Comprehensive analysis of neonicotinoids in Chinese commercial honey and pollen: A corresponding health risk assessment for non-targeted organisms.

Neonicotinoids are broad-spectrum and highly effective insecticides that work by affecting neural activity in insects. Neonicotinoids are systemic pesticides that are absorbed by plants, transported, and accumulated in plant tissues, including nectar and pollen. Currently, there is a lack of a comprehensive assessment of the level of neonicotinoid contamination and the associated health risks to non-targeted organisms in commercial honey and pollen produced in China. This study collected 160 batches of honey and 26 batches of pollen from different regions and plant sources in China, analyzed the residue patterns of neonicotinoid pesticides, and comprehensively evaluated the exposure risks to non-targeted organisms including bees (adults and larvae) and humans. Furthermore, this study addresses this imperative by establishing a high-throughput, rapid, and ultra-sensitive indirect competitive enzyme-linked immunosorbent assay (ic-ELISA) based on broad-spectrum monoclonal antibodies to detect and quantify neonicotinoids, with validation conducted using the LC-MS/MS method. The findings indicated that 59.4 % of honey samples contained at least one of eight neonicotinoids, and the ic-ELISA rapid detection and calculation method could detect all the samples containing neonicotinoids. Additionally, the dietary risk assessment for humans and honeybees indicates that the consumption of a specific quantity of honey may not pose a health risk to human due to neonicotinoid intake. However, the Risk Quotient values for imidacloprid to adult bees and bee larvae, as well as clothianidin to bee larvae, were determined to be 2.22, 5.03, and 1.01, respectively-each exceeding 1. This highlights the elevated risk of acute toxicity posed by imidacloprid and clothianidin residues to honey bees. The study bears significant implications for the safety evaluation of non-targeted organisms in the natural food chain. Moreover, it provides scientific guidance for protecting the diversity and health of the ecosystem.

Determination of mycobiota and aflatoxin contamination in commercial bee pollen from eight provinces and one autonomous region of China.

The co-occurrence of fungi and mycotoxins in various foods has been frequently reported in many countries, posing a serious threat to the health and safety of consumers. In this study, the mycobiota in five types of commercial bee pollen samples from China were first revealed by DNA metabarcoding. Meanwhile, the content of total aflatoxins in each sample was investigated by high-performance liquid chromatography with fluorescence detection. The results demonstrated that Cladosporium (0.16 %-89.29 %) was the most prevalent genus in bee pollen, followed by Metschnikowia (0-81.12 %), unclassified genus in the phylum Ascomycota (0-81.13 %), Kodamaea (0-73.57 %), and Penicillium (0-36.13 %). Meanwhile, none of the assayed aflatoxins were determined in the 18 batches of bee pollen samples. In addition, the fungal diversity, community composition, and trophic mode varied significantly among five groups. This study provides comprehensive information for better understanding the fungal communities and aflatoxin residues in bee pollen from different floral origins in China.

[Health risk assessment of exogenous harmful pollutants in Chinese medicine: a review].

In recent years, the quality and safety problems have been limiting the internationalization of Chinese medicine. The pollutants in Chinese medicine, particularly the exogenous harmful pollutants mainly including mycotoxins, pesticide residues, heavy metals, harmful elements, and sulfur dioxide, are of high risks for people. Therefore, the World Health Organization(WHO) and relevant national organizations have clearly defined the maximum residue limits(MRLs) of such pollutants. Chinese Pharmacopoeia(2020 edition, volume Ⅳ) also demonstrates the detection methods, MRLs and preliminary risk assessment methods for four typical exogenous harmful pollutants in Chinese medicine. Therefore, continuous optimization of the health risk assessment system can further help further raise the quality and safety of Chinese medicine. This paper reviews the research on the health risk assessment of four typical exogenous harmful pollutants in Chinese medicine and discusses the problems of and challenges for the assessment system, which is expected to lay a scientific basis for the establishment of the risk warning mode and response measures suitable for specific types of Chinese medicine.

[Domestic and international research progress of edible and medicinal Arecae Semen].

