Simultaneous Analysis of 272 Pesticides in Agricultural Products by the QuEChERS Method and Gas Chromatography with Tandem Mass Spectrometry.

The aim of this study is to develop a rapid and accurate method for simultaneous analysis of multi-residue pesticides and conduct pesticide monitoring in agricultural products produced by the production and distribution stage in Korea. The representative agricultural products were selected as brown rice, soybean, potato, mandarin, and green pepper and developed using gas chromatography with tandem mass (GC-MS/MS) for the analysis of 272 pesticide residues. The experimental samples were extracted by the QuEChERS-EN method and then cleaned up by using d-SPE, including MgSO4 and primary secondary amine (PSA) sorbents. The established method was validated in accordance with Codex CAC-GL/40, and the limit of quantitation (LOQ) was determined to be 0.01 mg/kg. A total of 243 pesticides satisfied the guidelines in five samples at three levels with values of 60 to 120% (recovery) and ≤45% (coefficient of variation, CV). The remaining 29 pesticides did not satisfy the guidelines, and these pesticides are expected to be used as a screening method for the routine inspection of agricultural products. As a result of analyzing 223 agricultural products in South Korea by applying the simultaneous analysis method, none of the detected levels in the samples exceeded the standard values based on maximum residue limits (MRLs). The developed method in this study will be used to inspect residual pesticides in agricultural products, and it is anticipated to contribute to the distribution of safe agricultural products to consumers.

Uptake and Biotransformation of Guvermectin in Three Crops after In Vivo and In Vitro Exposure.

Guvermectin, as a novel nucleoside-like biopesticide, could increase the rice yield excellently, but the potential environmental behaviors remain unclear, which pose potential health risks. Therefore, the uptake and biotransformation of guvermectin in three types of crops (rice, lettuce, and carrot) were first evaluated with a hydroponic system. Guvermectin could be rapidly absorbed and reached equilibrium in roots (12-36 h) and shoots (24-60 h) in three plants, and guvermectin was also vulnerable to dissipation in roots (t1/2 1.02-3.65 h) and shoots (t1/2 9.30-17.91 h). In addition, 8 phase I and 2 phase II metabolites, transformed from guvermectin degradation in vivo and in vitro exposure, were identified, and one was confirmed as psicofuranine, which had antibacterial and antitumor properties; other metabolites were nucleoside-like chemicals. Molecular simulation and quantitative polymerase chain reaction further demonstrated that guvermectin was metabolized by the catabolism pathway of an endogenous nucleotide. Guvermectin had similar metabolites in three plants, but the biotransformation ability had a strong species dependence. In addition, all the metabolites exhibit neglectable toxicities (bioconcentration factor <2000 L/kg b.w., LC50,rat > 5000 mg/kg b.w.) by prediction. The study provided valuable evidence for the application of guvermectin and a better understanding of the biological behavior of nucleoside-like pesticides.

Assessment of heavy metals and human health risk associated with the consumption of crops cultivated in industrial areas of Maputo, Mozambique.

This study aimed to evaluate heavy metals concentrations in soils and vegetables (cabbage, lettuce, and cassava) cultivated at Matola and Beluluane Industrial Parks, and to assess health risks linked to their consumption through estimated daily intake, hazard index (HI), and incremental lifetime cancer risk. Concentrations of Al, As, Co, Cd, Cr, Ni, Pb, and Zn were determined in the two sites. Soil concentrations of As at Beluluane site and As, Cd, and Cr at Matola site exceeded reference limits of the Food and Agriculture Organization/World Health Organization, showing heavy metal contamination. At Beluluane site, all studied vegetables presented As and Pb levels higher than reference limits, Cd concentrations were higher than the reference limit in cabbage, lettuce, and cassava leaves. At Matola site crops concentrations of As, Cd, Cr, and Pb exceeded the reference limits. Zinc exceeded the reference limit in all crops except in cabbage. HIs for vegetables from Beluluane exceeded 1.0 in cabbage (2.66), lettuce (2.27), and cassava leaves (2.37). Likewise, at Matola, HIs exceeded 1.0 in lettuce (1.67), cassava leaves (1.65), and root tubers (13). We found that vegetables cultivated in industrial parks present high carcinogenic risk due to heavy metal contamination, rendering them unsuitable for human consumption.

