High-performance Liquid Chromatography-inductively Coupled Plasma-mass Spectrometry Research Articles

The Fast Quantification of Vitamin B12 in Milk Powder by High-Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry.

This study presents a new technique for determining vitamin B12 in milk powder using high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS). We used ultrasonics with potassium ferrocyanide and zinc acetate solutions to extract the samples. 59Co was employed as the analytical target for cyanocobalamin. It was separated using a Phenomenex Luna 5 μm C18 (250 × 4.6 mm) chromatographic column with a mobile phase consisting of 1.6 mmol/L EDTA and 0.4 mmol/L KH2PO4 in a 60% v/v methanol solution (pH = 4.0). The sample has an excellent separating degree for free cobalt and cyanocobalamin, and isocratic elution can be finished within 4.0 min. To eliminate the matrix interference due to the presence of milk powder, we applied collision mode (KED). The linear range of cyanocobalamine ranged from 1.0 μg/L to 20 μg/L, with correlation coefficients (r2) of 0.9994. The limit of detection (LOD) was 0.63 μg/kg, and the limit of quantitation (LOQ) was 2.11 μg/kg. The mean recoveries were in the range of 87.4-103.6%. The accuracy and precision of the developed method are well suited for the fast quantification of the trace vitamin B12 in milk powder.

Trace Element Distribution and Arsenic Speciation in Toenails as Affected by External Contamination and Evaluation of a Cleaning Protocol.

Trace element concentrations in toenail clippings have increasingly been used to measure trace element exposure in epidemeological research. Conventional methods such as inductively coupled plasma mass spectrometry (ICP-MS) and high-performance liquid chromatography ICP-MS (HPLC-ICP-MS) are commonly used to measure trace elements and their speciation in toenails. However, the impact of the removal of external contamination on trace element quantification has not been thoroughly studied. In this work, the microdistribution of trace elements (As, Ca, Co, Cu, Fe, K, Mn, Ni, Rb, S, Sr, Ti, and Zn) in dirty and washed toenails and the speciation of As in situ in toenails were investigated using synchrotron X-ray fluorescence microscopy (XFM) and laterally resolved X-ray absorption near edge spectroscopy (XANES). XFM showed different distribution patterns for each trace element, consistent with their binding properties and nail structure. External (terrestrial) contamination was identified and distinguished from the endogenous accumulation of trace elements in toenails─contaminated areas were characterized by the co-occurrence of Co, Fe, and Mn with elements such as Ti and Rb (i.e., indicators of terrestrial contamination). The XANES spectra showed the presence of one As species in washed toenails, corresponding to As bound to sulfhydryl groups. In dirty specimens, a mixed speciation was found in localized areas, containing AsIII-S species and AsV species. ArsenicV is thought to be associated with surface contamination and exogenous As. These findings provide new insights into the speciation of arsenic in toenails, the microdistribution of trace elements, and the effectiveness of a cleaning protocol in removing external contamination.

The study on biological exposure index of occupational exposure to arsenic and its inorganic compounds

Objective: To establish biological exposure index (BEI) of occupational exposure to arsenic and its inorganic compounds through occupational epidemiology and the regression analysis of internal and external exposure of workers. Methods: In November 2021, 125 workers with occupational exposure to arsenic and its inorganic compounds and 49 office administrators in a non-ferrous metal smelter in Yunnan Province were selected as the exposure group and control group, respectively. Air samples from the workplace of the study subjects on weekdays were collected and arsenic concentrations were determined. Urine samples were collected in end-of-work weekend and high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) was used to detect the levels of trivalent inorganic arsenic (iAs(3+)) , pentavalent inorganic arsenic (iAs(5+)) , monomethyl arsenic (MMA) and dimethyl arsenic (DMA) in urine. The correlations between arsenic concentration in the workplace air and arsenic species in urine of workers were analyzed. Arsenic exposure concentration and the level of urinary arsenic (ΣiAs+MMA+DMA) of workers was analyzed by linear regression and the BEI of arsenic and its inorganic compounds in the workplace was proposed based on the results of micronucleus test. Results: The median of time-weighted average concentration (C(TWA)) of arsenic in the workplace air of the exposure group was 0.0116 mg/m(3), and the over-standard rate was 71.2% (89/125) . The concentrations of iAs(3+), iAs(5+), inorganic arsenic (iAs=ΣiAs(3+)+iAs(5+)) 、MMA、DMA and urinary arsenic in the exposure group were higher than those in the control group at the end of shift, and the differences were statistically significant (P<0.05) . The concentration of arsenic in the workplace air had the strongest correlation with the concentration of urinary arsenic at the end of the shift (r(s)=0.909, P<0.001) . The regression equation was lg (y) =7.662+2.968lg (x) (r=0.821, P<0.05) . According to the occupational exposure limit (OEL) of arsenic in China, the concentration of urinary arsenic in the end-of-work weekend was calculated to be 53.2 μg/L. Combined with the results of micronucleus test, the BEI of occupational exposure to arsenic and its inorganic compounds in the workplace was proposed to be 50 μg/L. Conclusion: The urinary arsenic in the end-of-work weekend can be used as a biomarker of occupational exposure to arsenic, and its BEI is recommended to be 50 μg/L.

