Agricultural Chemical Residues Research Articles

First Detection of Food-Derived Agricultural Chemicals Residues in Waste Wool Fibers by Ultrasound-Assisted Extraction-QuEChERS Cleanup-UPLC-MS/MS.

Food-derived agricultural chemical residues (FACRs) accumulate gradually in organisms and can damage their nervous system, endocrine system and reproductive system, posing significant harm. Currently, there is little literature on the detection of FACRs in waste wool fibers. In this paper, an ultrasound-assisted extraction-QuEChERS (Quick, Easy, Cheap, Effective, Rugged, Safe) cleanup-UPLC-Ms/Ms method was applied for the qualitative analysis and quantitative determination of trace FACRs in waste wool fibers with 0.2% formic acid-methanol as extraction solvent and multi-selective ion scanning. Using the external standard method, it was shown that the 13 target FACRs showed good linearity in the mass concentration range of 0.1-50μg/kg. The limits of detection were 1.0-10.0μg/kg and the limits of quantification were 4.0-40.0μg/kg. The recoveries of the 13 target FACRs ranged from 78 to 112.6% at the 5-, 10- and 20-fold detection limit spiked levels, and the intra- or inter-day relative standard deviations were 2.05-6.98% or 1.98-6.99%, respectively. This method satisfied the detection requirements and can be used in applications.

Expression of CYP76C6 Facilitates Isoproturon Metabolism and Detoxification in Rice

Agricultural chemical residues in farmland and crops is one of the serious public issues that constantly threatens crop production, food security, and human health. Understanding their decay mechanism in crops for accelerating their degradative metabolism is important. In this study, a rice uncharacterized cytochrome P450 gene encoding CYP76C6 was functionally identified in rice exposed to isoproturon (IPU). To verify the role of CYP76C6 in rice resistance to IPU toxicity, CYP76C6 overexpression (OEs) and knockout mutant rice by CRISPR/Cas9 were generated through genetic transformation and gene-editing technologies. Assessment of growth and physiological responses revealed that the growth of OE lines was improved, the IPU-induced cellular damage was attenuated, and IPU accumulation was significantly repressed, whereas the Cas9 lines displayed a contrasting phenotype compared to the wild-type. Both relative contents of IPU metabolites and conjugates in OE lines were reduced and those in Cas9 line were increased, suggesting that CYP76C6 plays a critical role in IPU degradation. Our study unveils a new regulator, together with its mechanism for IPU decay in rice crops, which will be used in reality to reduce environmental risks in food safety and human health.

Detection of amoxicillin residues in egg extract with a molecularly imprinted polymer on gold microchip using surface plasmon resonance and quartz crystal microbalance methods.

In this study, surface plasmon resonance (SPR) and quartz crystal microbalance (QCM) sensors were prepared for the detection of amoxicillin from the commercial and local chicken eggs by using molecular imprinting technique. Amoxicillin imprinted poly(hydroxyethyl methacrylate-methacrylic acid) polymeric film was synthesized onto the surface of the SPR and QCM chips by ultra violet polymerization to determine lower concentrations of amoxicillin. Ellipsometry, contact angle analysis, and atomic force microscopy measurements were used for the surface morphology of the polymeric film layer. The ellipsometric thickness of AMOX imprinted and nonimprinted SPR and QCM chip surfaces were measured as 35 ± 0.9nm,32.89 ± 1.9nm,30 ± 0.6nm, and 28 ± 0.22nm,respectively. Contact angles of bare gold surfaces, AMOX imprinted SPR and QCM chip surfaces were measured to be as 82.3° ± 0.15, 79.2° ± 0.14, 75.01° ± 1.07, and 69.11° ± 0.89, respectively. The range of linearity was measured as 0.1 to 10ng/mL for amoxicillin imprinted SPR and QCM sensors. The maximum residue limit of AMOX in eggs is at 10µg/kg in accordance with the "Positive List System for Agricultural Chemical Residues in Foods." The response time for the test, including adsorption, desorption, and regeneration, was approximately 45min. The limit of detections for SPR and QCM sensors were found to be 0.0005 and 0.0023ng/mL, respectively. The reusabilities of amoxicillin imprinted SPR and QCM sensors were observed by the equilibration-binding-regeneration. Validation studies of the AMOX imprinted SPR and QCM sensors were performed by liquid chromatography-tandem mass spectrometry.

