Arsenic Speciation Analysis Research Articles

Trace element contamination in fish impacted by bauxite red mud disposal in the Cassidaigne canyon (NW French Mediterranean)

From 1966 to 2015, the Gardanne alumina refinery discharged some 20 million tons of bauxite residue (called red mud) into the Cassidaigne Canyon (northwest French Mediterranean) with impacts on local ecosystem functioning. Although these red muds contained high levels of trace elements (TE), in particular titanium (Ti), vanadium (V), aluminum (Al) and arsenic (As), surprisingly, their impacts on fish contamination levels and the risk related to fish consumption have been little studied until now. Here, 11 trace elements (Al, As, Cd, Cr, Co, Cr, Mn, Ni, Pb, Ti and V) were analyzed in muscle and, when possible, liver, from 1308 fish of 26 species from an impacted zone in the vicinity of the Cassidaigne Canyon and a reference zone, unaffected by red mud disposals. Moreover, 66 arsenic speciation analyses were performed. Although the impact of human activities on the levels of fish contamination by trace elements is generally not easy to assess in situ because it is blurred by interaction with biological effects, we highlighted significant contamination of the fish species collected from the Cassidaigne Canyon, especially by the main trace elements attributable to the discharges of the Gardanne alumina refinery, namely Al, V and Ti. Moreover, inorganic toxic As concentrations were higher in the impacted zone. The results of this baseline research also confirmed the concern previously raised regarding Hg in Mediterranean organisms and that trace element contamination levels in fish are generally negatively related to fish length for all TE except Hg.

Arsenic Species Analysis at Trace Level by High Performance Liquid Chromatography with Inductively Coupled Plasma Mass Spectrometry

A sensitive and accurate simultaneous continuous analysis for six arsenic species including arsenobetaine (AsB), arsenocholine (AsC), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), arsenite (AsIII), and arsenate (AsV) has been developed by high performance liquid chromatography with inductively coupled plasma mass spectrometry (HPLC-ICP-MS). An anion-exchange column of Hamilton PRP-X100 (Switzerland) was applied for separation of the six arsenic species with gradient elution of 1.25 mmol/L Na2HPO4 and 11.0 mmol/L KH2PO4 as the mobile phase A and 2.5 mmol/L Na2HPO4 and 22.0 mmol/L KH2PO4 as the mobile phase B. The linearity ranges for AsB, AsC, MMA, DMA, AsIII, and AsV were between 0.5 and 50.0 μg/L, and the detection limits of the six arsenic species were all within 0.01–0.35 ng/L. The relative standard deviations (RSDs) were within 2.26–3.68% and the recovery rates of samples ranged from 95 to 103%. The proposed method was applied for the arsenic speciation analysis of sediment pore-water samples, which were taken from the supernatant after centrifugation and filtration.

Replacing fish meal with insect meal in the diet of Atlantic salmon (Salmo salar) does not impact the amount of contaminants in the feed and it lowers accumulation of arsenic in the fillet

ABSTRACTInsects are promising sources of protein and lipid in feeds for farmed animals. In the European Union, the use of insect meal (IM) and insect oil is permitted in fish feed. However, the European Food Safety Authority has highlighted the lack of data regarding the chemical safety of insects and products thereof. In this study, Atlantic salmon (Salmo salar) were fed diets in which fish meal (FM) was partially or fully substituted with IM, resulting in four diets with an FM replacement of 0%, 33%, 66% and 100% by IM. The IM was produced from Black soldier fly (Hermetia illucens) larvae fed media containing 60% seaweed (Ascophyllum nodosum). After 16 weeks of feeding, fish fillet samples were collected. The concentrations of undesirable substances, e.g., heavy metals, arsenic, dioxins, mycotoxins, pesticides, in the IM, the diets and fillets were determined. The concentrations of the analysed compounds in the IM were all below EU maximum levels for feed ingredients, except for arsenic. However, for complete feeds the concentrations of these compounds in the feeds, including arsenic, were all below EU MLs. Arsenic was transferred from seaweed to IM, resulting in arsenic levels in IM similar to what has been documented for FM. Transfer of arsenic from feed to fillet was observed; however, total arsenic concentrations in the fillet significantly decreased when fish were fed diets with more IM and less FM. Arsenic speciation analysis of the diets showed that although total arsenic levels were similar, the arsenic species were different. Arsenobetaine was the major organoarsenic species in the diets containing FM, while in diets containing IM several unidentified arsenic species were detected. The results suggest that the lower feed-to-fillet transfer of arsenic when FM is replaced by IM may be due to the presence of arsenic species with low bioavailability in the IM.