Urine Self-Sampling Kit Combined with an Automated Preparation-Sampler Device for Convenient and Reliable Analysis of Arsenic Metabolites by HPLC-ICPMS.

Speciation analysis of arsenic in urine is essential for the studies of arsenic metabolism and biological effects, but the unstable arsenic species represented by MMAIII and DMAIII pose a huge challenge to analytical accuracy. Herein, a novel urine self-sampling (USS) kit combined with an automated preparation-sampler (APS) device is rationally designed and used for convenient analysis of arsenic metabolites by high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICPMS). The subject can collect urine into a sampling vial at home and use a homemade syringe to pump argon to displace oxygen in the vial, thereby inhibiting the oxidation of MMAIII and DMAIII. After USS and transportation, the sampling vial is loaded directly onto the APS device, where the urine sample can be automatically mixed with diluent, filtered, and loaded into HPLC-ICPMS for arsenic speciation analysis under anaerobic conditions. For a single sample, the sampling time and the analysis time are <8 and <18 min, respectively. The recoveries of MMAIII and DMAIII in urine over 24 h at 4 °C are 86 and 67%, surpassing the conventional sampling method by 28 and 67%, respectively. When the APS is coupled to HPLC-ICPMS, the detection limits of AsC, iAsIII, MMAIII, DMAV, MMAV, DMAIII, and iAsV are 0.03-0.10 μg L-1 with precisions of <10%. The present method provides a convenient and reliable tool for the storage and analysis of unstable arsenic species in urine and lays the foundation for studying the metabolic and biological effects of methylated trivalent arsenicals.

Speciation and cycling of iodine in the subtropical North Pacific Ocean

Iodine intersects with the marine biogeochemical cycles of several major elements and can influence air quality through reactions with tropospheric ozone. Iodine is also an element of interest in paleoclimatology, whereby iodine-to-calcium ratios in marine carbonates are widely used as a proxy for past ocean redox state. While inorganic iodine in seawater is found predominantly in its reduced and oxidized anionic forms, iodide (I−) and iodate (IO3−), the rates, mechanisms and intermediate species by which iodine cycles between these inorganic pools are poorly understood. Here, we address these issues by characterizing the speciation, composition and cycling of iodine in the upper 1,000 m of the water column at Station ALOHA in the subtropical North Pacific Ocean. We first obtained high-precision profiles of iodine speciation using isotope dilution and anion exchange chromatography, with measurements performed using inductively coupled plasma mass spectrometry (ICP-MS). These profiles indicate an apparent iodine deficit in surface waters approaching 8% of the predicted total, which we ascribe partly to the existence of dissolved organic iodine that is not resolved during chromatography. To test this, we passed large volumes of seawater through solid phase extraction columns and analyzed the eluent using high-performance liquid chromatography ICP-MS. These analyses reveal a significant pool of dissolved organic iodine in open ocean seawater, the concentration and complexity of which diminish with increasing water depth. Finally, we analyzed the rates of IO3− formation using shipboard incubations of surface seawater amended with 129I−. These experiments suggest that intermediate iodine species oxidize to IO3− much faster than I− does, and that rates of IO3− formation are dependent on the presence of particles, but not light levels. Our study documents the dynamics of iodine cycling in the subtropical ocean, highlighting the critical role of intermediates in mediating redox transformations between the major inorganic iodine species.

Arsenic Contents, Speciation and Toxicity in Germinated Rice Alleviated by Selenium.

