Rapid and simultaneous detection of cadmium and mercury in foods based on solid sampling integrated electrothermal vaporization technique.

This work presents an innovative solid sampling (SS) integrated electrothermal vaporization (ETV) approach for simultaneous determination of Cd and Hg based on differentiated elemental vaporization and transportation behavior characteristics. A miniature N2/H2 generator, only consuming electricity and H2O, was utilized to yield reducing atmosphere for Cd vaporization; MgO filler was modified to absorb matrix interferent and keep Hg and Cd transportation via 1st catalytic pyrolysis furnace (CPF); and a gearing was employed to move 2nd CPF to receive and trap (amalgamation) the vaporized Hg from ETV and then thermo-release them for simultaneous detection. Under optimized conditions, the limits of detection of Cd and Hg reached 0.02-0.04 ng/g using 0.4 g sample size. The linearities (R2) exceeded 0.998 and recoveries were 85.0-111.9%, indicating favorable analysis precision and accuracy within ∼3 min without sample digestion process. The proposed HgCd analyzer is suitable for rapid monitoring food with simplicity, green and safety.

A portable solid sampling visualization nano-sensor for soil Cd based on "three-phase transforming" technique.

Direct analysis of solid samples is always challenging for ionic sensors due to solidified elemental presence and matrix interference. In this work, a "three-phase transforming" technique was first established to make solid sampling elemental sensors and visual detection possible in the future. For Cd transforming from soil samples, a metal ceramic heater (MCH) electrothermal vaporizer (ETV) coupled with a dielectric barrier discharge quartz trap (DBD-QT) was first utilized to fulfill the solid sampling and preconcentration of Cd in soil; for on-site analysis, a colorimetric sensor based on the trithiocyanuric acid (TMT) functionalized gold nanoparticles (AuNPs) was chosen as a chromogenic analysis model. The portable and miniature ETV-DBD apparatus directly introduced Cd from soil and then captured Cd, consuming only <130 W and 4.5 kg weight; finally, only 200 µL water was injected as eluent to dissolve Cd for the following colorimetric detection. Herein, the Cd analyte underwent a "three-phase transforming" from solid (Cd compounds in soil), to aerosol (vaporization and transportation), to solid (Cd oxides trapped on quartz surface) and to liquid (Cd2+ in eluate). Under optimized conditions, the method limit of detection (LOD) reached 0.04 mg/kg Cd (50 mg sample), fulfilling fast monitoring of Cd contamination in soil, with <20 % relative standard deviations (RSDs). The analysis time was <10 min excluding sample digestion and acid application, as well as the interference of Pb2+ on the AuNPs sensor can be eliminated via the "three-phase transforming" process, proving an excellent anti-interference for solid analysis. This "three-phase transforming" processing technique coupled with colorimetric sensor holds a great potential for direct and on-site analysis in solid samples without complicated handling, providing a fantastic methodology for the application of ionic sensors and making solid sampling elemental sensor and visual detection possible.

A novel functionalized graphdiyne oxide membrane for efficient removal and rapid detection of mercury in water.

In practice, efficient, rapid and simple removal of Hg(II) from water using nano adsorbents remains an extreme challenge at present. In this work, a novel Hg(II) adsorbent based on functionalized graphdiyne oxide (GDYO-3M) membrane was designed for the purpose of effective and prompt removal of Hg(II) from environmental water for the first time. Through filtration, the proposed GDYO-3M membrane (4 cm diameter size) fulfilled an exceeding 97% removal efficiency in > 10 L water containing 0.1 mg/L Hg(II) within 1 h. Due to the presence of -SH groups, the GDYO-3M membrane demonstrates an excellent selectivity for Hg(II) vs. 14 co-existing metal ions. In the meantime, the GDYO-3M membrane represents a favorable reproducibility (above 95% Hg(II) removal) after 9 successive adsorption-desorption cycles. For the mechanism, it is believed that the active sites in the adsorption process mainly include -SH groups, oxygen-containing functional groups, and alkyne bonds. Further, the GDYO-3M membrane can be utilized as an enrichment approach for sensitive analysis of Hg(II) in water based on energy dispersion X-ray fluorescence spectrometry (ED-XRF), whose detection limit (LOD) reaches 0.2 µg/L within 15 min. This work not only provides a green and efficient method for removing Hg(II), but also renders an approach for rapid, sensitive and portable Hg(II) detection in water.