Potential use of cuminic acid as a botanical fungicide against Valsa mali.

Valsa canker caused by Valsa mali is commonly present in eastern Asia and cause large economic losses. Because of limited agricultural measures and chemical residues of commonly used fungicides there is an urgent need of alternative plant protecting agents. On this background the activity of cuminic acid, a plant extract from the seed of Cuminum cyminum L, was assessed. The median effective concentration (EC50) values for inhibition of mycelial growth of seven V.mali strains ranged from 3.046 to 8.342μg/mL, with an average EC50 value of 4.956±0.281μg/mL. The antifungal activity was the direct activity of cuminic acid instead of the influence on the pH of media by cuminic acid. After treated with cuminic acid, mycelia dissolved with decreased branches and swelling; cell membrane permeability increased while pectinases activity decreased significantly. Moreover, peroxidase (POD) activity of the apple leaves increased after treated with cuminic acid. Importantly, on detached branches of apple tree, cuminic acid exhibited both protective and curative activity. These results indicated that cuminic acid not only showed the antifungal activity, but also could improve the defense capacity of the plants. Taken together, cuminic acid showed the potential as a natural alternative to commercial fungicides or a lead compound to develop new fungicides for the control of Valsa canker.

Monitoring Pesticide Residues in Fruits and Vegetables at Two of the Biggest Fresh Produce Markets in Africa

In most countries, fresh produce sold at local markets is usually not analyzed for agricultural chemical residues as export products are, which raises concerns about the perceived safety levels of local food supplies in contrast with exported products. The aim of this study was to determine pesticide residue levels in fruits and vegetables sold at two of the biggest fresh produce markets in Africa. A total of 199 fruit and vegetable samples were collected between 2012 and 2014 and analyzed for 74 pesticides commonly used in the horticultural sector. Of the samples analyzed, 91% were compliant with set maximum residue levels (MRLs). The remaining samples either contained unregistered chemicals (8%) or exceeded set MRL values (1%). Products containing more than one pesticide residue constituted 4.02% of all samples tested. Imazalil and iprodione were found to be the most frequently detected pesticides (12 samples each). Boscalid, endosulfan, profenofos, and procymidone were associated with the most noncompliance, including exceeding MRL values or being unregistered for the specific crop. The establishment of a national pesticide monitoring program is essential for the country and would ensure that pesticides are used in accordance with good agricultural practices.

Determination of Diphenylamine in Agricultural Products by HPLC-FL.

A method for the determination of diphenylamine in agricultural products was developed. Diphenylamine was extracted with acetonitrile from a sample under an acidic condition, passed through a C18 cartridge column, re-extracted with n-hexane, cleaned up on a PSA cartridge column, determined by HPLC with fluorescence detector and confirmed by liquid chromatography with tandem mass spectrometry. Average recoveries (n=5) from brown rice, corn, soybeans, potato, cabbage, eggplant, spinach, orange, apple and green tea were in the range from 76.7 to 94.9%, and the relative standard deviations were from 0.6 to 5.8% at concentrations equal to the maximum residue limits (MRLs). The quantification limits were 0.01 mg/kg, which is the uniform limit in the positive list system for agricultural chemical residues in food in Japan.

Monitoring and surveillance testing for residual veterinary drugs and pesticides in domestic meat between 2012 and 2013

The Korean National Residue Program (KNRP) use three plans for the sampling of domestic meats: monitoring, surveillance, and exploratory testing. We analyzed the results of monitoring and surveillance for residual veterinary drugs and pesticides in meat during 2012 and 2013. KNRP targets food-producing animals including cattle, pigs, chickens, ducks, sheep (goats), and horses. Sampling mainly focuses on veterinary drugs and pesticide residues found in tissues such as muscle, kidney, and liver. A total of 548 residue violations occurred between 2012 and 2013, mainly in pigs (427 violations) and cattle (113 violations). The most commonly found compounds were antimicrobials such as penicillins, fluoroquinolones, aminoglycosides, tetracyclines, sulfonamides, and macrolides. Pig residue violations were mainly for the presence of penicillins (34%) and fluoroquinolones (28%), while most residue violations in cattle were due to the presence of penicillins (32%) and aminoglycosides (27%). The overall rates of violations were 0.21% in 2012 and 0.10% in 2013. A major cause of violations was the failure to follow the appropriate withdrawal periods (68.8%). The results of the KNRP were analyzed to provide information on agricultural chemical residues that are of public health concern and to help control and prevent residue violations for ensuring food safety.