Rice can accumulate more organic and inorganic arsenic (iAs) than other crop plants. In this study, the localization of As in rice grains was investigated using High Performance Liquid Chromatography-Inductively Coupled Plasma Mass Spectrometry (HPLC-ICP-MS) based on 26 rice varieties collected from two provinces. In all the samples, the total As contents in polished rice were 0.03-0.37 mg/kg, with average values of 0.28 and 0.21 mg/kg for two sample sets. The results of the determination of arsenic speciation in different components of rice grain showed that in the polished and brown rice the mean value of arsenite (As(III)) was nearly twice than that of arsenate (As(V)). The regional difference was observed in both total As contents and As speciation. The reason may be that As(III) is more mobile than As(V) in a dissociated form and because of soil properties, rice varieties, and the growing environment. The proportion of iAs and the total As in rice bran was higher than that in polished rice, and this is because As tends accumulate between the husk and the endosperm. In our study, selenium could alleviate the risk of arsenic toxicity at the primary stage of rice growth. Co-exposure to As and Se in germinated rice indicated that the reduction in As accumulation in polished rice reached 73.8%, 76.8%, and 78.3% for total As, As(III), and As(V) when compared with rice treated with As alone. The addition of Se (0.3 mg/kg) along with As significantly reduced the As amount in different parts of germinated rice. Our results indicated that Se biofortification could alleviate the As accumulation and toxicity in rice crops.

Quantitative analysis of arsenic containing hydrocarbons in marine samples by GC-MS

Environmental context The marine ecosystem is highly elevated in arsenic in comparison to the terrestrial environment. More than 100 different naturally occurring organoarsenic compounds have been found in different marine organisms. In order to understand how highly toxic AsHCs are formed and bioaccumulate in different marine organisms, large scale monitoring of AsHCs from a range of different laboratories is necessary. Despite their toxicity, AsHCs have not been extensively studied due in part to the lack of low-cost analytical methods and the lack of commercially available standards.Rational This study aims to develop a new analytical method for the quantitative determination of arsenic-containing hydrocarbons (AsHCs) with gas chromatography–mass spectrometry (GC-MS). The new method is an alternative approach to determine these compounds in environmental samples.Methodology AsHCs were extracted and purified from fish oil and seaweed samples. Due to the thermal conversion of oxo-AsHCs to their trivalent forms in the injection port of the GC, the conversion is incomplete resulting in low signal intensities and large carry overs. We therefore chemically reduced AsHCs to their trivalent forms and analysed them with GC-MS, gas chromatography–tandem mass spectrometry (GC-MS/MS) and high performance liquid chromatography–inductively coupled plasma mass spectrometry (HPLC-ICPMS). The possibility for compound independent quantification with commercially available standards was investigated.Results After optimisation of conditions for reduction of AsHCs, these compounds could be determined in marine samples using authentic standards with the new method. Results showed good agreement with results from HPLC-ICPMS. The novel GC-MS method showed compound independent quantification using triphenylarsine (TPA) as a commercially available standard.Discussion With the developed method we could demonstrate the applicability of GC-MS for the quantitative determination of AsHCs in marine samples for the first time. The compound independent quantification with TPA opens up a quantification for AsHCs species for which no standards are commercially available. The broad applicability might enhance screening for these toxic compounds in the environment.

An online internal standard technique for high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS).

An online internal standard correction technique for high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) was designed using an autosampler system equipped with HPLC to improve the analytical precision. The autosampler was programed to operate in the following sequence: it first takes up a portion of sample solution, rinses the nozzle, sucks air as a spacer, takes an internal standard solution and finally injects all of them into a sampling loop through an injection valve. The repeatability of the sampling (amount 20 μL) was improved from 2.5 to 1.2% using the online internal standard technique. This technique was applied to As speciation in food samples, since food safety monitoring requires high precision and high sample throughput. Rhenium was very suitable as an internal standard element due to its retention time, peak shape and water solubility. This technique effectively improved the analytical precision of the As speciation and got rid of the operation of adding an internal standard solution into samples.