Rapid and robust speciation/quantitative analysis of arsenous acid and related metabolites in serum by liquid chromatography–inductively coupled plasma-tandem mass spectrometry

Arsenic, especially inorganic trivalent species, is one of the most important poisons in the field of forensic toxicology. There are many reports on the speciation analysis of arsenic species in biological specimens by liquid chromatography–inductively coupled plasma-mass spectrometry (LC–ICP-MS). The aim of this study was to develop a rapid and robust analytical method for speciation/quantitative analysis of arsenic species in serum by LC–ICP-tandem mass spectrometry (MS/MS). An analytical method for arsenous acid and its metabolites, dimethylarsinic acid, monomethylarsonic acid, and arsenic acid in serum was tested through the analysis of serum samples by an LC–ICP-MS/MS system consisting of different anion exchange columns and different mobile phases. Rapid pretreatment of serum samples by ultrafiltration was also tested. Robust speciation/quantitative analysis of arsenic in serum samples with LC–ICP-MS/MS was achieved by using a mildly acidic mobile phase. The limits of detection for the four arsenic species were in the range 0.19–0.68 ngAs/mL, and the well-known interference by argon chloride ion was removed by the MS/MS apparatus. This method was precise enough for quantitative analysis of four arsenic compounds in serum (0.24–3.68% precision; 97.0–104% accuracy; and 101–112% recovery for all analytes at 5 and 50 ngAs/mL). The total analytical time was 30 min (20-min pretreatment and 10-min analysis), and multiple serum samples could be pretreated simultaneously. A rapid, sensitive, interference-free and robust speciation/quantitative analysis of toxic arsenous acid and related metabolites in serum by LC–ICP-MS/MS was developed. To our knowledge, this is the first report to use LC–ICP-MS/MS for analysis of arsenic species in human blood/serum samples.

Sequential determination and chemical speciation analysis of inorganic As and Sb in airborne particulate matter collected in outdoor and indoor environments using slurry sampling and detection by HG AAS.

In this work, fast sequential determination and chemical speciation analysis of inorganic arsenic and antimony in airborne particulate matter collected in outdoor and indoor environments using slurry sampling and detection by hydride generation atomic absorption spectrometry (HG-AAS) is proposed. A Doehlert design was applied to optimise the hydride generation conditions of As and Sb for fast sequential determination in the same aliquot of particulate matter samples after preparation of the slurry. The limits of quantification (LoQ) obtained for As and Sb were 0.3 and 0.9 ng m-3, respectively. The accuracy of the analytical method was confirmed by analysis of the certified reference material of urban particulate matter (SRM NIST 1648a), presenting concordance with certified values of 92.7±7.7% for As and 91.2±9.5% for Sb. Precision was expressed as relative standard deviation (% RSD, n=3), with our results presenting values better than 3.4% and 4.2% for total inorganic As and Sb, respectively. For all analysed samples, total As concentrations and its inorganic species were below the LoQ of the analytical method (<0.3 ng m-3). However, the averages of total inorganic Sb concentrations in airborne particulate matter, collected as total suspended outdoor particles (TSPoutdoor), inhalable particulate matter (PM10), and total suspended indoor particles (TSPindoor), were 3.1±0.5, 2.4±0.6, and 2.6±0.4 ng m-3, respectively. Trivalent Sb (Sb3+) was the predominant inorganic species in all samples investigated, with mean percentages of 76%, 72%, and 73% in TSPoutdoor, PM10, and TSPindoor, respectively. The presence of Sb and its predominant inorganic form (Sb3+) can be attributed to vehicular traffic close to the sampled urban areas. Therefore, fast sequential determination of As and Sb and their inorganic species in particulate matter samples prepared as slurry by FS-HG-AAS is an efficient, accurate, and precise method and can be successfully applied to routine analysis.