Arecae Semen, as the first place among "Four South Medicines" in China, has great dual-use value of medicine and food. The research of Arecae Semen was mainly focused on the active ingredients and efficacy value, and its potential safety hazards were also concerned. Until now, there is still a lack of clear boundaries between medicine and food, resulting in its safety cannot be guaranteed. Therefore, it is of great significance to establish clear boundaries of medicine and food use and health risk assessment. In this paper, the differences of pretreatment and application methods of Arecae Semen were analyzed, and the research progress of Arecae Semen in chemical composition identification and toxicology research and safety evaluation were reviewed emphatically. Finally, the differences of quality control and safety evaluation of Arecae Semen in pharmacopoeias or standards were analyzed at home and abroad. It was expected to provide reference value for quality control, safety evaluation and international standardization research of Arecae Semen.

[Safety evaluation of heavy metals contaminated Astragalus membranaceus using health risk assessment model].

To evaluate the safety of heavy metals contaminated Astragalus membranaceus,an appropriate protocol was established to study the heavy metals pollution level by health risk assessment. This study provided a detailed procedure to assess the medicinal herbs in quality control and safety evaluation,and expected to create awareness among the public on the safety of consuming of A. membranaceus or any other kinds of medicinal herbs. The heavy metals content of Cu,As,Cd,Pb and Hg in a total of 45 batches of A. membranaceus were carefully analyzed with a developed inductively coupled plasma mass spectrometry( ICP-MS). Besides,the heavy metal contamination level was further evaluated through 4 main assessment parameters,including maximum residue limit( MRL) set by International Standard Organization,estimated daily intake( EDI) set by IUPAC,target hazard quotients( THQ) and Total THQ set by USEPA and total THQs in raw herbs of A. membranaceus. In addition,the recommended MRLs of 5 main heavy metals aimed to A. membranaceus were calculated based on the regulated consumption quantity. The result showed that,under the ISO international standard of Chinese medicine-Chinese herbal medicine heavy metals,the unqualified rate was 8. 89% for A. membranaceus,which including 4 batches of A. membranaceus exceeded the MRL of As. Here,the standard THQ value of A. membranaceus was firstly proposed as 0. 02 and 0. 011 25 for adults and children,respectively,which were calculated with the recommended consumption quantity of 30 g and 9 g for adults and children. Furthermore,the values of THQ for As and total THQs in adults and children were exceeded the standard THQ in A. membranaceus,and the recommended MRLs of Pb,Cd,Hg and Cu in above medicinal materials that calculated based on health risk assessment model were higher than the regulated MRLs that set by ISO and Chinese Pharmacopeia. The research showed that the contents of heavy metals in A. membranaceus were not in the safe range and the certain non-carcinogenic risks to human body cannot be neglected. Based on above investigation result,it is easily known that the common evaluation method for raw herbs based on the comparison of MRL of heavy metals was not precise enough,and the international model of health risk assessment should be built for each medicinal herb. Above all,this study provided a more realistic research approach for safety evaluation of any other kinds of heavy metals contaminated medicinal herbs,including the establishment of heavy metals standard limit in a specified medicinal herb under recommended consumption quantity,and it is expected to create awareness among the public on the safety of consuming any other medicinal herbs.

Nanoadsorbents Based on NIPAM and Citric Acid: Removal Efficacy of Heavy Metal Ions in Different Media.

Heavy metal ions in aqueous solutions are harmful to human health, but exploring and exploiting nanoadsorbents with a high adsorption capacity and low cost should be an effective method for overcoming this problem. In this study, a novel nanoadsorbent termed poly(N-isopropylacrylamide-co-citric acid) (PNCA) was designed and synthesized via free-radical polymerization. PNCA exhibits good solubility in aqueous solutions and can self-assemble into spherical nanoaggregates with a mean hydrodynamic diameter of approximately 723.1 nm. After freeze-drying, the solid powder of PNCA exhibited a loose porous structure. When PNCA is dissolved in water, the resulting copolymer solution exhibits high removal rates for Cu2+ and Pb2+ of over 80%; meanwhile, over 97% of the PNCA is precipitated with metal ions. The adsorption process of PNCA chelated with Cu2+ ions fit the Freundlich model. The adsorption capacity is independent of the media pH, but could be affected by the temperature. Except for herbal medicines with alkaloids as active ingredients, PNCA also presents good adsorption capacity for Cu2+ in herbal medicine decoctions, with a removal rate of over 80%. The cell cytotoxicity in vitro and system toxicity in vivo demonstrate the desirable biosafety of PNCA. These results suggest that PNCA with good biosafety can be utilized as a nanoadsorbent to remove the metal ions, especially Cu2+, in different media.

[Current situation of heavy metal pollution,detection and removal techniques in medicinal marine organisms in China].