Speciation analysis of iodine in seaweed: optimisation of extraction procedure and chromatographic separation

Environmental context Seaweed is a good natural dietary source of iodine and some types of seaweed are rich in iodine. Iodine has a diverse chemistry in seaweeds and may exist as different chemical species; however, the occurrence and identity of the individual species are still not fully elucidated. Hence, development of sensitive and selective iodine speciation methods for studies of iodine chemistry and biotransformation in seaweeds are needed.Rationale Iodine is an essential element required for human health and metabolism. Seafood and especially seaweed can accumulate iodine to high amounts. Iodine may exist in different chemical forms (species) in seaweeds.Methodology The present study describes the development and optimisation of a method for iodine speciation analysis in seaweed based on high performance liquid chromatography–inductively coupled plasma–mass spectrometry (HPLC-ICP-MS). The extraction procedure was conducted in two steps, pancreatic enzymatic extraction followed by alkaline extraction with tetramethylammonium hydroxide for optimum extraction efficiency without compromising species integrity.Results and discussion Total iodine and iodine species were determined in a range of brown (6 samples), red (6 samples) and green (3 samples) seaweeds. A large variation in the total iodine content of the different seaweeds was observed (33–5611 µg g–1 dry weight) with the highest levels encountered in brown seaweed. Iodine speciation analysis revealed differences in the speciation profile of the different types of seaweed. In all seaweeds iodide was the predominant species, and minor contents of MIT (monoiodotyrosine) and DIT (diiodotyrosine) were found in most seaweeds. Furthermore, peaks originating from six unknown iodine-containing species were observed in the chromatograms, especially in red and green seaweeds, while less abundant in brown seaweeds. The speciation method presented here will be valuable in future studies on iodine speciation in seaweed and an important tool for the investigation of iodine speciation and biotransformation in marine algae.

Determination of six arsenic species in urine by high-performance liquid chromatography-inductively coupled plasma-mass spectrometr

Objective: Establishing an analysis method for the detection of six arsenic compounds trivalent arsenic, pentavalent arsenic, methyl arsenic, dimethyl arsenic, arsenical choline and arsenical betaine in urine by high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) and providing a theoretical basis for health assessment of arsenic poisoning patients. Methods: HPLC-ICP-MS was used to detect six arsenic compounds with the hamilton PRP-X100 column and aqueous ammonium phosphate in a gradient elution as mobile phase. Results: There was a good linear relationship in the selected range of six arsenic compounds evidenced by a linear correlation coefficient greater than 0.999. The detection limit of 6 arsenic compounds was 0.46~0.57 μg/L, and the minimum quantitative concentration were 1.52~1.91 μg/L. The recovery rates of six arsenic compounds were 96.5%~106.4%, The within-run and between-run relative standard deviation was 2.9%~6.2% and 3.8%~8.7%. Conclusion: The established method with high accuracy and precision is suitable for detecting arsenic levels in urine of occupational arsenic exposure population.

Inorganic arsenic speciation analysis in food using HPLC/ICP-MS: Method development and validation.

Arsenic (As) compounds can be classified as organic or inorganic, with inorganic arsenic (iAs) having significantly higher toxicity than organic As. As may accumulate in food materials that have been exposed to As-contaminated environments. Thus, the "Sanitation Standard for Contaminants and Toxins in Foods" published by the Ministry of Health and Welfare set the standard limits for iAs content in rice, seaweed, seafood, and marine oils to safeguard public health. Therefore, a robust analytical method must be developed to selectively and quantitatively determine iAs content in rice, seaweed, seafood, and marine oils. Herein, we reported and verified the method of combined high-performance liquid chromatography/inductively coupled plasma-mass spectrometry (HPLC/ICP-MS) to determine iAs content in a wide variety of food. The fish oil samples were spiked with different concentrations of the As(III) standard solution, and their iAs analyzes were obtained via extraction procedures using the 1% (w/w) nitric acid (HNO3) solution containing 0.2 M hydrogen peroxide (H2O2) under sonication. The extracts were subsequently analyzed for their As(V) contents using HPLC/ICP-MS with aqueous ammonium carbonate as the mobile phase. The As(III) species had completely oxidized into the As(V) species, which prevented interferences between organic and iAs during chromatography. The method showed good extraction efficiencies (generally >90%) for the iAs samples, and their limits of quantification in fish oil were 0.02 mg/kg. The method was verified via the iAs speciation analytes of rice, seaweed, seafood, and marine oil matrices. The average recoveries for the fortified samples of each matrix ranged from 87.5 to 112.4%, with their coefficients of variation being less than 10%. Surveillance studies were conducted on the iAs contents of food samples purchased from local Taiwanese markets. The results showed that the only Hijiki (Sargassum fusiforme) higher than the maximum limit of the sanitation standard for iAs in seaweed, whereas the remaining samples met their corresponding requirements. This method is quick and straightforward, and it can be applied for the routine analysis of iAs content in a wide variety of food products to ensure public health safety.