Functions of Basic Helix-Loop-Helix (bHLH) Proteins in the Regulation of Plant Responses to Cold, Drought, Salt, and Iron Deficiency: A Comprehensive Review.

Abiotic stresses including cold, drought, salt, and iron deficiency severely impair plant development, crop productivity, and geographic distribution. Several bodies of research have shed light on the pleiotropic functions of BASIC HELIX-LOOP-HELIX (bHLH) proteins in plant responses to these abiotic stresses. In this review, we mention the regulatory roles of bHLH TFs in response to stresses such as cold, drought, salt resistance, and iron deficiency, as well as in enhancing grain yield in plants, especially crops. The bHLH proteins bind to E/G-box motifs in the target promoter and interact with various other factors to form a complex regulatory network. Through this network, they cooperatively activate or repress the transcription of downstream genes, thereby regulating various stress responses. Finally, we present some perspectives for future research focusing on the molecular mechanisms that integrate and coordinate these abiotic stresses. Understanding these molecular mechanisms is crucial for the development of stress-tolerant crops.

Characterization of starches isolated from Mexican pulse crops: Structural, physicochemical, and rheological properties.

This work aimed to characterize and compare the physicochemical properties of four pulse starches: bean, chickpea, lentil, and pea. Chemical proximate analysis, elemental composition, morphological grain characterization, crystalline structure, thermal analysis, FTIR analysis, and pasting properties were conducted. The proximate analysis shows that these starches have low fat, mineral, and protein content but high amylose values ranging from 29 to 36 % determined by colorimetry. Despite the high amylose content, the starches did not exhibit the typical behavior of an amylose-rich starch, with high peak viscosity and low breakdown and setback. It was found that this behavior was likely due to the large granule size of the ellipsoidal, spherical, and kidney-shaped granules and the high content of some minerals such as Na, Mg, K, Fe, Mn, P, and Si. The study also found that all pulse starches simultaneously contain monoclinic and hexagonal crystals, making them C-type starches. The findings were verified through the Rietveld analyses of X-ray diffraction patterns and differential scanning calorimetry, in which bimodal endothermic peaks evidenced both types of crystals being gelatinized.

Perennial Baki™ Bean Safety for Human Consumption: Evidence from an Analysis of Heavy Metals, Folate, Canavanine, Mycotoxins, Microorganisms and Pesticides.

Global food production relies on annual grain crops. The reliability and productivity of these crops are threatened by adaptations to climate change and unsustainable rates of soil loss associated with their cultivation. Perennial grain crops, which do not require planting every year, have been proposed as a transformative solution to these challenges. Perennial grain crops typically rely on wild species as direct domesticates or as sources of perenniality in hybridization with annual grains. Onobrychis spp. (sainfoins) are a genus of perennial legumes domesticated as ancient forages. Baki™ bean is the tradename for pulses derived from sainfoins, with ongoing domestication underway to extend demonstrated benefits to sustainable agriculture. This study contributes to a growing body of evidence characterizing the nutritional quality of Baki™ bean. Through two studies, we investigated the safety of Baki™ bean for human consumption. We quantified heavy metals, folate, and canavanine for samples from commercial seed producers, and we quantified levels of mycotoxins, microorganisms, and pesticides in samples from a single year and seed producer, representing different varieties and production locations. The investigated analytes were not detectable or occurred at levels that do not pose a significant safety risk. Overall, this study supports the safety of Baki™ bean for human consumption as a novel pulse crop.

Mercury pollution risks of agricultural soils and crops in mercury mining areas in Guizhou Province, China: effects of large mercury slag piles.

The historical large mercury slag piles still contain high concentrations of mercury and their impact on the surrounding environment has rarely been reported. In this study, three different agricultural areas [the area with untreated piles (PUT), the area with treated piles (PT), and the background area with no piles (NP)] were selected to investigate mercury slag piles pollution in the Tongren mercury mining area. The mercury concentrations of agricultural soils ranged from 0.42 to 155.00 mg/kg, determined by atomic fluorescence spectrometry of 146 soil samples; and mercury concentrations in local crops (rice, maize, pepper, eggplant, tomato and bean) all exceeded the Chinese food safety limits. Soil and crop pollution trends in the three areas were consistent as PUT > PT > NP, indicating that mercury slag piles have exacerbated pollution. Mercury in the slag piles was adsorbed by multiple pathways of transport into soils with high organic matter, which made the ecological risk of agricultural soils appear extremely high. The total hazard quotients for residents from ingesting mercury in these crops were unacceptable in all areas, and children were more likely to be harmed than adults. Compared to the PT area, treatment of slag piles in the PUT area may decrease mercury concentrations in paddy fields and dry fields by 46.02% and 70.36%; further decreasing health risks for adults and children by 47.06% and 79.90%. This study provided a scientific basis for the necessity of treating large slag piles in mercury mining areas.