As an important branch of traditional medicines,medicinal marine organisms have many advantages,including biological diversity,remarkable biological activity,especial for the treatment of anti-cancer,anti-virus,anti-coagulation,analgesia,anti-bacterial,cardiovascular and cerebrovascular diseases. In recent years,with the continuous exploration of marine organisms by human beings,many marine organisms with specific biological activities and medicinal prospects have been found,which have attracted great attention around the world and thus called " new hope" to solve human health problems. However,due to the rapid development of modern industry,heavy metal pollution not only poses a great threat to medicinal marine living resources,but also hinders the development of marine biomedical industry and threatens human health. In view of this,this paper introduced the development trend of medicinal marine organisms and the current situation of heavy metal pollution and focusing on the analysis technology and chemical removal technology of heavy metals in medicinal marine organisms,which is to provide reference for the heavy metals control in marine medicines and the development and utilization of marine medicines.

[Establishment of health risk assessment model for assessing medicinal and edible plants contaminated by heavy metals--take Astragali Radix,Codonopsis Radix and Laminariae Thallus as examples].

With the improvement of living standard,the theory of " medicine and food homology" has developed rapidly in the field of diet,medicine and health preservation. In recent years,many literatures have been reported on the active ingredients and pharmacological effects of medicinal and edible plants,but relatively few reports have been reported on their safety investigation. Therefore,to further evaluate the quality and safety of medicinal and edible plants,Astragali Radix,Codonopsis Radix and Laminariae Thallus were selected as our research objects in this study. Moreover,the pollution level and the potential health risk of heavy metals were deeply assessed in different types of medicinal and edible plants. Especially,the contents of chromium,copper,arsenic,cadmium,mercury and lead in these three herbs were determined by inductively coupled plasma mass spectrometry( ICP-MS),and their health risk level was evaluated by target hazard coefficient method. The results showed that under the international heavy metal limit standard( ISO 18664-2015,GB 2762-2017),the over-standard rates were 25%,77% and 100% in 16 batches of Astragali Radix,26 batches of Codonopsis Radix and 9 batches of Laminariae Thallus,respectively. Besides,the values of target hazard quotients( THQ) for adults and children are 0. 028 244,0. 063 505 and 0. 014 485,0. 032 568 in Astragalus membranaceus and Codonopsis pilosula,respectively,which were higher than the standard values of 0. 02 and 0. 011 25. While,the total heavy metals THQ values for adults and children are 0. 023 734 and 0. 020 287 in Laminariae Thallus,which were much higher than the standard values of 0. 008 0 and 0. 007 5. However,the CR values of As,Cd and Pb in the three herbs were lower than 1×10~(-6). Above results indicated that those six harmful elements have certain health hazards to the exposed population,but there is no potential carcinogenic effect. It can be seen that,there were still presence of the pollution of harmful elements,and it is necessary to establish the reasonable limit standards and quality control methods of medicinal and edible plants in time.

[Pollution level and health risk assessment of heavy metals and hazardous elements in Bombyx Batryticatus].

In order to comprehensively analyze the pollution level and bioaccessibility of different types of heavy metals and hazardous elements in animal medicine,this paper selected Bombyx Batryticatus as the research object,and used inductively coupled plasma mass spectrometry( ICP-MS) to detect As,Cu,Hg,Pb,Ni,Cr,Zn and Cd. Based on the artificial gastrointestinal digestion model and the health risk assessment model of Chinese medicinal materials,the pollution level,in vivo and in vitro transfer rate and health risk grade of eight harmful elements in the above-mentioned medicinal materials of Bombyx Batryticatus were obtained respectively. The test result was found that under the ISO international standard of Chinese medicine-Chinese herbal medicine heavy metals,the unqualified rate was 50% for Bombyx Batryticatus,which including 2 batches of As and 4 batches of Cr exceeded the MRL. In artificial gastrointestinal digestion solution,the transfer rates of heavy metals As,Cu,Hg,Pb,Ni,Cr,Zn and Cd were 36. 849%,72. 372%,41. 152%,75. 354%,46. 603%,27. 981%,19. 707% and 76. 282%,respectively. The data of risk assessment model showed that the total THQ values of the most polluted batches for adults and children was 0. 021 548 and 0. 018 418,respectively. After digestion,the THQ values decreased to 0. 012 599 for adults and 0. 010 769 for children,which were still higher than the THQ standard values of animal medicine Bombyx Batryticatus. However,the CR value of carcinogenic risk is less than 1×10-6,so the potential non-carcinogenic risk caused by taking this batch of Bombyx Batryticatus medicines is higher and the carcinogenic risk can be ignored. To sum up,heavy metals and hazardous elements in Bombyx Batryticatus still exceed the standard,but the health risk level caused by heavy metals still needs to be investigated according to different medicinal materials,in order to provide data support for further improving the quality and safety of animal medicine.