Elevated Urbanization-Driven Plant Accumulation of Metal(loid)s Including Arsenic Species and Assessment of the Kłodnica River Sediment Contamination

The impact of water and bottom sediment pollution of a river subjected to a strong industrial anthropogenic pressure of metal(loid) (including arsenic and its species) accumulation in riverbank plants such as Solidago virgaurea L., Phragmites L. and Urtica dioica L. was investigated. The high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) technique was used to study organic and inorganic arsenic species in selected plants and their response to heavy metal and arsenic contamination. The modified BCR extraction results showed that arsenic was mainly bound to the mobile reducible and organic-sulfide fractions in the Kłodnica River bottom sediments. Research has shown that the bottom sediments of the Kłodnica River are contaminated with metals, including Pb, Zn, Ni, As, and among arsenic species, the As(V) form dominated quantitatively, with its highest concentration being 49.3 mg kg−1 and the organic species occurred extremely rarely. The highest concentration of arsenic, among the tested plants, occurred in Phragmites communis L. The evaluation of the bottom sediment pollution was performed using Sb/As factor, geoaccumulation index (Igeo), enrichment factor (EF) and pollution load index (PLI). The ability of the plant to assimilate metals from the substrate was studied by calculation of the bioaccumulation factor (BAF). Values of the Igeo change in a wide range from class 1 (uncontaminated to moderately polluted for Cu and Zn) at the first sampling point, to 5 (highly to extremely polluted for Ba and Fe) at the K4 sampling point. The Igeo results show an increase in the contamination with elements toward the runoff of the Kłodnica River.

Simultaneous speciation of chromate, molybdate and arsenate in lysimetric water from geotechnical composites installed in field lysimeters

Anion-exchange high performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS) was used for simultaneous speciation of chromate, molybdate and arsenate. The repeatability of measurement tested for multielemental standard solution of chromate, molybdate and arsenate (50 ng mL−1 of Cr, Mo and As, pH 12) was ± 0.9%, ± 4.9% and ± 4.1%, respectively. Limits of quantification (LOQs) were low (0.53 ng mL−1 for chromate and arsenate and 1.03 ng mL−1 for molybdate, expressed as elemental concentrations). A wide linear concentration range (from LOQs to 500 ng mL−1) was obtained. The performances of this method enabled simultaneous speciation analysis in samples of water from lysimeters, in which three geotechnical composites, made of recycled waste, were installed in parallel in compacted and uncompacted, 20 times less dense form. The release of toxic chemical species of elements into lysimetric waters from each composite was studied. The results revealed that the degree of compaction and the composition of composites both have a significant influence on leaching of chromate, molybdate and arsenate. The study proved that multielemental speciation analysis is fast and cost-effective method for investigations of environmental impacts of materials, made from recycled waste, and can be used in other similar applications.

Dietary contribution to total urinary arsenic in Mexican women

Exposure to inorganic arsenic (iAs) damages health in many ways. The main routes of human exposure are consumption of contaminated water and diet, but evidence regarding the dietary contribution of iAs is limited. The objective of this work was to determine the foods and beverages that contribute to urinary total arsenic levels (TAs). This is a secondary analysis of an original study of breast cancer cases and population controls carried out in northern Mexico during the period 2007–2011, from which 1,462 women without a history of diabetes were selected. We estimated the consumption of the food and beverage groups with a frequency questionnaire. We measured the concentrations of urinary iAs metabolites by high performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS). Total arsenic ranged from 0.5 to 2,360 µg/g creatinine. After adjusting for covariates, we observed a positive association between TAs (with arsenobetaine) with non-bottled drinking water intake, as well as the consumption of root vegetables, vegetables and fruits rich in water, eggs, fish and shellfish. Our findings highlight the relevance of water consumption and some foods for TAs exposure. Food quality monitoring deserves attention in high-risk regions of arsenic contamination.

Elution with 1,2-Hexanediol Enables Coupling of ICPMS with Reversed-Pase Liquid Chromatography under Standard Conditions.