Rapid and sensitive determination of Se and heavy metals in foods using electrothermal vaporization inductively coupled plasma mass spectrometry with a novel transportation system.

Rapid, sensitive and simultaneous determination of trace multi-elements in various plant food samples such as grain, oilseed, vegetable and tea is always a challenge thus far. In this work, a rapid determination method for Se, Cd, As and Pb in food samples by inductively coupled plasma mass spectrometry (ICP-MS) using slurry sampling electrothermal vaporization (SS-ETV) was developed. To improve the analytical sensitivity and precision as well as eliminate the memory effect, a gas turbulator line and signal delay device (SDD) were for the first time designed for the graphite furnace (GF) ETV coupled with ICP-MS. The signal acquisition parameters of ICP-MS, ashing and vaporization conditions, and the flow rates of carrier gas and gas turbulator were investigated for Se, Cd, As and Pb in food samples. Under the optimized conditions, the limits of determination (LODs) for Se, Cd, As and Pb were 0.5 ng g-1, 0.3 ng g-1, 0.3 ng g-1 and 0.6 ng g-1, respectively; the limits of quantification (LOQs) for Se, Cd, As and Pb were 1.7 ng g-1, 1.0 ng g-1, 1.0 ng g-1 and 1.9 ng g-1, respectively; linearity (R2) in the range of 1 to 4,000 ng g-1 was >0.999 using the standard addition method. This method was used to analyze 5 CRMs including rice, tea and soybeans, and the concentrations detected by this method were within the range of the certified values. The recoveries of Se, Cd, As and Pb in plant food matrices including grain, oilseed, celery, spinach, carrot and tea samples were 86-118% compared to the microwave digestion ICP-MS method; and the relative standard deviations (RSDs) were 1.2-8.9% for real food sample analysis, proving a good precision and accuracy for the simultaneous determination of multi-elements. The analysis time was less than 3 min, slurry preparation time < 5 min without sample digestion process. The proposed direct slurry sampling ICP-MS method is thus suitable for rapid and sensitive determination of Se, Cd, As and Pb in food samples with advantages such as simplicity, green and safety, as well as with a promising application potential in detecting more elements to protect food safety and human health.

Rapid and Portable Detection of Hg and Cd in Grain Samples Based on Novel Catalytic Pyrolysis Composite Trap Coupled with Miniature Atomic Absorption Spectrometry.

As toxic metals, Hg and Cd are a concern for food safety and human health; their rapid and portable analysis is still a challenge. A portable and rapid Hg-Cd analyzer constructed from a metal-ceramic heater (MCH)-based electrothermal vaporizer (ETV), an on-line catalytic pyrolysis furnace (CPF), a composite Pt/Ni trap, and a homemade miniature atomic absorption spectrometer (AAS) was proposed for grain analysis in this work. To enhance sensitivity, a new folded light path was designed for simultaneous Hg and Cd analysis using charge coupled device (CCD) in AAS. To eliminate the grain matrix interference, a catalytic pyrolysis furnace with aluminum oxide fillers was utilized to couple with a composite Pt/Ni trap. The method limits of detection (LODs) were 1.1 µg/kg and 0.3 µg/kg for Hg and Cd using a 20 mg grain sample, fulfilling the real sample analysis to monitor the grain contamination quickly; linearity R2 > 0.995 was reached only using standard solution calibration, indicating the sample was free of grain matrix interference. The favorable analytical accuracy and precision were validated by analyzing real and certified reference material (CRM) grains with recoveries of 97-103% and 96-111% for Hg and Cd, respectively. The total analysis time was less than 5 min without sample digestion or use of any chemicals, and the instrumental size and power consumption were <14 kg and 270 W, respectively. Compared with other rapid methods, this newly designed Hg-Cd analyzer is proven to be simple, portable, and robust and is, thus, suitable to quickly monitor Hg and Cd contamination in the field to protect grain and food safety.