Chemical residues, food additives and natural toxicants in food – the cocktail effect

SummaryFood might contain residues of agricultural chemicals (e.g. pesticides), additives (e.g. colourants) and/or natural toxins (e.g. solanine in potatoes) which present health risks to consumers. The risks of such residues, additives and natural toxins are generally low (i.e. acceptable) when considered in isolation. However, an average meal is likely to contain a cocktail of residues, additives and/or natural toxins that might have additive or synergistic effects. This review explores potential cocktail effects with reference to two case examples, organophosphorus pesticides (OPs) and xenoestrogens, and concludes that we should extend our thinking to encompass interactions between residues, additives and natural toxins when assessing food risk.

A psychological study on the efficacy of graphic design for agricultural chemical residues

A psychological study on the efficacy of graphic design for agricultural chemical residues

Australian farmed Yellowtail Kingfish (Seriola lalandi) and Mulloway (Argyrosomus hololepidotus): Residues of metallic, agricultural and veterinary chemicals, dioxins and polychlorinated biphenyls

Composite samples of Australian farmed Yellowtail Kingfish (Seriola lalandi) (YTKF) (n=27), Mulloway (Argyrosomus hololepidotus) (n=6) and manufactured feed (n=5) were analysed to benchmark levels of a broad range of residues and contaminants of potential public health and trade significance. A subset of these samples [YTKF (n=5), Mulloway (n=2) and feed (n=5)] was analysed for dioxins and polychlorinated biphenyls (PCBs). The mean concentration of dioxins in YTKF was 0.6pg TEQg−1 (range 0.22–0.8) and in Mulloway was 0.16pg TEQg−1 (range 0.16–0.16). The mean concentration of dioxins and dioxin-like PCBs in YTKF was 2.6pg TEQg−1 (range 1.4–3.5), while Mulloway had a mean concentration of 0.67pg TEQg−1 (range 0.57–0.76). The mean concentration of PCBs in YTKF was 21μgkg−1 (range 8.6–29) and in Mulloway was 5.4μgkg−1 (mean 4.7–6). The mean concentration of dioxin-like PCBs in YTKF was 2.1pg TEQg−1 (range 1.2–2.8) and in Mulloway was 0.51pg TEQg−1 (range 0.41–0.61). The mean mercury concentration in YTKF was 0.03mgkg−1 (range 0.02–0.05) and in Mulloway it was 0.02mgkg−1 (range 0.02–0.04). There were no detectable levels of any pesticide or antimicrobial compounds in any sample of YTKF or Mulloway. Attention is drawn to technical differences in port of entry testing programs such as sampling strategies, portion tested, laboratory methodology, residue definitions and reporting conventions that exporters’ products may be subject to. All residues and contaminants were either undetectable or present at very low levels when judged against Australian, Japanese and European Union regulatory standards (where set).

Problems on LC-MS/MS Analysis to Ensure Food Safety

An accurate analysis is required to address various issues concerning the food safety. Many risk factors, such as agricultural chemical residues, residual veterinary drugs, mycotoxins, food additives, and carcinogens produced during food processing may be present in foodstuffs. High-performance liquid chromatograph-tandem mass spectrometry (LC-MS/MS) is an analytical system advanced in terms of sensitivity, selectivity, and flexibility. The system has been widely applied to food analysis. Food contains a wide variety of nutritional components, which may cause interference with food analyses. Then, sample preparation to remove such interference and an appropriate choice of an analytical technique is required. Even with LC-MS/MS, the analytical reliability may be reduced by matrix effects, due to interference from food components. In this review, we summarize issues on using LC-MS/MS to achieve good analyses for the food safety and discuss how to address it. The topic especially focuses on matrix effects.