The inductively coupled plasma mass spectrometry (ICPMS) has been attracting increasing attention for many applications as an element-selective chromatographic detector. A major and fundamental limitation in coupling ICPMS with liquid chromatography is the limited compatibility with organic solvents, which has so far been addressed via a tedious approach, collectively referred to as the “organic ICPMS mode”, that can decrease detection sensitivity by up to 100-fold. Herein, we report 1,2-hexanediol as a new eluent in high-performance liquid chromatography–ICPMS which enables avoiding the current limitations. Unlike commonly used eluents, 1,2-hexanediol was remarkably compatible with ICPMS detection at high flow rates of 1.5 mL min–1 and concentrations of at least 30% v/v, respectively, under the standard conditions and instrumental setup normally used with 100% aqueous media. Sensitivity for all tested elements (P, S, Cl, Br, Se, and As) was enhanced with 10% v/v 1,2-hexanediol relative to that of 100% aqueous media by 1.5–7-fold depending on the element. Concentrations of 1,2-hexanediol at ≤30% v/v were superior in elution strength to concentrations at >90% v/v of the common organic phases, which greatly decreases the amount of carbon required to elute highly hydrophobic compounds such as lipids and steroids, enabling detection at ultra-trace levels. The proposed approach was applied to detect arsenic-containing fatty acids in spiked human urine, and detection limits of <0.01 μg As L–1 were achieved, which is >100-fold lower than those previously reported using the organic ICPMS mode. Nontargeted speciation analysis in Allium sativum revealed the presence of a large number of hydrophobic sulfur-containing metabolomic features at trace levels.

Determination of arsenic in Chinese mitten crabs (Eriocheir sinensis): Effects of cooking and gastrointestinal digestion on food safety

This study used the sexually mature Chinese mitten crabs as the research object, and the total arsenic and six major species were determined by high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS). The influence of three common cooking methods on the forms of arsenic and content in different edible parts of crabs were explored. Furthermore, the bioavailability of arsenic and its different forms in the crabs were studied by in vitro gastrointestinal digestion. Based on the risk assessment of arsenic in gastrointestinal digestion, the results showed that the Target Hazard Quotient (THQ) of arsenic was less than 1, which did not pose a significant health risk, but the risk of carcinogenesis of arsenic can not be ignored. Considering the effects of cooking and gastrointestinal digestion into account, a more realistic estimate of the risk associated with the consumption of Chinese mitten crabs can be deciphered.

Speciation and Bio-Imaging of Chromium in Taraxacum officinale Using HPLC Post-column ID-ICP-MS, High Resolution MS and Laser Ablation ICP-MS Techniques.

A new analytical procedure for the speciation of chromium (Cr) in plants by high performance liquid chromatography inductively coupled plasma mass spectrometry (HPLC-ICP-MS) was developed using a strong anion-exchange Mono Q column for the separation of the Cr species. To optimize the analytical procedure, Cr complexes were first synthesized from Cr-nitrate with the addition of an excess of ligand (90°C). Cr-oxalate, Cr-malate, Cr-citrate, Cr-aconitate and Cr-quinate complexes and Cr-nitrate (pH 6.5) were chromatographically separated from Cr(VI) by applying linear gradient elution from 100% water to 100% NH4Cl at a flow rate of 1.5 ml min−1 in 10 min. The column recoveries ranged from 100 to 104%. The exception was Cr-aconitate (column recovery 33%), where a quantitative synthesis was not possible. Good repeatability of the measurements (relative standard deviations better than ± 3%) and low limits of detection (below 0.37 ng ml−1 Cr) were achieved for the individual Cr species. The developed analytical procedure was applied to Cr speciation for dandelions (Taraxacum officinale) grown in soil with a high Cr content and a study of the uptake and metabolism of Cr species in dandelions grown in soil with a low Cr content treated with solutions of Cr(VI) or Cr-nitrate (5000 ng ml−1 Cr, pH 6.5) for 48 h. The separated Cr species were quantified by post-column isotope dilution ICP-MS, while the identification was based on retention times and was also supported by mass spectra obtained with high resolution mass spectrometry (HR-MS). The data indicate that for dandelions grown in Cr-rich soil and that treated with Cr-nitrate (pH 6.5), the Cr was mainly accumulated in the roots, while in plants treated with Cr(VI) (pH 6.5), the Cr was evenly distributed between the roots and the leaves. The Cr species found in dandelion roots and leaves were Cr-aconitate, Cr-malate, and Cr-quinate. The results revealed that Cr(VI) was completely reduced and metabolized to Cr(III) complexes. LA-ICP-MS data showed that the Cr in a leaf of dandelion grown in Cr-rich soil was localized mainly at the apex of the leaf.