Arsenic speciation analysis in rice milk using LC-ICP-MS

The consumption of rice milk has increased, mainly by individuals intolerant to lactose or allergic to cow milk. However, rice milk contains As. In this sense, the concentration of As in rice milk should be controlled. In the present study it is proposed a methodology for determination of As(III), dimethylarsenic (DMA), monomethylarsenic (MMA) and As(V) species in rice milk using LC-ICP-MS. The main features of the methodology are fast analysis, easy and simple sample preparation, where the sample is 3-fold diluted in the mobile phase and then filtered. The four arsenic species investigated were detected in the analysed samples, being As(V) the main species. The limit of quantification of the method ranges from 0.25 to 0.43 μg L−1 As. The analyte recovery ranged from 81 to 116% for samples spiked to 1.00 μg L−1 or 5.00 μg L−1 As and the relative standard deviation was better than 5%.

Exposure to microplastics lowers arsenic accumulation and alters gut bacterial communities of earthworm Metaphire californica

Ubiquitous contamination of microplastics and arsenic in soil ecosystems can induce many health issues to nontarget soil organisms, and will also cause many potential threats to the gut bacterial communities of soil fauna. However, the changes in the gut bacterial communities of soil fauna after exposure to both microplastics and arsenic remain unknown. In this study, the toxicity and effects on the gut microbiota of earthworm Metaphire californica caused by the combined exposure of microplastics and arsenic were examined by using arsenic species analysis and high throughput sequencing of gut microbiota. Results showed that total arsenic and arsenic species in the earthworm gut and body tissues after exposure to combination of microplastics with arsenate (As(V)) were significantly different from that treated with As(V) alone. Microplastics lessened the accumulation of total arsenic and the transformation rate of As(V) to arsenite (As(III)). Microplastics alleviated the effect of arsenic on the gut microbiota possibly via adsorbing/binding As(V) and lowering arsenic bioavailability, thus prevented the reduction of As(V) and accumulation of total arsenic in the gut which resulted in a lower toxicity on the earthworm. The study broadens our understanding of the ecotoxicity of microplastics with other pollutants on the soil animals and on their gut microbiota.

Speciation analysis of arsenic in urine samples from APL patients treated with single agent As2O3 by HPLC-HG-AFS

Arsenic trioxide [As2O3, arsenite (AsIII) in solution] has been applied successfully for the treatment of acute promyelocytic leukemia (APL). The arsenic speciation analysis of urine is critical to reveal the metabolic mechanism and the relationship between arsenic species and the clinical response. To characterize the arsenic species in urine, a simple and robust HPLC-HG-AFS method was developed and validated to quantify the levels of arsenic species [AsIII and its metabolites, monomethylarsonic acid (MMAV), dimethylarsinic acid (DMAV), and arsenate (AsV)] in urine samples from 66 patients with APL. Patients received As2O3 (0.16 mg/kg/day) via continuous slow-rate infusion or conventional infusion. Urine samples were collected at steady state before the start of the next daily administration. The relative proportions (median) of arsenic species in urine were: AsIII, 33.00% (IQR: 24.34%–46.82%); DMAV, 36.42% (IQR: 25.82%–51.98%); MMAV, 23.89% (IQR: 19.52%–27.19%); and AsV, 2.22% (IQR: 1.293%–3.665%). The levels and proportions of arsenic species vary widely among individual patients. DMAV and un-metabolized AsIII were the dominant arsenic compounds excreted from the urine of patients with APL treated with As2O3. AsV was the least abundant arsenic species in all urine samples. Good positive correlations were found between the levels and proportions of arsenic species in urine and those in plasma; thus, urinary arsenic can reflect the levels of arsenic in plasma. Urinary arsenic is a critical biomarker to evaluate the metabolism and toxicity of arsenic in the clinical application of As2O3.