Ultra-high-efficiency capture of lead ions over acetylenic bond-rich graphdiyne adsorbent in aqueous solution.

A satisfactory material with high adsorption capacity is urgently needed to solve the serious problem of environment and human health caused by lead pollution. Herein, hydrogen-substituted graphdiyne (HsGDY) was successfully fabricated and employed to remove lead ions from sewage and lead-containing blood. The as-prepared HsGDY exhibits the highest adsorption capacity of lead among the reported materials with a maximum adsorption capacity of 2,390 mg/g, i.e., ~five times larger than that of graphdiyne (GDY). The distinguished hexagonal hole and stack mode of HsGDY allows the adsorption of more lead via its inner side adsorption mode in one single unit space. In addition, the Pb 6s and H 1s hybridization promotes the strong bonding of lead atom adsorbed at the acetylenic bond of HsGDY, contributing to the high adsorption capacity. HsGDY can be easily regenerated by acid treatment and showed excellent regeneration ability and reliability after six adsorption-regeneration cycles. Langmuir isotherm model, pseudo second order, and density functional theory (DFT) demonstrated that the lead adsorption process in HsGDY is monolayer chemisorption. Furthermore, the HsGDY-based portable filter can handle 1,000 µg/L lead-containing aqueous solution up to 1,000 mL, which is nearly 6.67 times that of commercial activated carbon particles. And, the HsGDY shows good biocompatibility and excellent removal efficiency to 100 µg/L blood lead, which is 1.7 times higher than that of GDY. These findings suggest that HsGDY could be a promising adsorbent for practical lead and other heavy metal removal.

Rapid detection of ultratrace urinary arsenic by direct sampling microplasma vaporization based on silicon nitride.

At present, immediate monitoring urinary arsenic is still a challenge for treating arsenic poisoning patients. Thus, a fast, reliable and accurate analytical approach is indispensable to monitor ultratrace arsenic in urine sample for health warning. In this work, a silicon nitride (SN) rod was first integrally utilized as a sample carrier for ≤50 µL urinary aliquot, an electric heater for removing water and ashing sample as well as a high voltage electrode for dielectric barrier discharge vaporization (DBDV). The direct analytical method of arsenic in urine without sample digestion was thus developed using atomic fluorescence spectrometer (AFS) as a model detector. After 4 V electrically heating the SN rod for 60 s, urine sample was dehydrated and ashed outside; then, DBD was exerted under 0.8 A with 0.8 L/min H2 + Ar (1:9, v:v) for 20 s to vaporize arsenic analyte from the SN rod. After optimization, 0.014 µg/L arsenic detection limit (LOD) was reached with favorable analytical precision (RSD <5%) and accuracy (91-110% recoveries) for real sample analysis. As a result, the whole analysis process only consumes <3 min to exclude complicated sample preparation; furthermore, the designed DBDV system only occupies 25 W and <2 kg, which renders a miniature sampling component to hyphenate with a miniature detector to detect arsenic. Thus, this direct sampling DBDV method extremely fulfills the fast, sensitive and precise detection of ultratrace arsenic in urine sample.

Novel Platinum-Nickel Composite Trap for Simultaneous and Direct Determination of Mercury and Cadmium in Soil and Its Mechanism Study.