Widespread Occurrence of the Highly Toxic Dimethylated Monothioarsenate (DMMTA) in Rice Globally.

Arsenic (As) accumulation in rice is of global concern for human health and international trade. Rice is typically reported to contain inorganic As (iAs) and dimethylated arsenate (DMA), with current food guidelines limiting toxic iAs but not less-toxic DMA. Here, we show that the highly toxic dimethylated monothioarsenate (DMMTA) is also found in rice worldwide and has been unknowingly determined as less-toxic DMA by previous routine analytical methods. Using enzymatic extraction followed by high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) analysis with a C18 column, DMMTA was detected in rice grains (n = 103) from a field survey from China and in polished rice grains (n = 140) from a global market-basket survey. Concentration ranged from <0.20 to 34.8 μg/kg (median 10.3 μg/kg), accounting for 0 to 21% of total As. A strong linear correlation was observed in all rice samples between DMA and DMMTA (being 30 ± 8% of DMA) concentrations. This robust relationship allows an estimation of DMMTA in rice grains from the DMA data reported in previous market-basket surveys, showing a general global geographical pattern with DMMTA concentration increasing from the equator toward high-latitude regions. Based on the global occurrence and potential high toxicity, DMMTA in rice should be considered in health risk assessments and for setting food regulations.

Study on the speciation of arsenic in the genuine medicinal material honeysuckle

Abstract Arsenic (As) accumulated in genuine medicinal materials will not only deteriorate the original medicinal properties of the medicinal materials but also harm the eater’s body. In this study, inductively coupled plasma mass spectrometry (ICP-MS) technology was used to investigate the total As content of honeysuckle in four regions, namely Fengqiu, Henan, Xinmi, Shandong, and Julu, Hebei, as well as the speciation and content of As in the roots, stems, and leaves of honeysuckle. This research shows that the total As content of honeysuckle in the four regions was 0.25–0.3 mg/kg. At 1.5 mol/L H3PO4, 200 W, we performed ultrasonic extraction for 30 min at 60°C and adopted high performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) to analyze the As speciation of honeysuckle plants. The soil As speciation mainly exists in the form of As(v). In the medicinal part of honeysuckle, the amount of different As speciation is ranked in the descending order as As(v) &gt; As(iii) &gt; dimethyl As acid &gt; monomethyl As acid &gt; AsC. As(v) is the main speciation, accounting for 64.5% of the total, followed by the most toxic As(iii), which is 18.8%. As(v) absorbed by the root system of honeysuckle from the soil tends to transform to As(iii) when transported upwards, and the transformation process mainly occurs in the roots.

MIL-125-NH2 catalyzed photochemical vapor generation coupled with HPLC-ICPMS for speciation analysis of selenium

An on-line photochemical vapor generation (PCVG) method for highly sensitive speciation analysis of selenium was proposed by using metal organic framework (MOF) MIL-125-NH2 as a catalyst. When it was coupled with HPLC (high performance liquid chromatography)-ICPMS (inductively coupled plasma mass spectrometry) for Se separation and detection, inorganic selenium species (Se(IV) and Se(VI)) were firstly separated in HPLC with Na2CO3-NaHCO3 as an eluent, and then mixed with MIL-125-NH2 nanoparticles and formic acid in the PCVG reactor to form gaseous selenium-containing species under ultraviolet irradiation, which was introduced into ICPMS for selenium measurement after gas–liquid separation from the reaction solution. Experimental factors of HPLC separation, PCVG reaction and ICPMS detection were carefully investigated. Under the optimized conditions, the limits of detection (LOD) for Se(IV) and Se(VI) were found to be both as low as 0.8 ng/mL. The relative standard deviation (RSD) of Se(IV) and Se(VI) were 4.6% and 3.7% at 20 ng/mL (n = 11), respectively. Certified reference materials and bottled natural mineral water samples were successfully analyzed by the proposed method.