[Safety evaluation of heavy metals contaminated Xiaochaihu Tang using health risk assessment model].

In order to further improve the quality and safety evaluation standards of traditional Chinese medicine compound preparation,Xiaochaihu Tang compound preparations were selected to analyze the pollution level of heavy metals deeply,and the potential health risks were evaluated under taking such kind of compound preparations. In this study,the contents of copper( Cu),arsenic( As),cadmium( Cd),mercury( Hg),and lead( Pb) in different Xiaochaihu Tang compound preparations were determinated by the method of inductively coupled plasma mass spectrometry( ICP-MS). Moreover,combined with target hazard coefficient method and in vitro artificial system,the bioaccessibility and health risk level was investigated in three main consumption ways including powder,decoction and granule. The result was showed that,under the maximum residual limit set by International Standard Organization,only one batch of raw herb was eight times exceeded the Hg MRL,however,in water decoctions and granules,the heavy metal residue rate was reduced to 2. 02%( Hg in granules)-42. 85%( Cd in granules). So,the heavy metal pollutions and health risks can be reduced to safe region in spite of the serious pollution in raw herbs. Besides,the THQ and CR values of the three consumption methods were lower than the standard values of non-carcinogenic and carcinogenic risks of each heavy metal. It can be seen that even if the heavy metals in the raw herbs exceed the standard,the use of Xiaochaihu Tang decoction and granules can reduce the harm of heavy metals to the human body. Above all,the establishment of this health risk assessment model can be provided experimental basis and reference value for improving the safety evaluation standard of other heavy metals contained traditional Chinese medicine( TCM) compound preparations,and further improving the quality control methods of other different toxic compounds in clinical use.

[Analysis of arsenic speciation in Sepiae Endoconcha and research on its limit standard].

Sepiae Endoconcha is a common marine animal medicine,which generally contains high concentration of arsenic( As).The Chinese Pharmacopoeia( 2010 edition,part I) stipulated that the total As content of Sepiae Endoconcha should not exceed 2 mg·kg~(-1),while this limit was revised to 10 mg·kg~(-1) in the 2015 edition. So far,there is no research on the speciation of As in Sepiae Endoconcha,which made it hard to accurately evaluate its security risk. In this study,32 batches of Sepiae Endoconcha from different sources were collected. The safety risk assessment was carried out by determining the total As content and As speciation,inorganic As[As( Ⅲ),As( Ⅴ) ]and organic As( MMA,DMA,As C,As B) by HPLC-ICP-MS,and then the limit standard was discussed. The results showed that As B was the main form of As in Sepiae Endoconcha,followed by DMA and As( Ⅴ) ． Of the 32 batches of Sepiae Endoconcha,9 batches( accounting for 28%) were detected possessing i As. The maximum concentration of As( Ⅲ) was 103. 3 µg·kg~(-1),and the maximum concentration of As( Ⅴ) was 222. 4 µg·kg~(-1). According to the limit of i As in food,18. 75% of the samples exceeded the standard. The results indicate that there is no simple positive correlation between total As and As morphology in Sepiae Endoconcha. Besides,there is a risk in the total As limit,especially after the relaxation of the total As limit. The problem of high i As content caused by pollution and other factors is difficult to regulate. Since the toxicity of inorganic As is much higher than that of organic As,it is of great practical significance to establish inorganic As form limits in Sepiae Endoconcha.

Contamination Parts and Residue Levels of Multi-Mycotoxins in Medicinal and Edible Locust.