In this work, following a metal-ceramic heater (MCH) as an electrothermal vaporizer (ETV), a novel composite Pt/Ni trap based on platinizing the foamed nickel was first fabricated to trap Hg and Cd simultaneously. So, a solid sampling Hg-Cd analyzer was developed to simultaneously detect trace Hg and Cd in soil samples, mainly consisting of an MCH, a composite Pt/Ni trap, and an atomic fluorescence spectrometer (AFS). This small-size MCH-ETV system only consumes 100 W for the complete vaporization of Hg and Cd in soil matrices. The Pt/Ni trap fulfills the complete trapping of Hg and Cd following the solid sampling MCH-ETV system and then fast releases them by heating. It was proved that trapped and released Hg and Cd by the Pt/Ni trap are atomic species using X-ray photoelectron spectroscopy (XPS) and other approaches; specially, the effective cotrapping of Hg and Cd might be due to forming alloys of Hg + Pt and Cd + Ni on the Pt/Ni trap. Under the optimized conditions, the method detection limits (LODs) of Hg and Cd reached 0.4 µg/kg and 0.04 µg/kg for a 20 mg sample size, the relative standard deviations (RSDs) were within 12% and 8% for soil samples, respectively, and the recoveries ranged from 96% to 105%, indicating favorable analytical sensitivity, precision, and accuracy. The whole analysis time can be controlled within 5 min without the soil digestion process. The proposed Hg-Cd analyzer is thus suitable for rapid detection of Hg and Cd in soil samples with advantages such as simplicity, green, and safety. Further, the proposed solid sampling ETV-composite trap method has a promising application potential in the field and rapid detection for multielements.

Fast and Sensitive Determination of Cadmium and Selenium in Rice by Direct Sampling Electrothermal Vaporization Inductively Coupled Plasma Mass Spectrometry.

In this work, a direct solid sampling device based on modified graphite furnace electrothermal vaporization (GF-ETV) with inductively coupled plasma mass spectrometry (ICP-MS) was established for the simultaneous detection of trace selenium and cadmium in rice samples. A bypass gas was first designed in GF-ETV to improve the device's analytical sensitivity and precision. The ashing and vaporization conditions, the flow rates of the Ar carrier and the bypass gases of ICP-MS were all investigated. Under the optimized conditions, the limits of detection (LODs) for Se and Cd were 0.5 µg kg−1 and 0.16 µg kg−1, respectively; the relative standard deviations (RSDs) of repeated measurements were within 8% (n = 6). The recoveries of Cd and Se in rice samples were in the range of 89−112% compared with the microwave digestion ICP-MS method, indicating good accuracy and precision for the simultaneous detection of Se and Cd in rice matrix. The whole analysis time is <3 min without the sample digestion process, fulfilling the fast detection of Se and Cd in rice samples to protect food safety.

Solid Sampling Pyrolysis Adsorption-Desorption Thermal Conductivity Method for Rapid and Simultaneous Detection of N and S in Seafood.

In this work, a rapid method for the simultaneous determination of N and S in seafood was established based on a solid sampling absorption-desorption system coupled with a thermal conductivity detector. This setup mainly includes a solid sampling system, a gas line unit for controlling high-purity oxygen and helium, a combustion and reduction furnace, a purification column system for moisture, halogen, SO2, and CO2, and a thermal conductivity detector. After two stages of purging with 20 s of He sweeping (250 mL/min), N2 residue in the sample-containing chamber can be reduced to <0.01% to improve the device's analytical sensitivity and precision. Herein, 100 s of heating at 900 °C was chosen as the optimized decomposition condition. After the generated SO2, H2O, and CO2 were absorbed by the adsorption column in turn, the purification process executed the vaporization of the N-containing analyte, and then N2 was detected by the thermal conductivity cell for the quantification of N. Subsequently, the adsorbed SO2 was released after heating the SO2 adsorption column and then transported to the thermal conductivity cell for the detection and quantification of S. After the instrumental optimization, the linear range was 2.0−100 mg and the correlation coefficient (R) was more than 0.999. The limit of detection (LOD) for N was 0.66 µg and the R was less than 4.0%, while the recovery rate ranged from 95.33 to 102.8%. At the same time, the LOD for S was 2.29 µg and the R was less than 6.0%, while the recovery rate ranged from 92.26 to 105.5%. The method was validated using certified reference materials (CRMs) and the measured N and S concentrations agreed with the certified values. The method indicated good accuracy and precision for the simultaneous detection of N and S in seafood samples. The total time of analysis was less than 6 min without the sample preparation process, fulfilling the fast detection of N and S in seafood. The establishment of this method filled the blank space in the area of the simultaneous and rapid determination of N and S in aquatic product solids. Thus, it provided technical support effectively to the requirements of risk assessment and detection in cases where supervision inspection was time-dependent.