Extraction of arsenic(III) in aqueous two-phase systems: A new methodology for determination and speciation analysis of inorganic arsenic

This work utilizes the liquid–liquid extraction technique of aqueous two-phase systems (ATPS) formed by a polymer and electrolyte to develop a novel methodology for the extraction, determination, and speciation analysis of inorganic arsenic. To optimize the methodology, the following parameters were studied: pH of the system, nature of the ATPS-forming electrolyte and the polymer, tie-line length (TLL) of the system, type and concentration of extractants, and the mass ratio of the top and bottom phases. The highest extraction (%E = 98%) was obtained for an ATPS composed of L64 + Na2SO4 + H2O, at pH = 6.00, TLL = 33.55% w/w using the ammonium pyrrolidine dithiocarbamate (APDC) extractant in a molar ratio (APDC/As(III)) of 960, and with a mass ratio of 1/4. In these same conditions, As(V) was not extracted satisfactorily (%E = 18%) to ATPS top phase, with a separation factor equal to 530 after three extractions, showing the great potential of the system for the speciation analysis of inorganic arsenic. Moreover, the method was validated employing HG-ICP OES with a coefficient of determination of 0.9957 and limits of detection and quantification equal to 0.20 μg kg−1 and 0.66 μg kg−1, respectively, proving that the method is capable of detecting the low concentrations required by legislation. The relative standard deviation (RSD) values varied between 4.88 and 9.45%, and the RSD in inter-day precision was 11.07%, which are in accordance with the limits of the validation guide used by the National Institute of Metrology, Quality and Technology, COD-CGCRE-008. Furthermore, relative error rates ranged from −7.44 to 9.90% and recovery percentages were between 92.6 and 110% for the accuracy studies. This method was also applied in a spiked tap water sample, presenting a recovery value equal to 87.10%.

Speciation Analysis of Trace Arsenic, Mercury, Selenium and Antimony in Environmental and Biological Samples Based on Hyphenated Techniques.

In order to obtain a well understanding of the toxicity and ecological effects of trace elements in the environment, it is necessary to determine not only the total amount, but also their existing species. Speciation analysis has become increasingly important in making risk assessments of toxic elements since the toxicity and bioavailability strongly depend on their chemical forms. Effective separation of different species in combination with highly sensitive detectors to quantify these particular species is indispensable to meet this requirement. In this paper, we present the recent progresses on the speciation analysis of trace arsenic, mercury, selenium and antimony in environmental and biological samples with an emphasis on the separation and detection techniques, especially the recent applications of high performance liquid chromatography (HPLC) hyphenated to atomic spectrometry or mass spectrometry.

Multi-functionalization of magnetic graphene by surface-initiated ICAR ATRP mediated by polydopamine chemistry for adsorption and speciation of arsenic

Multi-functionalized magnetic graphene was prepared by surface-initiated initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) mediated by polydopamine chemistry. The obtained multi-functionalized magnetic graphene was used as an adsorbent for application in adsorption and speciation of arsenic. Adsorption kinetics and isotherms of arsenic were investigated by batch adsorption experiments. The adsorbent displayed simultaneous or selective removal ability for As(III) and As(V) within different pH ranges. The adsorption of both As(III) and As(V) agreed well with the Freundlich isotherm model, and they were effectively adsorbed through chelation and electrostatic interaction, respectively. Moreover, the functionalized magnetic graphene was examined as a column packing material for speciation analysis of arsenic using solid phase extraction technique. As(III) and As(V) could be effectively separated through a sequential elution strategy. An alkaline solution was firstly employed to selectively elute As(V), and then an acidic solution was utilized to elute As(III). The developed adsorbent in the present study was successfully applied to the determination of As(III) and As(V) in natural and environmental water samples with satisfactory results.