Comprehensive multiresidue chromatographic methods for monitoring pesticides in agricultural areas and corresponding plant protection zones.

This article reports a comprehensive analytical method for the identification and quantification of a broad range of pesticides in green plant crops. The sample preparation method for pesticides involved an optimization of the QuEChERS-based extraction protocol, with sample mass, volume of added water, and the type of cleanup sorbent as variables. A sorbent combination based on ENVI-Carb and ChloroFiltr was examined. A highly efficient method was developed for the purification of plant extracts with 900 mg MgSO4, 150 mg PSA, and 15 mg ENVI-Carb at the d-SPE stage, combined with gas chromatography and liquid tandem mass spectrometry for the determination of 197 pesticides in crop plants containing chlorophyll. The method was validated in accordance with the requirements of international guidelines SANTE/11312/2021. The method was applied to quantify pesticide residues in 29 pairs of green crop plants and plants from the corresponding crop protection zone to verify whether the zones are effective barriers to prevent pesticides from penetrating outside agricultural areas. The number and types of agrochemical preparations were chosen by farmers. In total, more than 60 one- and several-component pesticide formulations were applied to the crops included in the study. The pesticide residues were detected in 21 crop samples and 3 samples from protection zones. Epoxiconazole, an active substance that was banned for use in 2021, was found in a spring barley sample. Based on the conducted research, the effectiveness of the protection zones has been clearly demonstrated, and it has been proven that environmental migration of pesticides and unauthorized agricultural practices pose a risk to ecosystems.

Ingestion exposure of public to natural radionuclides and committed effective dose and cancer risk through tuber crops cultivated in Ebonyi State, Nigeria.

Internal exposure of public to radiation arising from ingestion of natural radionuclides in tuber crops of Ebonyi State origin was investigated in this study. Committed effective doses and lifetime cancer risk of 40K, 226Ra, and 232Th in cassava, cocoyam, water yam, and white yam were calculated. The average activity concentrations of 40K, 226Ra, and 232Th determined by gamma spectrometric Na (TI) detector were, respectively, 199.15 ± 23.51, 77.57 ± 7.98, and 118.20 ± 10.72 Bq/kg in cassava; 146.62 ± 40.69, 43.42 ± 7.63, and 75.61 ± 2.89 Bq/kg in cocoyam; 162.81 ± 20.43, 63.17 ± 11.36, and 81.50 ± 10.27 Bq/kg in water yam; and 184.50 ± 20.22, 80.23 ± 10.93, and 116.29 ± 5.93 Bq/kg in white yam. The total committed effective dose via ingestion aligned in this order of cassava (7.05 mSv/year) > white yam (4.38 mSv/year) > water yam (0.42 mSv/year) > cocoyam (0.21 mSv/year) with overall average dose of 3.12 mSv/year. The values of dose were higher than world average of 0.29 mSv/year given by United Nations Scientific Committee on the Effects of Atomic Radiation (UNSCEAR). The lifetime cancer risk values were above tolerance level of >10-4 prescribed by United States Environmental Protection Agency (USEPA), suggesting probable evolvement of radiogenic cancer morbidity. The data presented in this study contributes to baseline information on radiological characteristics of tuber crops in Ebonyi, which would be valuable to WHO/FAO food safety policy in Nigeria and rest of the world.

Cassava (Manihot esculenta Crantz): A Systematic Review for the Pharmacological Activities, Traditional Uses, Nutritional Values, and Phytochemistry.