Determination of Carbendazim, Thiophanate, Thiophanate-methyl and Benomyl Residues in Agricultural Products by Liquid Chromatography-Tandem Mass Spectrometry

A simple and reliable liquid chromatographic-tandem mass spectrometric (LC-MS/MS) method was developed for carbendazim (MBC), thiophanate (TE), thiophanate-methyl (TM) and benomyl (BM) in agricultural products. These compounds were extracted from agricultural products with methanol after addition of sodium L-ascorbate. BM was hydrolyzed to MBC during the extraction with methanol. TE and TM were cyclized to ethyl 2-benzimidazole carbamate (EBC) and MBC by refluxing at 120 °C for 30 min with copper acetate in 50% acetic acid. MBC and EBC were cleaned up by an n-hexane wash and extraction with ethyl acetate and determined by LC-MS/MS. The mean recoveries from 10 agricultural products were in the range of 75.8-100.0%, and the relative standard deviations of 5 experiments were in the range of 1.5-9.2% at concentrations equal to the maximum residue limits (MRLs). The calibration curves were made by using commercial MBC and EBC as reference analytical standards without refluxing. The quantification limits were 0.01 mg/kg (as MBC), which is the uniform limit in the positive list system for agricultural chemical residues in foods in Japan.

Dissipation and Evaluation of Hexaflumuron Residues in Chinese Cabbage Grown in Open Fields

The dissipation and residue behavior of hexaflumuron in Chinese cabbage ( Brassica pekinensis ) under different treatments were investigated at two main cabbage-growing areas in China. The dissipation rates of hexaflumuron in cabbages and soils fit a first-order decay process very well. The dissipation times for 50% of the hexaflumuron in cabbage and soil were 3.37 and 3.01 days from Hunan province and 5.58 and 3.68 days in Tianjin, respectively, when Chinese cabbage was treated with 180 g of active ingredient (ai)/ha. Hexaflumuron residual times in cabbage and soil were influenced strongly by the application rate and frequency. The application regimen of hexaflumuron in the cabbage field, a rate of 120 g of ai/ha with two applications at a 7 day interval and a 21 day preharvest interval, was recommended from the point of view of ensuring food safety. The residual levels of hexaflumuron in cabbages were lower than the standards of the "Positive List System for Agricultural Chemical Residues in Foods" based on the recommended application regimen.

Monitoring of pesticides and veterinary drugs in Australian cattle: verification of the residue control system

The Australian National Residue Survey in partnership with the Australian Quarantine and Inspection Service and industry routinely monitors beef to ensure that regulatory requirements for residues are being met. In the 10-year period from 1997 to 2006 a total of 128,902 samples were subjected to residue testing covering veterinary drugs and veterinary and agricultural pesticides in a random monitoring program. Residues of agricultural and veterinary chemicals exceeded the Australian standard in 13 and 7 samples, respectively. Greater than 99% of samples did not contain detectable residues above the Australian standard while greater than 90% of samples did not contain any residues of compounds included in the survey. The results of the surveys provide verification that the Australian residue control system is appropriate and that the requirements of countries importing Australian meat products can be satisfied. The surveys have also demonstrated that industry based programs and state based regulatory controls over sites contaminated with organochlorine residues are effective in managing residues of these chemicals in cattle.

Multi-Residue Analysis of 205 Crop Pesticides Using Mini-Solid Phase Extraction–Large Volume Injection–GC–MS

A simple, rapid, and sensitive multi-residue method has been developed for the determination of 205 pesticides commonly used for crop protection. Pesticide residues were extracted from samples with acetonitrile and a mini-solid phase extraction filter. No additional concentration or clean-up steps were necessary. Analyses were performed via large volume gas chromatography injection using a stomach-shaped inlet liner. The developed method was linear over the range assayed (5–50 μg L−1), with determination coefficients >0.99. The limits of quantification were in the range 0.0005–0.6 mg kg−1 and the limits of detection were between 0.00015 and 0.2 mg kg−1. The majorities of them were lower than the maximum residue set by the Japanese government in “Positive System for Agricultural Chemical Residues in Food” directive in apple. This method was applied to determine pesticide levels in vegetables, fruits, and beans.