Occurrence, toxicity, and speciation analysis of arsenic in edible mushrooms

Owing to the strong concentration and biotransformation of arsenic, the influence of some edible mushrooms on human health has attracted widespread attention. The toxicity of arsenic greatly depends on its species, so the speciation analysis of arsenic is of critical importance. The aim of the present review is to highlight recent advances in arsenic speciation analysis in edible mushrooms. We summarized the contents and distribution of arsenic species in some edible mushrooms, the methods of sample preparation, and the techniques for their identification and quantification. Stability of the arsenic species during sample pretreatment and storage is also briefly discussed.

Low-density solvent-based dispersive liquid-liquid microextraction followed by HPLC-ICP-MS for speciation analysis of phenylarsenics in lake water

ABSTRACTA simple and fast method of low-density solvent based dispersive liquid-liquid microextraction (LDS-DLLME) followed by high-performance liquid chromatography-inductively coupled plasma mass spectrometry (HPLC-ICP-MS) has been developed for the speciation analysis of organoarsenic and inorganic arsenic in water samples. The low-density solvent (octanol) was given as the organic phase and injected into the aqueous sample (donor phase) with methanol as the disperser. With As (V), As (III), p-APAA, 4-HPAA, ROX and PAA as target species, factors of LDS-DLLME including pH value, anionic carriers, elution conditions and extractant, were studied in detail. Besides, volumes of solvents were further optimised by response surface methodology. Under the optimal conditions, the limits of detection for four phenylarsenics and arsenate were in the range of 0.001–0.039 μg L−1. The relative standard deviations (RSDs) were 3.6–9.4% and the enrichment factors varied from 6.2 to 70.8. The proposed method of LDS-DLLME-HPLC-ICP-MS was satisfactorily applied to the determination of six arsenic compounds in water samples with recoveries of 81.8–111.7% for the spiked lake water samples.

Arsenic speciation in aerosols of a respiratory therapeutic cave: A first approach to study arsenicals in ultrafine particles

Arsenic is ubiquitous in the environment and of special concern due to its varying toxicity depending on the chemical form present. Less is known about arsenic in air, especially about organoarsenicals, their sources and fate. There is also a lack of knowledge regarding arsenic in airborne nanoparticles that are critical for understanding with respect to human health effects due to their size. Here we show results from an arsenic speciation analysis in size-resolved airborne particles with aerodynamic diameters down to 15 nm. Analysis of aerosols from a respiratory therapeutic cave showed temporarily higher concentrations of trimethylarsine oxide than inorganic arsenic and substantial amounts of organoarsenicals, especially in smaller particles. Our method provides guidance for future studies investigating arsenicals in ultrafine particles and their health implications. Furthermore, the method developed can be used to widely monitor particle-bound organoarsenicals to fully understand the importance of As biovolatilization in the environment.

Establishment of arsenic speciation analysis method and application in rice

Objective: A new ion exchange column technology was used to establish an efficient and sensitive method for the detection of inorganic arsenic. Methods: Based on the new As Specia Fast Column, the pretreatment methods, liquid phase separation and mass spectrometry determination conditions of inorganic arsenic in rice were optimized. Finally, arsenic compounds were separated by As Specia Fast Column and detected by liquid chromatography inductively coupled plasma mass spectrometry. The external standard method was used for quantitative analysis. The detection limit, precision and accuracy of the method were determined by measuring the content of arsenic compounds in rice samples and rice standard samples. At the same time, three Guangdong rice samples were selected as the experimental samples of this study, and 1 g of each sample was weighed and measured in parallel three times. The method was compared with the method of liquid chromatography-atomic fluorescence spectrometry (LC-AFS) and liquid chromatography-inductively coupled plasma mass spectrometry (LC-ICP-MS) in the national standard. Results: The inorganic arsenic in rice was extracted with 0.5% nitric acid solution at 65 ℃ for 15 h, and the pH was adjusted to alkaline. The mobile phase A (8 mmol/L HNO(3), 50 mmol/L NH(3)·H(2)O) and mobile phase B (40 mmol/L HNO(3), 80 mmol/L NH(3)·H(2)O) were used as the mobile phase gradient elution (93%) . Five arsenic compounds can reach baseline separation under the conditions of RF power of 1 500 W and atomization gas flow of 0.97 L/min. The detection limits ranged from 0.114 to 0.331 μg/L, and the inorganic arsenic content in rice samples ranged from 0.063 to 0.232 mg/kg. The results of determination of arsenic compounds in rice flour reference materials were all within the uncertainty range indicated by the standard. The recoveries were 86.7%~106.7%, and the precision was 1.9%-12.5%. Compared with national standards, the results of determination of arsenate in rice were relatively close (using this method, LC-AFS, LC-ICP-MS to detect the content of arsenate in rice samples 1 was 0.231, 0.226, 0.236 mg/kg, respectively). However, due to insufficient sensitivity, the national standard method is difficult to detect low levels of arsenic compounds (Arsenobetaine was not detected in rice sample 1). The method can detect the content of arsenobetaine in rice sample 1 was 0.023 mg/kg. Conclusion: The established method can meet the requirements of inorganic arsenic determination in rice, and it is more rapid and accurate than the current national standard. It can better monitor and evaluate the content of i-As in rice, and provide accurate data for comprehensively grasping and evaluating the safety of rice consumption of residents.