Cassava (Manihot esculenta Crantz) is considered one of the essential tuber crops, serving as a dietary staple food for various populations. This systematic review provides a comprehensive summary of the nutritional and therapeutic properties of cassava, which is an important dietary staple and traditional medicine. The review aims to evaluate and summarize the phytochemical components of cassava and their association with pharmacological activities, traditional uses, and nutritional importance in global food crises. To collect all relevant information, electronic databases; Cochrane Library, PubMed, Scopus, Web of Science, Google Scholar, and Preprint Platforms were searched for studies on cassava from inception until October 2022. A total of 1582 studies were screened, while only 34 were included in this review. The results of the review indicate that cassava has diverse pharmacological activities, including anti-bacterial, anti-cancer, anti-diabetic, anti-diarrheal, anti-inflammatory, hypocholesterolemic effects, and wound healing properties. However, more studies that aim to isolate the phytochemicals in cassava extracts and evaluate their pharmacological property are necessary to further validate their medical and nutritional values.

Dataset of metals and metalloids in food crops and soils sampled across the mining region of Moquegua in Peru.

In recent years, there has been an increase in interest in the accumulation of heavy metals and metal(loid)s (HMM) in areas where agriculture and mining exist side by side. As a contribution to this body of knowledge, we report the first dataset into HMM concentrations in food crops and agricultural soils in Moquegua, which is a typical mining region and contains one of Peru's largest copper deposits. Thanks to its geographic diversity, samples were taken in different agroecological regions at altitudes between 9 and 3,934 m. For food crops, 31 elements were measured using inductively coupled plasma mass spectrometry and atomic absorption spectrometry. For soils, 23 elements were measured using inductively coupled plasma optical emission spectrometry. Thus, the dataset includes a total of 13,828 observations from 341 sampling sites. We hope that this dataset will facilitate a wide range of agricultural and food safety studies, as well as serving as a reference for monitoring changes in pollution over time or comparing HMM levels with other farmlands influenced by mining activities.

A review on the identification of transgenic oilseeds and oils.

Transgenic technology can increase the quantity and quality of vegetable oils worldwide. However, people are skeptical about the safety of transgenic oil-bearing crops and the oils they produce. In order to protect consumers' rights and avoid transgenic oils being adulterated or labeled as nontransgenic oils, the transgenic detection technology of oilseeds and oils needs careful consideration. This paper first summarized the current research status of transgenic technologies implemented at oil-bearing crops. Then, an inspection process was proposed to detect a large number of samples to be the subject rapidly, and various inspection strategies for transgenic oilseeds and oils were summarized according to the process sequence. The detection indicators included oil content, fatty acid, triglyceride, tocopherol, and nucleic acid. The detection technologies involved chromatography, spectroscopy, nuclear magnetic resonance, and polymerase chain reaction. It is hoped that this article can provide crucial technical reference and support for staff engaging in the supervision of transgenic food and for researchers developing fast and efficient monitoring methods in the future.

Development of Analytical Methods to Analyze Pesticide Residues.

Pesticides are compounds applied on crops to eliminate or control pests, diseases and weeds and it is known that their use provides unquestionable benefits in increasing agricultural production [...].

Pesticide mixtures detected in crop and non-target wild plant pollen and nectar.

Cultivation of mass flowering entomophilous crops benefits from the presence of managed and wild pollinators, who visit flowers to forage on pollen and nectar. However, management of these crops typically includes application of pesticides, the presence of which may pose a hazard for pollinators foraging in an agricultural environment. To determine the levels of potential exposure to pesticides, their presence and concentration in pollen and nectar need assessing, both within and beyond the target crop plants. We selected ten pesticide compounds and one metabolite and analysed their occurrence in a crop (Brassica napus) and a wild plant (Rubus fruticosus agg.), which was flowering in field edges. Nectar and pollen from both plants were collected from five spring and five winter sown B. napus fields in Ireland, and were tested for pesticide residues, using QuEChERS and Liquid Chromatography tandem mass spectrometry (LC-MS/MS). Pesticide residues were detected in plant pollen and nectar of both plants. Most detections were from fields with no recorded application of the respective compounds in that year, but higher concentrations were observed in recently treated fields. Overall, more residues were detected in B. napus pollen and nectar than in the wild plant, and B. napus pollen had the highest mean concentration of residues. All matrices were contaminated with at least three compounds, and the most frequently detected compounds were fungicides. The most common compound mixture was comprised of the fungicides azoxystrobin, boscalid, and the neonicotinoid insecticide clothianidin, which was not recently applied on the fields. Our results indicate that persistent compounds like the neonicotinoids, should be continuously monitored for their presence and fate in the field environment. The toxicological evaluation of the compound mixtures identified in the present study should be performed, to determine their impacts on foraging insects that may be exposed to them.

