). Lower recoveries of dichlorvos were obtained with the method and iprodione determination was compromised in the green beans by an interfering peak. Typical limits of detection were 0.005-0.01 mg/kg with the method.