Arsenic Speciation Analysis Research Articles

Growth substrate limitation enhances anaerobic arsenic methylation by Paraclostridium bifermentans strain EML.

Microbial arsenic methylation is established as a detoxification process under aerobic conditions (converting arsenite to monomethylated arsenate) but is proposed to be a microbial warfare strategy under anoxic conditions due to the toxicity of its main product, monomethylarsonous acid (MMAs(III)). Here we leveraged a paddy soil-derived anaerobic arsenic methylator, Paraclostridium bifermentans strain EML, to gain insights into this process. Strain EML was inoculated into a series of media involving systematic dilutions of Reinforced Clostridial Broth (RCB) with 25 µM arsenite to assess the impact of growth substrate concentration on arsenic methylation. Growth curves evidenced the sensitivity of strain EML to arsenite, and arsenic speciation analysis revealed the production of MMAs(III). Concentrations of MMAs(III) and arsenic methylation gene (arsM) transcription were found to be positively correlated with RCB dilution, suggesting that substrate limitation enhances arsM gene expression and associated anaerobic arsenic methylation. We propose that growth substrate competition among microorganisms may also contribute to an increase in anaerobic arsenic methylation. This hypothesis was further evaluated in an anaerobic co-culture system involving strain EML and either wild-type Escherichia coli K-12 MG1655 (WT) or E. coli expressing the MMAs(III)-resistance gene (arsP) (ArsP E. coli). We observed increased MMAs(III) production in the presence of E. coli than its absence and growth inhibition of WT E. coli to a greater extent than ArsP E. coli, presumably due to the MMAs(III) produced by strain EML. Collectively, our findings suggest an ecological role for anaerobic arsenic methylation, highlighting the significance of microbe-microbe competition and interaction in this process.IMPORTANCEMicrobial arsenic methylation is highly active in rice paddy fields under flooded conditions, leading to increased accumulation of methylated arsenic in rice grains. In contrast to the known detoxification process for aerobic arsenic methylation, the ecological role of anaerobic arsenic methylation remains elusive and is proposed to be an antibiotic-producing process involved in microbial warfare. In this study, we interrogated a rice paddy soil-derived anaerobic arsenic-methylating bacterium, Paraclostridium bifermentans strain EML, to explore the effect of growth substrate limitation on arsenic methylation in the context of the microbial warfare hypothesis. We provide direct evidence for the role of growth substrate competition in anaerobic arsenic methylation via anaerobic prey-predator co-culture experiments. Moreover, we demonstrate a feedback loop, in which a bacterium resistant to MMAs(III) enhances its production, presumably through enhanced expression of arsM resulting from substrate limitation. Our work uncovers the complex interactions between an anaerobic arsenic methylator and its potential competitors.

Direct ion chromatographic method for speciation micro analysis of arsenic forms in industrial samples with “rich” matrix composition

The speciation analysis of arsenic has consistently been a subject of great interest. However, it remains challenging to analyze complex matrix samples that contain both arsenic and interfering components. In this case, it can be hard to choose the right combinations of different instrumental methods, or a separation method followed by detection, which is usually done using a spectral approach (hybrid methods). In the production control of copper electrorefining, the determination of the concentration of As (III) and As (V) helps to improve the quality of the cathode copper produced. This work investigated the possibility of directly determining both arsenic forms and total As in an electrolyte bath using ion chromatography (IC) with conductometric detection. The use of the ion chromatographic approach for the determination of As(V) in complex matrix samples such as copper electrolyte must take into account the presence of potential interferences from anions such as sulphates, sulfites, selenites, selenates, etc. The results revealed that the method is accurate and precise, with As(V) quantification limits of 15 µg.L-1 and detection limits of 5 µg.L-1. This method is suitable for assessing various types of arsenic in the production of electrolytic copper, with the aim of replacing the current technique that requires liquid-liquid extraction and ICP-OES detection. This led to the following improvements: Enhanced efficiency: The method eliminates the need for extensive and time-consuming sample preparation for the initial separation of arsenic forms. At the same time, the method's characteristics are comparable to those of ICP-OES with liquid-liquid extraction, which is often used in the speciation analysis of arsenic. The method is environmentally friendly as it avoids the use of organic and poisonous extractants. The method can simultaneously analyze other anions (PO43-, SO42-, F-, Cl-, etc.) with arsenates with appropriate calibration.