Preparation of thiol- and amine-bifunctionalized hybrid monolithic column via “one-pot” and applications in speciation of inorganic arsenic

A thiol- and amine-bifunctionalized organic-inorganic hybrid monolithic column was prepared for the first time via one-pot co-condensation of 3-mercaptopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane and tetraethylorthosilicate, and utilized for separation and enrichment of inorganic arsenic species. Various parameters of solid phase microextraction (SPME) operation and analytical performance were also investigated systematically. Under the optimum condition, both As(III) and As(V) can be adsorbed over a wide pH range (3.0–8.0) and eluted in turn, in which 3% HNO3 (v/v) was firstly used to selectively release As(V), and then 3% HNO3 with 0.01 mol L−1 KIO3 or 15% mercaptosuccinic acid (MSA) (m/v) to selectively release As(III). Meanwhile, the elution mechanism of As(III) and As(V) was elucidated comprehensively, and notably, the novel eluent, HNO3 + MSA, was recommended for eluting As(III). Therefore, the thiol- and amine-bifunctionalized organic-inorganic hybrid monolithic column as an ideal SPME matrix for the speciation analysis of arsenic in environmental waters has the merits of facile preparation, low cost, high adsorption capacity and selective desorption. In addition, compared with thiol- and amine-bifunctionalized mesoporous silica, the bifunctional hybrid monolith based SPME protocol with less time and reagent consumption is promising to be applied not only to filed sampling but also to on-line analysis.

Analysis of Arsenic Species in Processed Rice Bran Products Using HPLC-ICP-MS.

This study could provide analysis necessary of As for defining an accurate risk assessment of products and tablets containing rice bran powder. In addition with this study, the regulations for As contents in rice bran power products would be set.

Speciation analysis of inorganic and organic arsenic in Canadian seafoods by chemical separation and neutron activation

A new method consisting of methanol–methyl isobutyl ketone (MIBK)–water extraction and open-column cation exchange chromatography followed by HPLC was developed for the separation of total, residual, lipid-soluble, and five water soluble arsenic species including AsB, MMA, DMA, As(III), and As(V) in selected Canadian seafood samples. The mass fractions of arsenic were determined by neutron activation analysis with a detection limit of less than 20 µg kg−1. The method was validated by analyzing reference materials. The MIBK phase contained most of the lipid-soluble arsenic and indicated a linear relationship between the lipid content and lipid-soluble arsenic.