Portable and miniature mercury analyzer using direct sampling inbuilt-metal ceramic electrothermal vaporization.

In this work, a small-size inbuilt-metal ceramic heater (IMCH) was for the first time utilized as a solid sampling electrothermal vaporizer (ETV), and then a novel direct sampling mercury analyzer coupled with a miniature atomic absorption spectrometer was thereby fabricated for sensitive determination of mercury in soil. The mercury analyzer is mainly composed of an IMCH-ETV, a catalytic pyrolysis furnace (CPF) using Al2O3 particles as a new filler, an atomic absorption spectrometer (AAS) and a miniature air pump for carrier gas; herein, the mostly used gold amalgamation was canceled. The IMCH with 30 W heating fulfills the 100% vaporization of mercury from up to 80 mg soil samples using 0.1 L min-1 air carrier. Under the optimized conditions, the method detection limit (LOD) was 0.4 ng g-1 for a 50 mg sample and the RSD of 11 repeated measurements of GSS-3a soil certified reference material (CRM) was 4%. Furthermore, the measured Hg values in various soil CRMs and real soil samples were within their certified values and consistent with that using the Chinese standard method (solid sampling catalytic pyrolysis AAS with gold amalgamation); and the recoveries were 85-113%, which proved favorable analytical accuracy and precision. This fabricated instrumentation only occupies 5 kg and 200 W power consumption vs. more than 25 kg and 1000 W for the traditional Hg analyzer. Therefore, the proposed IMCH-ETV-AAS method is very suitable for portable and rapid detection of mercury in soil.

Fast Detection of Cadmium in Chocolate by Solid Sampling Electrothermal Vaporization Atomic Absorption Spectrometry and Its Application on Dietary Exposure Risk Assessment.

In this work, a rapid detection method using solid sampling electrothermal vaporization atomic absorption spectrometry (SS-ETV-AAS) was established for cadmium in chocolate. The instrumental system includes a solid sampling ETV unit, a catalytic pyrolysis furnace, an AAS detector, and a gas supply system with only an air pump and a hydrogen generator. Herein, MgO material with 1.0−1.5 mm particle size was first employed to replace the kaolin filler previously used to further shorten the peak width and to thereby improve the sensitivity. With 350 mL/min of air, a chocolate sample was heated for 25 s from 435 to 464 °C to remove water and organic matrices; then, after supplying 240 mL/min hydrogen and turning down air to 120 mL/min, a N2/H2 mixture gas was formed to accelerate Cd vaporization from chocolate residue under 465 to 765 °C. Under the optimized conditions, the detection limit (LOD) was obviously lowered to 70 pg/g (vs. previous 150 pg/g) with R2 > 0.999; the relative standard deviations (RSD) of repeated measurements for real chocolate samples ranged from 1.5% to 6.4%, indicating a favorable precision; and the Cd recoveries were in the range of 93−107%, proving a satisfied accuracy. Thus, the total analysis time is less than 3 min without the sample digestion process. Thereafter, 78 chocolate samples with different brands from 9 producing countries in China market were collected and measured by this proposed method. Based on the measured Cd concentrations, a dietary exposure assessment was performed for Chinese residents, and the target hazard quotient (THQ) values are all less than 1, proving no significant health risk from intaking chocolate cadmium for Chinese residents.