Arsenic speciation analysis in human urine for long term epidemiological studies: The Multi-Ethnic Study of Atherosclerosis (MESA)

Arsenic is a ubiquitous toxic metalloid causing serious health problems. Speciation analysis of arsenic in human urine provides valuable insights for large-scale epidemiological studies and informs on sources of exposure as well as human metabolism. The Multi-Ethnic Study of Atherosclerosis (MESA) is a valuable cohort for assessing chronic low-moderate arsenic exposure and health effects in an ethnically diverse US population. We present a state-of-the-art arsenic speciation analysis methodology and its application to 7677 MESA spot urine samples based on high-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry. This method is fast, robust and detects a total of 11 individual As species at method detection limits of 0.02–0.03 μg arsenic/L urine for each individual species. Our analytical approach features excellent mean method accuracy (98%) and precision (5%) for the main arsenic species in urine (arsenobetaine, methylarsonic acid, dimethylarsinic acid, and total inorganic As); intra- (3–6%) and inter-day coefficients of variability (5–6%); column recovery (96 ± 7%); and spike recovery (97 ± 6%). The main arsenic species were detectable in ≥95% of urine samples due to the implementation of an oxidation step. Each individual minor arsenic species was detectable in ≤25% of all urines, although at least one of them was detected in almost half the participants. We identified two minor urinary arsenic species as dimethylarsinoylacetic acid and dimethylarsinoylpropionic acid, potential metabolites of seafood-related arsenicals. We observed differences in individual As species excretion by race/ethnicity, with Asian-American participants featuring 3–4 times higher concentrations compared to other participants. We also found differences by site, body mass index, smoking status, rice intake, and water arsenic levels, potentially indicating different exposures or related to individual bio-metabolism. The proposed approach is suitable for epidemiological studies and the collected data will constitute the base for future research on potential health effects of chronic low-level arsenic exposure.

Facilitating inorganic arsenic speciation and quantification in waters: Polymer inclusion membrane preconcentration and X-ray fluorescence detection

BackgroundArsenic, classified as a priority pollutant and human carcinogen by the IARC, is subject to stringent regulatory limits in food and water. Among various arsenic species found in water samples, arsenite (As(III)) is identified as the most toxic form. Given the limitations of conventional spectroscopic techniques in speciation analysis, there is a crucial need for innovative and sustainable methodologies that enable arsenic speciation. Simplifying these methodologies is essential for widespread applicability and effective environmental monitoring. ResultsThis study proposes a simple and cost-effective analytical methodology for speciating inorganic arsenic in water samples. The method involves extracting As(III) into a polymer inclusion membrane (PIM) containing the extractant Cyanex 301 (bis(2,4,4-trimethylpentyl) dithiophosphinic acid), followed by analysis using energy dispersive X-ray fluorescence (EDXRF) spectrometry. The concentration of arsenate was measured after a reduction step using a thiosulfate/iodide mixture. This simple methodology allows a limit of quantification for trivalent arsenic (2 μg L−1), which is well below the World Health Organization's recommended maximum permissible level of As in drinking water (10 μg L−1). The method that is developed allows the determination of As at trace levels in waters with naturally occurring arsenic. Significance and noveltyThis study represents a significant advance in the field, providing a novel and efficient methodology for arsenic speciation analysis in water samples. By combining the advantages of polymer inclusion membrane (PIM) extraction with energy dispersive X-ray fluorescence (EDXRF) spectrometry, this study offers a cost-effective and environmentally friendly approach to address the critical issue of arsenic contamination in water sources, thereby contributing to enhanced environmental monitoring and public health protection.