[Threshold of Se-rich Soil Based on Available-Se and Influencing Factors of Available-Se].

Available selenium (Se) in soil was the predominant factor affecting the content of Se in crops. In order to reasonably delineate the Se-rich soil range and propose theoretical guidance for the cultivation of natural Se-rich crops in a region where the surface soils had a high level of available-Se and a low level of total-Se, 8814 samples in surface soil and 195 root-crop matching samples were collected in Shizuishan in northern Ningxia. On the basis of the main line of analysis of available-Se, the following research was conducted: by synthetically studying the total-Se and available-Se in surface soil and root soil, the morphology of Se in surface soil, as well as Se in crops, deep and coordinated analyses of content among total-Se, available-Se, and Se in root-crop matching samples were carried out, and the suitable threshold for Shizuishan was confirmed. A multiple regression model of available-Se was established to determine the main physical and chemical indexes affecting available-Se, which were expected to improve the Se enrichment rate of crops through the enhancement of available-Se. The results demonstrated that ω(Se) and ω(Seavailable)in the surface soil in Shizuishan were 0.26 mg·kg-1 and 12.85 µg·kg-1, respectively, and the characteristics of Se and available-Se in root-crop matching samples could represent those in surface soil. Thus, it was recommended to use 0.24 mg·kg-1 as the suitable threshold of Se-rich soil. The multiple regression model of available-Se showed that the increase in total-Se and soil elements affecting soil fertility could promote the enrichment of available-Se.

[Accumulation Characteristics and Health Risk Assessment of Heavy Metals in Soil-Crop System Based on Soil Parent Material Zoning].

This study used both the element occurrence form analysis and the chronic health risk assessment method to investigate the accumulation characteristics of heavy metals in the soil-crop system and the health risk assessment of agricultural products in northeastern Yunnan, which is a typical area of Southwest China where heavy metals are enriched in soil. Based on the study of 1137 groups of agricultural products and corresponding root soils, the results showed that the soil cadmium (Cd) and lead (Pb) in the lead-zinc ore concentration area were higher than the risk-intervention values of the "Soil Environmental Quality Risk control standard for soil contamination of agricultural land" (GB 15618-2018), whereas the soil Cd in the other parent material areas was within the screening-intervention buffer zone, and Pb was below the minimum risk-screening value. According to the National Food Safety Standard of China (GB 2762-2017), the heavy metal Cd in potatoes and soybeans in the area seriously exceeded the standard, the heavy metal Pb in tartary buckwheat and walnut exceeded the limit value, and the exceeding rate of heavy metal Cd in crops from these parent material areas showed: clastic rock>basalt>lead-zinc ore>carbonate ≈ Quaternary sedimentary>sand (mud) rock. According to the U.S. Environmental Protection Agency's assessment method for the chronic health risk of heavy metal intake by humans, the grains and potatoes, staple foods, and fruits had low chronic health risks of heavy metal intake. Agricultural products from the parent material area of clastic rock, sand (mud) rock, Quaternary sedimentary, and lead-zinc ore concentration showed health risks; with the change in soil physical and chemical properties and the increase in the types of edible crops, the risk will gradually increase. Based on this research, it is urgent to carry out real-time monitoring of agricultural products in the area.

Metabotyping of Andean pseudocereals and characterization of emerging mycotoxins.

Pseudocereals are best known for three crops derived from the Andes: quinoa (Chenopodium quinoa), canihua (C. pallidicaule), and kiwicha (Amaranthus caudatus). Their grains are recognized for their nutritional benefits; however, there is a higher level of polyphenism. Meanwhile, the chemical food safety of pseudocereals remains poorly documented. Here, we applied untargeted and targeted metabolomics approaches by LC-MS to achieve both: i) a comprehensive chemical mapping of pseudocereal samples collected in the Andes; and ii) a quantification of their contents in emerging mycotoxins. An inventory of the fungal community was also realized to better know the fungi present in these grains. Metabotyping permitted to add new insights into the chemotaxonomy of pseudocereals, confirming the previously established phylotranscriptomic clades. Sixteen samples from Peru (out of 27) and one from France (out of one) were contaminated with Beauvericin, an emerging mycotoxin. Several mycotoxigenic fungi were detected, including Aspergillus sp., Penicillium sp., and Alternaria sp.