Ultratrace mercury speciation analysis in rice by in-line solid phase extraction - liquid chromatography - atomic fluorescence spectrometry.

For the first time, Hg2+ and methylmercury speciation analysis was accomplished by in-line SPE-LC-AFS. After modification with 0.1 mL of 0.001% (m:v) sodium diethyldithiocarbamate, a C18 microcolumn retained Hg2+ and MetHg in rice extract within 3 min; the captured Hg species were separated within 12 min in 0.25% (v:v) 2-mercaptoethanol + 60 mmol L-1 (m:v) ammonium acetate + 4% (v:v) acetonitrile. Under optimized conditions, the detection limits were 0.3 ng L-1 for Hg2+ and 0.2 ng L-1 for MetHg, respectively, with 10 mL injection vs. 0.1 mL eluent; in-line SPE achieved âˆ¼ 100x enrichment. Method precision and accuracy were satisfactory at < 2% relative standard deviations (RSDs) for 20 ng L-1 of Hg2+ and MetHg and 95-102% recoveries for real rice samples. In-line SPE obviated human involvement and avoided invalid transportation between interfaces, rendering this SPE-LC-AFS method easy, compact, robust, yet sensitive in mercury speciation analysis to uphold food safety.

Novel Dielectric Barrier Discharge Trap for Arsenic Introduced by Electrothermal Vaporization: Possible Mechanism and Its Application.

In this work, a novel integrated dielectric barrier discharge (IDBD) reactor coupled to an electrothermal vaporizer (ETV) was established for arsenic determination. It is for the first time gas-phase enrichment (GPE) was fulfilled based on the hyphenation of ETV and DBD. The mechanisms of evolution of arsenic atomic and molecular species during vaporization, transportation, trapping, and release processes were investigated via X-ray photoelectron spectroscopy (XPS) and other approaches. Tentative mechanisms were deduced as follows: the newly designed DBD atomizer (DBDA) tube upstream to the air inlet fulfills the atomization of arsenic nanoparticles in vaporized aerosol, leading to free arsenic atoms that are indispensable for forming arsenic oxides; the DBD trap (DBDT) tube traps arsenic oxides under an O2-domininating atmosphere and then releases arsenic atoms under H2-dominating atmospheres. In essence, this process is a physical-chemical process rather than an electrostatic particle deposition. Such a trap and release sequence separates matrix interference and enhances analytical sensitivity. Under the optimized conditions, the method detection limit (LOD) was 0.04 mg/kg and the relative standard deviations (RSDs) were within 6% for As standard solution and real seafood samples, indicating adequate analytical sensitivity and precision. The mean spiked recoveries for laver, kelp, and Undaria pinnatifida samples were 95-110%, and the results of the certified reference materials (CRMs) were consistent with certified values. This ETV-DBD preconcentration scheme is easy and green and has low cost for As analysis in seafood samples. DBD was proved a novel ETV transportation enhancement and preconcentration technique for arsenic, revealing its potential in rapid arsenic analysis based on direct solid sampling ETV instrumentation.

Trace arsenic analysis in edible seaweeds by miniature in situ dielectric barrier discharge microplasma optical emission spectrometry based on gas phase enrichment.