Quantification of arsenic in real samples using a spectrophotometric cloud point extraction of the formed ion pair with astrazon orange G

A novel cloud-point extraction (CPE) procedure for the determination of ultra-trace amounts of arsenic species in real samples, purchased from the local market by spectrophotometer was developed. Inorganic arsenic species analysis in water, beverages, and foods has become increasingly important in recent years, as arsenic species are considered carcinogenic and are assessed at significant levels in samples. The technique is established on a selective ternary complex of As(V) with astrazon orange G (AOG+) in the presence of tartaric acid and polyethylene glycol tertoctylphenyl ether (Triton X-114) at pH 4.0. The calibration curve developed within range 3.0–160 ng/mL with a correlation coefficient of 0.9988 for As(V) provided a preconcentration factor of 200 and a limit of detection (3S blank/m) of 0.88 ng/mL under optimum investigation conditions. The results of molar absorptivity and Sandell sensitivity are calculated and found to be 4.38 × 105 L/mol cm and 0.018 ng cm−2, respectively. The statistical treatment of data obtained from the proposed and GF-AAS procedures are compared in terms of Student’s t-tests and variance ratio F-tests has revealed no significant differences. The methodology has been effectively confirmed by assessing real samples and comparing it to the GF-AAS method statistically.

Advanced electrochemical detection of arsenic using platinum-modified boron-doped diamond by anodic stripping voltammetry

Background: Platinum-modified boron-doped diamond (BDD) electrodes were effectively fabricated through a combination of wet seeding and electrodeposition techniques. Methods: This research involved the utilization of various chemicals and apparatus, the modification of boron-doped diamond (BDD) electrodes with platinum using wet seeding and electrodeposition, and the detection of As3+ and As5+ using a phosphate buffer solution and anodic stripping voltammetry (ASV). Findings: Characterization using Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS) confirmed the successful deposition of 1.54% platinum on the BDD surface. These modified electrodes were employed as sensors for arsenic species (As³⁺ and As⁵⁺) using anodic stripping voltammetry (ASV) in a 0.1 M phosphate buffer solution at pH 6. Under optimal conditions, including a deposition potential of -500 mV, a deposition time of 150 s, and a scan rate of 200 mV/s, the linear detection of As³⁺ and As⁵⁺ was achieved within a concentration range of 0 to 100 ppb (R² = 0.9797 and 0.9903, respectively). Prior to ASV detection of As⁵⁺, a pretreatment step involving the addition of 0.1 M NaBH₄ was necessary to reduce As⁵⁺ to As³⁺. The detection limits for As³⁺ and As⁵⁺ were determined to be 16.50 ppb and 8.19 ppb, respectively. Conclusion: This research highlights the potential of BDD/Pt electrodes in environmental monitoring and arsenic detection applications and demonstrates the method's efficacy for the speciation analysis of arsenic species. Novelty/Originality of this Study: This research pioneers the use of platinum-modified boron-doped diamond electrodes for the speciation analysis of arsenic, offering a promising new approach for environmental monitoring applications.

Unveiling New Arsenic Compounds in Plants via Tailored 2D-RP-HPLC Separation with ICP and ESI MS Detection.

Arsenic (As) speciation analysis is scientifically relevant due to the pivotal role the As chemical form plays in toxicity, which, in turn, directly influences the effect it has on the environment. The objective of this study was to develop and optimize a method tailored for studying As compounds in plant samples. Different extraction procedures and HPLC methods were explored to assess their efficiency, determine mass balance, and improve the resolution of compounds in the chromatograms. Conventionally applied anion-exchange chromatography facilitated the separation of well-documented As compounds in the extracts corresponding to 19 to 82% of As present in extracts. To gain insight into compounds which remain undetectable by anion chromatography (18 to 81% of As in the extracts), but still possibly metabolically relevant, we explored an alternative chromatographic approach. The procedure of sample purification and preconcentration through solid-phase extraction, facilitating the detection of those minor As compounds, was developed. The system was further refined to achieve an online 2D-RP-HPLC system, which was employed to analyze the extracts more comprehensively with ICP and ESI MS. Using this newly developed method, As(III)-phytochelatins, along with other arseno-thio-compounds, were detected and identified in extracts derived from the tree roots of seedlings grown in the presence of As(III) and As(V), and a group of arseno lipids was detected in the roots of plants exposed to As(V).