Locust is esteemed as a traditional Chinese medicine, as well as one of the most important nutritional foods especially in Asian countries. However, some toxic secondary metabolites such as mycotoxins are usually found in different parts of locust to affect its quality and safety. This study aimed to investigate the aflatoxins (AFs) contaminated parts by observing Aspergillus flavus, spores' diameter, amount and distribution on head, tentacle, wing, belly and shank parts of the locust with scanning electron microscopy (SEM). Furthermore, to assess the residue levels of multi-mycotoxins in the locust, the high performance liquid chromatography with fluorescence detection (HPLC-FLD) was adopted. The technique was used to determine the contents of AFs, zearalenone (ZON) and α-zearalenol (α-ZOL) in locust and the positive samples were confirmed by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The chromatographic conditions, MS/MS parameters and the method of sample extraction were carefully optimized. Results revealed that obvious differences of Aspergillus flavus strains and spores were found, while the spores' diameter ranged from 3.0 to 13.0 µm in different contaminated parts of the locust samples. The HPLC-FLD method for multi-mycotoxins analysis showed good selectivity, linearity, recovery and precision. Limits of quantification (LOQs) were lower than 27.6 µg/kg, while limits of detection (LODs) were in the range of 0.02-8.6 µg/kg. The accuracy of the developed method was validated regarding recoveries of 80.1-118.1% with relative standard deviation (RSD) ≤ 11.4%. Finally, the developed multi-mycotoxin method was applied for screening of these mycotoxins in 11 commercial locust samples. Only AFB1 and AFB2 were found in six samples, and the contamination levels ranged from 0.12 to 4.4 µg/kg, which were lower than the maximum residue limit and can be used safely. This is the first report on the exploration of contamination parts and levels of multi-mycotoxins in medicinal and edible locust. The combined method of SEM and HPLC-FLD exhibited advantages of low cost, high sensitivity, rapid determination, convenience and especially intuitive judgment, which is proposed for contamination parts observation, for the large-scale quantification of multi-mycotoxins in other medicinal animal matrices.

A Rapid Label-Free Fluorescent Aptasensor PicoGreen-Based Strategy for Aflatoxin B1 Detection in Traditional Chinese Medicines.

Aflatoxin B1 (AFB1) is a very hazardous carcinogen, readily contaminating foodstuffs and traditional Chinese medicines (TCMs) that has inspired increasing health concerns due to dietary exposure. Colloidal nanocrystals have been proposed as optical labels for aptasensor assembly, but these typically require tedious multistep conjugation and suffer from unsatisfactory robustness when used for complex matrices. In the present study, we report a rapid and sensitive method for screening for trace AFB1 levels in TCMs using a label-free fluorescent aptasensor PicoGreen dye-based strategy. Using PicoGreen to selectively measure complementary double-stranded DNA, fluorescence enhancement due to dsDNA is 'turned off' in the presence of AFB1 due binding of aptamer target over complementary sequence. Self-assembly of a label-free fluorescent aptasensor based on AFB1 aptamer and PicoGreen dye was performed. Due to competition between the complementary sequence and AFB1 target, this rapid method was capable of highly sensitive and selective screening for AFB1 in five types of TCMs. This proposed approach had a limit of detection as low as 0.1 µg·L-1 and good linearity with a range of 0.1-10 µg·L-1 (0.1-10 ppb). Among the 20 samples tested, 6 batches were found to be contaminated with AFB1 using this method, which was confirmed using sophisticated liquid chromatography-electrospray ionization-tandem mass spectrometry/mass spectrometry analysis. The results of this study indicate the developed method has the potential to be a simple, quick, and sensitive tool for detecting AFB1 in TCMs.

Pectin-conjugated silica microcapsules as dual-responsive carriers for increasing the stability and antimicrobial efficacy of kasugamycin.

Kasugamycin is an aminoglycoside antibiotic originally isolated from Streptomyces kasugaensis, which has been widely used for the management of plant diseases. However, photo-thermal instability and low efficiency limit its application. Therefore, it is an urgent task to prevent unwanted loss of kasugamycin and ensure maximum bioactivity at target site. In this work, a novel formulation of kasugamycin that responds to different biological stimuli produced by pests was prepared using silica microcapsules crosslinked with pectin via special disulfide bonds. The results demonstrated that the silica-SS-pectin microcapsules had a high loading efficiency (20% w/w) and could effectively enhance the thermal and light stability of kasugamycin. The microcapsules displayed excellent pectinase and glutathione dual-responsive properties and the release kinetics investigated by Riger-Peppas model suggested combination of various release mechanisms. Compared with kasugamycin wettable powder, the microcapsules possessed sustained and improved antimicrobial efficacy against Erwinia carotovora. Thus, the dual-responsive microcapsules potentially have agricultural application as a controlled release system.