In this work, a novel method using low-cost miniaturized hydride generation optical emission spectrometry equipment coupled with an in situ dielectric barrier discharge trap (HG-in situ DBD trap-OES) was established for the determination of As in edible seaweed samples. An improved peak volume algorithm, where the start time point and end time point of the spectrum at each concentration are determined according to the unified judgment criteria, was first proposed to extend the linear range from 1-100 µg L-1 to 1-200 µg L-1, and increase the sensitivity by about 30%. In addition, a modification was done on the DBD implementation, providing an enhancement of sensitivity by a factor of about 4 for As. All in all the detection limit (LOD) was improved from 0.5 µg L-1 to 0.2 µg L-1. By applying the method to seaweed samples, a method detection limit (MD) of 0.25 mg kg-1 was achieved, with less than 3% relative standard deviations (RSDs). The calibration linearity reached R2 > 0.990 in the 1.25-250 mg kg-1 range. Results obtained by the proposed method showed good agreement with that of certified reference materials (CRMs), and spiked recoveries were 103% to 114%, indicating favorable accuracy. The proposed method is attractive in terms of instrumentation size (0.6 m × 0.5 m × 0.3 m), power consumption (<60 W), manufacturing cost, and gas consumption (300 measurements for 4 L compressed Ar/H2 gas), and therefore more advantageous than conventional atomic spectrometric methods.

Baicalin regulates mRNA expression of VEGF-c, Ang-1/Tie2, TGF-ß and Smad2/3 to inhibit wound healing in streptozotocin-induced diabetic foot ulcer rats.

Diabetic foot ulcer (DFU) is biggest life threats globally and increases their severity increases health complications for health of patients. The present study was investigated to recover the wound healing activity of baicalin in STZ-induced DFU rats by evaluating biochemical and molecular markers. The experimental animals induced with diabetes and excision wounds were treated with different doses of baicalin (25, 50, and 100 mg/kg). The serum glucose level, body weight and food intake were measured. In addition, DFU rat groups showed decreased food intake and increased body weight. The tissue was subjected to biochemical evaluation, histopathology, quantitative polymerase chain reaction and Western blot analysis. Histopathology reports revealed that diabetic wound control (DWC) + baicalin (100 mg/kg) treated group showed more than 90% recovery with more epithelization and remarkably improved angiogenesis and infiltration of the inflammatory cells. In this study we also proved that upregulated the p-ERK, ERK, HSP27, and p-HSP27 protein expression and mRNA expression of Ang-1, VEGF-c, TGF-ß, Tie-2, and SMAD2/3 implicating the potential antidiabetic and wound healing property of baicalin. Thus, baicalin is a potential therapeutic candidate for a diabetic foot ulcer and chronic wounds treatment.

Analytical Methodologies for Agrometallomics: A Critical Review.

Agrometallomics, as an independent interdiscipline, is first defined and described in this review. Metallic elements widely exist in agricultural plants, animals and edible fungi, seed, fertilizer, pesticide, feedstuff, as well as the agricultural environment and ecology, and even functional and pathogenic microorganisms. So, the agrometallome plays a vital role in molecular and organismic mechanisms like environmetallomics, metabolomics, proteomics, lipidomics, glycomics, immunomics, genomics, etc. To further reveal the inner and mutual mechanism of the agrometallome, comprehensive and systematic methodologies for the analysis of beneficial and toxic metals are indispensable to investigate elemental existence, concentration, distribution, speciation, and forms in agricultural lives and media. Based on agrometallomics, this review summarizes and discusses the advanced technical progress and future perspectives of metallic analytical approaches, which are categorized into ultrasensitive and high-throughput analysis, elemental speciation and state analysis, and spatial- and microanalysis. Furthermore, the progress of agrometallomic innovativeness greatly depends on the innovative development of modern metallic analysis approaches including, but not limited to, high sensitivity, elemental coverage, and anti-interference; high-resolution isotopic analysis; solid sampling and nondestructive analysis; metal chemical species and metal forms, associated molecular clusters, and macromolecular complexes analysis; and metal-related particles or metal within the microsize and even single cell or subcellular analysis.

Fast and High Sensitive Analysis of Lead in Human Blood by Direct Sampling Hydride Generation Coupled with in situ Dielectric Barrier Discharge Trap.