Simultaneous microwave digestion for total arsenic and inorganic arsenic in local shrimp and prawn commodities of Brunei Darussalam for regulatory and safety monitoring

The data gap in food safety regulations have created misinformation leading to the rejection of commodities for trade. The evidence presented is the local regulation of arsenic in sea produce which is based on total arsenic, tAs, instead of toxic inorganic arsenic, iAs. Furthermore, tAs data in animal origin seafood has been widely proven to be dominated by the non-toxic Arsenobetaine, AsB. Therefore, if arsenic regulatory limit was set based only on tAs without reference to iAs data, seafood products might be wrongfully rejected for trade because of non-compliance to tAs limit. We provided analysis of tAs and iAs of 14 local prawn and shrimp commodities from three shrimp/prawn sector namely aquaculture (n = 3), capture (n = 5) and processed (n = 6) using effective extraction, as well as, a fit-for-purpose analytical method for iAs. A HVG-AAS method was developed and validated for iAs with LoQ of 1.6 ppb, analytical range of 0–6 ppb, repeatability RSDr of 0.5–3.1 %, coefficient of determination R2 of 0.9975, and percentage recovery of 90.9 %, while an existing method using ICP-MS was used to verify the tAs. Based on the AOAC Official Method 999.10 2005 with minor adjustments, seafood samples were digested with concentrated nitric acid and hydrogen peroxide under pressure in a closed vessel heated by a microwave digester. An additional step for iAs determination was necessary to ensure compatibility in HVG-AAS analysis. Further subdivision of the aquaculture and capture samples was done by dividing them into 3 fractions, namely head, flesh and peel. Comparison of tAs in all the three fractions indicated that for aquaculture sector, the highest tAs were found in the flesh (2nd highest in % weight) whereas for the capture sector, the highest amount of tAs correlated with the highest % weight of the fraction. On regulatory aspects, speciation analysis on the iAs indicated samples with quantifiable iAs value were in-compliance despite tAs were initially found to be higher than the national limits. Risk assessment of iAs indicated there were no risk for human daily intake based on the BDML0.5 value of 3.0 μg/kg b.w per day for an average 70 kg man. All findings concluded the need for doing arsenic speciation analysis of iAs along with tAs for routine monitoring of prawn/shrimp samples and to revise the local limits from tAs to iAs particularly for seafood commodities.

Dynamic Stomach Model-Capillary Electrophoresis-ICPMS for Evaluation of Release and Transformation Behaviors of Arsenic Species from Microplastics during Digestion.

Microplastics (MPs) can act as carriers of environmental arsenic species into the stomach with food and release arsenic species during digestion, which threatens human health. Herein, an integrated dynamic stomach model (DSM)-capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICPMS) is developed for online monitoring of the release and transformation behaviors of arsenic species loaded on MPs (As-MPs) in the simulated human stomach. The 3D-printed DSM with a soft stomach chamber enables the behaviors of gastric peristalsis, gastric and salivary fluid addition, pH adjustment, and gastric emptying (GE) to be controlled by a self-written program after oral ingestion of food with As-MPs. The gastric extract during digestion is introduced into the spiral channel to remove the large particulate impurity and online filtered to obtain the clarified arsenic-containing solution for subsequent speciation analysis of arsenic by CE-ICPMS. The digestion conditions and pretreatment processes of DSM are tracked and validated, and the release rates of As-MPs digested by DSM are compared with those digested by the static stomach model and DSM without GE. The release rate of inorganic arsenic on MPs is higher than that of organic arsenic throughout the gastric digestion process, and 8% of As(V) is reduced to As(III). The detection limits for As(III), DMA, MMA, and As(V) are 0.5-0.9 μg L-1 using DSM-CE-ICPMS, along with precisions of ≤8%. This present method provides an integrated and convenient tool for evaluating the release and transformation of As-MPs during human gastric digestion and provides a reference for exploring the interactions between MPs and metals/metalloids in the human body.