Pesticide and PCB residues in the aquatic ecosystems of Laguna de Terminos, a protected area of the coast of Campeche, Mexico

The coastal lagoon system of Laguna de Terminos, Campeche, Mexico, a natural reserve since 1994, was investigated for contamination by agricultural and industrial chemical residues. Water, sediment and biota samples were analyzed for a wide variety of organochlorine and organophosphorus compounds. Chlorpyrifos was detected in water in concentrations up to 72 pg L −1 and, amongst organochlorine compounds, ∑PCB were measured averaging 1177 pg L −1 and ∑DDT 279 pg L −1. Residues of chlorinated compounds were present in sediments and in biota with ∑DDT averaging 190 pg g −1 and 5876 pg g −1 in sediment and oysters, respectively. Results show that the more widespread contaminants in the Laguna were residues of chlorinated hydrocarbons, such as DDTs, PCBs, endosulfan, and lindane. Concentrations of residues were not at an alarming level and were even lower than reported for other costal lagoons of the region. Still there is a need to implement control measures on persistent and bioaccumulative compounds that may reach the aquatic system of Laguna de Terminos.

The role of Food Safety Commission in the introduction of Positive List System for Agricultural Chemical Residues in Foods

The role of Food Safety Commission in the introduction of Positive List System for Agricultural Chemical Residues in Foods

Pesticide residues in Hungarian soils

The survey of pesticide active ingredients and residues in Hungarian soil and groundwater samples was carried out as part of a nationwide research program realised by the co-operation of Hungarian Academy of Sciences and Ministry of Environment. The program was justified by increasing human- and ecotoxicological concerns about pesticides and, at the same time, exact licensing and merchandising requirements, as well as strict (inter)national regulations of residue limits (e.g. joining the European Union). Based on earlier experiments related to analytical and ecotoxicological properties of pesticides; selected active ingredients acetochlor, atrazine, carbofuran, diazinon, fenoxycarb, metribuzin, phorate, prometryn, terbutryn, trifluralin were monitored using GC-MS in 24 soil and 56 groundwater samples. The samples were collected from specific reference points in Hungary during the winter sampling period. Regarding the soil medium, only atrazine was detected in two samples; at levels of 0.07 μg g − 1 (sample no. 3: I 1409) and 0.11 μg g − 1 (sample no. 12: I 0503). On the other hand, four of the target compounds (atrazine 166–3067 ng mL − 1 , acetochlor 307–2894 ng mL − 1 , diazinon 15–223 ng mL − 1 , prometryn 109–160 ng mL − 1 ) occurred in the samples from groundwater medium. Since atrazine is persistent in the environment and it was found even during the winter sampling period (therefore 8–9 months after pesticide application), there is a warning that environmental pollution caused by agricultural chemical residues requires enhanced monitoring action. Beside the investigated pesticide active ingredients, ten other pollutants – polycyclic aromatic hydrocarbons (PAH) –, as 5,6,7,7α-tetrahydro-4,4,7-2(4H) benzofuranon; 3,4,5,6,7,8-hexahydro-4,7-dimethyl-2H-1-benzopyran-2-on; methyl-(6R,S)-8-hydroxy-7-oxo-8,9 secolabdan-15-oat; 3,4,5,6,7,8-hexahydro-4,7-dimethyl-2H-1-benzopyran-2-on; 1-(2-hydroxy-5-methoxy-4-methyl-phenyl)-ethanon; 1-[1,1′ biphenyl]-3-yl-ethanon; 7(1H)-pteridinon; 7-methoxy 2,3 dihydro 1-benzfuran-3-acetic acid; 4-trifluor-methoxycarbonyl-benzaldehyde; 1,3 methano-octahydro-penthalene and orthorhombic sulphur were also identified by GC-MS spectrum library. Spatial distribution monitoring of soil and groundwater pollutants, as well as the database structure, allow several users without qualification in spatial informatics to gain site maps according to user-defined parameters; spatial search and on-line editing.

Positive List System for Agricultural Chemical Residues in Foods

Positive List System for Agricultural Chemical Residues in Foods

Agricultural Chemical Residues as a Source of Risk

Exposures to individual agricultural chemical residues are a relatively small source of risk across selected environmental and human health end points; nutrients in water, of which agricultural uses are only one source, may be an exception. This may explain recent policy decisions to tighten regulation of nutrients in water resources. However, uncertainty about nutrient damages hinders design of an efficient policy to deal with nutrients.