A direct sampling hydride generation (HG) system based on modified gas liquid separator (GLS) coupled with in situ dielectric barrier discharge (DBD) is first rendered to detect lead in blood samples. Herein, a triple-layer coaxial quartz tube was employed as DBD trap (DBDT) to replace the original atomizer of atomic fluorescence spectrometry (AFS) to satisfy the in situ preconcentration. After 40-fold dilution, foams generated from protein in a blood sample can be eliminated via the double-GLS set; and lead in a blood sample were generated as plumbane under 3.5% HNO3 (v:v) and 30 g/L NaOH with 8 g/L KBH4, 10 g/L H3BO3, and 5 g/L K3[Fe(CN)6]. Then, lead analyte was trapped on the DBD quartz surface by 9 kV discharging at 50 mL/min air; and subsequently released by 12 kV discharging at 110 mL/min H2. The absolute detection limit (LOD) for Pb was 8 pg (injection volume = 2 mL), and the linearity (R2 > 0.997) range was 0.05 - 50 µg/L. The results were in good agreement with that of blood certified reference materials (CRM), and spiked recoveries for real blood samples were 95 - 104% within a relative standard deviation of 5% (RSD). Via gas phase enrichment, the established method improved analytical sensitivity (peak height) by 8 times. The entire analysis time including blood sample preparation can be kept to within 10 min. The combination of modified GLS and DBDT can facilitate the quickness, accuracy, and sensitivity, revealing a promising future for monitoring lead in blood to protect humans, especially children's health.

Benefit-risk assessment of dietary selenium and its associated metals intake in China (2017-2019): Is current selenium-rich agro-food safe enough?

Dietary consumption of selenium-rich agro-food is an effective way to avoid selenium deficiency diseases, however, over consumption of selenium-rich agro-food will result in potential risk of selenosis and problems with associated metals. In this study, we measured the concentrations of selenium and its associated metals in 2756 common and 4894 selenium-rich agro-food samples in 10 regions of China. We found that selenium-rich rice, flour, edible fungi and algae, meat, and tea contain higher levels of associated metals than other selenium-rich agro-food samples. Increasing the consumption of selenium-rich agro-food could make the actual intakes (AIs) of selenium for all population to meet respective recommended daily intakes (RDIs). Benefit-risk assessment results indicated that increasing the consumption of selenium-rich agro-food make AIs of selenium for all populations meet RDIs, chromium intakes for people under 18 years old exceed provisional tolerated daily intake (PTDIs), while arsenic and cadmium intakes are close to PTDIs. The main dietary contributors of selenium, chromium, arsenic and cadmium were meat, edible fungi and algae, rice, and rice, respectively. The study supported the consumption of selenium-rich agro-food for effective selenium supplement, but also emphasized potential risk from associated metals in selenium-rich agro-food, especially chromium.

In situ preconcentration of lead by dielectric barrier discharge and its application to high sensitivity surface water analysis.

A novel dielectric barrier discharge (DBD) reactor was utilized to in situ enrich and atomize lead in gas phase. The structure of DBD reactor was optimized to broaden the acidity window of plumbane generation from 1% to 3.5%, bringing better analytical stability and practicability deriving from hydride generation process. For the first time DBD proved effective in lead preconcentration and broadening the acidity window of plumbane generation. Pb can be trapped quantitatively (~100%) on the quartz surface of DBD tube under O2-containing atmosphere and released (~100%) under H2-containing atmosphere. The absolute detection limit (LOD) for Pb was 4.1 pg (injection volume = 1.2 mL), and the linear (R2 > 0.999) range was 0.05-100 µg/L. The results were in good agreement with those of certified reference materials (CRMs), and spiked recoveries for surface water samples were 99-104% with 2-8% RSD. By gas phase analyte enrichment, the proposed method reduced absolute LOD by 10 times. It was deduced that plumbane was changed to lead oxide species trapped on the quartz tube surface and then released, and transported in form of atoms to the detection zone.