Determination of a novel pesticide cyetpyrafen and its two main metabolites in crops, soils and water.

Novel insecticide cyetpyrafen is frequently used in various crops, however, knowledge of its fate in crops and environments is largely unexplored. In this study, an effective method was firstly established for simultaneous determination of cyetpyrafen and its metabolites (M-309 and M-391) in 13 matrices (e.g., plants and soils) to explore their fate. Mean recoveries of the three compounds ranged from 73.1 % to 118.7 % with the relative standard deviations (RSDs) less than 17.9 %. Further, after 28 days of exposure in a field soil-strawberry system, cyetpyrafen and M-309 exhibited great accumulations in strawberry leaves by foliar spray while both compounds were predominately accumulated in roots by root irrigation, where cyetpyrafen was poorly translocated within plant. An equal amount of M-309 was measured in both strawberry plants and soils indicates the extensive transformation of cyetpyrafen in soil-strawberry system. Therefore, metabolism of cyetpyrafen in foods need to be considered for its better risk assessment.

Dissipation Kinetics and Safety Evaluation of Flonicamid in Four Various Types of Crops.

The chemical insecticide flonicamid is widely used to control aphids on crops. Differences among crops make the universality of detection methods a particularly important consideration. The aim of this study was to establish a universal, sensitive, accurate and efficient method for the determination of flonicamid residues in peach, cucumber, cabbage and cotton. QuEChERS pretreatment was combined with ultrahigh-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS). A satisfactory recovery rate of 84.3-99.3% was achieved at three spiking levels, and the relative standard deviation (RSD) was 0.41-5.95%. The limit of quantification (LOQ) of flonicamid in the four matrices was 0.01 mg/kg. The residue and dissipation kinetics of flonicamid in four types of crops in various locations were determined by using the optimized method. The results showed that flonicamid had a high dissipation rate in the four different types of crops and a half-life in the different matrices and locations of 2.28-9.74 days. The terminal residue of flonicamid was lower than the maximum residue limit (MRL). The risk quotient (RQ) of flonicamid was 4.4%, which is significantly lower than 100%. This result shows that the dietary risk presented by using flonicamid at the maximum recommended dose is low and acceptable. The comprehensive long-term dietary risk assessment of flonicamid performed in this study provides a reference for the protection of consumer health and safe insecticide use.

Presence of pesticides in the environment, transition into organic food, and implications for quality assurance along the European organic food chain - A review.

The use of synthetic pesticides is not allowed in organic production, but traces of synthetic pesticides are regularly detected in organic food. To safeguard the integrity of organic production, organic certifiers are obliged to investigate the causes for pesticide residues on organic food, entailing high costs to the organic sector. Such residues can have various origins, including both fraud and unintentional contamination from the environment. Because the knowledge about contamination from environmental sources is scattered, this review provides an overview of pathways for unintentional and technically unavoidable contamination of organic food with synthetic pesticides in Europe. It shows that synthetic pesticides are widely present in all environmental compartments. They originate from applications in the region, in distant areas or from historical use. Transition into the food chain has been demonstrated by various studies. However, large uncertainties remain regarding the true pesticide contamination of the environment, their dynamics and the contamination risks for the food chain. Organic operators can take certain measures to reduce the risks of pesticide contamination of their products, but a certain extent of pesticide contamination is technically unavoidable. The present paper indicates that (i) a potential risk for pesticide residues exists on all organic crops and thus organic operators cannot meet a 'zero-tolerance' approach regarding pesticide residues at the moment. (ii) Applying a residue concentration threshold to distinguish between cases of fraud and unavoidable contamination for all pesticides is not adequate given the variability of contamination. More reliable answers can be obtained with a case-by-case investigation, where evidence for all possible origins of pesticide residues is collected and the likelihood of unavoidable contamination and fraud are estimated. Ultimately, for organic certification bodies and control authorities it will remain a challenge to determine whether a pesticide residue is due to neglect of production rules or technically unavoidable.