An online preconcentration system for speciation analysis of arsenic in seawater by hydride generation flame atomic absorption spectrometry

In this paper, an on-line preconcentration system has been proposed for speciation analysis of inorganic arsenic in seawater. It is based on the selective reaction of As(III) with ammonium pyrrolidine dithiocarbamate (APDC) followed by sorption of the formed complex under a minicolumn containing polytetrafluoroethylene (PTFE). Afterward, arsenic sorbed has been eluted using a 2 mol L−1 hydrochloric acid solution. The preconcentration system was optimized employing multivariate techniques. A two-level full factorial design and a Doehlert matrix were performed to determining the critical conditions of the factors: the acidity of the sample, APDC concentration, and sample flow rate. So, the procedure using the optimized conditions allows the determination of As(III) with limits of detection and quantification of 0.02 and 0.07 μg L−1. Total arsenic has been determined after reduction of As(V) using thiourea in acid media and the limits achieved were 0.03 and 0.09 μg L−1, for detection and quantification, respectively. The precision estimated as the relative standard deviation (RSD) was 5.3%, which was calculated using seven replicates of As(III) solution with a concentration of 0.50 μg L−1. The accuracy of the method was confirmed by the analysis of the certified reference material CASS-4 seawater furnished by the National Research Council of Canada-NRCC. The system proposed was employed for speciation analysis of arsenic in five seawater samples collected from Todos os Santos Bay, Salvador, Brazil. The As(III) contents obtained varied from 0.09 to 0.51 and the total arsenic contents varied from 0.20 to 0.66 μg L−1. The results are in agreement with other data reported in the literature.

Bioaccessibility and risk assessment of heavy metals, and analysis of arsenic speciation in Cordyceps sinensis

BackgroundCordyceps sinensis (C. sinensis) is a famous and precious Traditional Chinese Medicine (TCM), while frequent reports of heavy metals, especially arsenic, exceeding standards in C. sinensis in recent years have raised concerns of its safety. Therefore, it is urgent for a research on heavy metals (Cu, Pb, As, Cd, Hg) in C. sinensis, of its bioaccessibility, dietary exposure estimation, arsenic speciation analysis and health risks assessment to human body.MethodsThree 30 g batches of mixed wild growth C. sinensis samples were collected from Qinghai Province and each batch were divided into three parts: the whole C. sinensis, the stroma and the caterpillar body. The in vitro gastrointestinal method was used to evaluate the bioaccessibility of the heavy metals in the samples. The arsenic speciation analysis in the in vitro gastrointestinal solutions and dilute nitric acid extracted solutions were conducted using high performance liquid chromatography–inductively coupled plasma mass (HPLC–ICP-MS) method. Finally, the target hazard quotient (THQ) developed by the US EPA (1989) was used to assess the health risks of heavy metals in C. sinensis.ResultsThe contents of Cu, Pb, Cd and Hg in the stroma were higher than those in the caterpillar body. In contrast, As was mainly found in the caterpillar body. In the whole C. sinensis, the average bio-accessibilities of Cu, Pb, As, Hg and Cd were 41.29, 40.11, 64.46, 18.91, and 81.14%, respectively. While in the caterpillar body, the corresponding bio-accessibilities values were 48.26, 42.92, 66.15, 12.86, 87.07%, respectively, and were 38.30, 30.53, 30.18, 7.46, and 82.30%, respectively in the stroma part. Different arsenic speciations of arsenite [As(III)], arsenate [As(V)] and trace amounts of methylarsonic acid [MMA] were detected. Of the total As, 8.69% was in inorganic form, which was also the major form of dissolved As. Among the extracted inorganic species, the concentrations of As(III) and As(V) were 0.56 ± 0.16 and 0.29 ± 0.06 mg kg−1, respectively. In the gastrointestinal solutions, only As(III) and As(V) could be detected; the sum content of the two species was 2.00–2.73%. The bioaccessibility target hazard quotient (BTHQ) values for Cu, Pb, As, Cd and Hg in C. sinensis were 0.0041, 0.0040, 0.5334, 0.0020 and 0.0005, respectively, all less than 1.ConclusionNone of the five heavy metals in C. sinensis can be 100% absorbed by human body. The content of arsenic in C. sinensis is high, but the strong toxic inorganic arsenic accounted for only 8.69%. The heavy metals in C. sinensis presented no obvious risks to human health in a reasonable taking way.