Speciation analysis of arsenic in honey using HPLC-ICP-MS and health risk assessment of water-soluble arsenic

It is well known that arsenic is one of the most toxic elements. However, measuring total arsenic content is not enough, as it occurs in various forms that vary in toxicity. Since honey can be used as a bioindicator of environmental pollution, in the present study the concentration of arsenic and its species (As(III), As(V), DMA, MMA and AsB) was determined in honey samples from mostly Poland and Ukraine using HPLC-ICP-MS hyphenated technique. The accuracy of proposed methods of sample preparation and analysis was validated by analyzing certified reference materials. Arsenic concentration in honey samples ranged from 0.12 to 13 μg kg-1, with mean value of 2.3 μg kg-1. Inorganic arsenic forms, which are more toxic, dominated in honey samples, with Polish honey having the biggest mean percentage of inorganic arsenic species, and Ukrainian honey having the lowest. Furthermore, health risks resulting from the consumption of arsenic via honey were assessed. All Target Hazard Quotient (THQ) values, for total water-soluble arsenic and for each form, were below 1, and all Carcinogenic Risk (CR) values were below 10-4, which indicates no potential health risks associated with consumption of arsenic via honey at average or recommended levels.

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.

Ion chromatography – nitrogen-sustained microwave inductively coupled atmospheric pressure plasma – mass spectrometry (IC-MICAP-MS) for arsenic speciation analysis in rice

Ion chromotagraphy is coupled to a nitrogen-sustained Microwave Inductively Coupled Atmospheric-Pressure Plasma Mass Spectrometer (MICAP-MS) for arsenic speciation analysis in rice.

Arsenic speciation analysis in cow's milk and plant-based imitation milks by HPLC-ICP-MS

Imitation milks based on vegetables have become relevant in recent years as a substitute for cow´s milk. Total and inorganic content of arsenic (As) determination in food is of utmost importance due to toxicological concerns. This study aimed to (1) optimize and validate a methodology for speciation analysis using anion exchange high performance liquid chromatography coupled to plasma mass spectrometry and (2) analyze the arsenic content in milk and imitation milks. Determination of As (III) and As (V) was done following a simple and innovative treatment, which consisted on the dilution of a small volume of sample in mobile phase and further filtration. Furthermore, acid microdigestion for total As determination with small amounts of acid and sample was optimized. The detection limits of the method ranged from 0.2 to 0.7 µg L−1. Regarding to arsenic content we found that imitation milks based on peanuts and nuts presented the lowest inorganic As content (between 1.7 and 1 µg L−1) whereas the highest values were found in imitations based on soy, rice and vetch (27.3, 13 and 8 µg L−1, respectively). The cow’s milk presented intermediate levels of inorganic As (4 µg L−1). Also, almond- and quinoa-based imitation milks showed inorganic As values below detection limits, so these imitation milks may be the safest to consume with respect to arsenic content.

Application of the liquid-liquid extraction method and subsequent icp-ms detection for speciation analysis of arsenic in wastewater samples

The current paper describes a method for determining As(III) and As(V) concentrations in wastewater samples. The approach is based on the extraction of As(III) from water samples using a non-polar organic solvent in a 10-12 M HCl medium. The extract contains As(III), while the raffinate contains As(V). Distilled water can be used to re-extract As(III) from the organic solvent. ICP-MS was used to analyze As concentrations in the reextract and the raffinate. The average recovery of arsenic by the proposed method is 99.6 %. It was calculated as the sum of As(III) and As(V) concentrations. The collected data demonstrated high repeatability. The standard addition procedure demonstrated the selectivity and accuracy of the employed method. The relative error of recovery of the standard As(III) addition is about 2 %, which is similar to the RSD found under repeatability conditions.

Speciation analysis of inorganic arsenic in water samples using thiol-ligand and cotton fibres followed by ICP-OES determination

ABSTRACT This research aimed to develop a method for the speciation analysis of arsenic species, including As(III) and As(V) in environmental samples. Cotton fibres and thiol-ligands, including ammonium pyrrolidine dithiocarbamate (APDC), L-cysteine, and diethyldithiocarbamic acid (DDTC), were used as a simple solid phase extraction (SPE) followed by arsenic determination using inductively coupled plasma optical emission spectrometry (ICP-OES). The separation parameters were thoroughly investigated, including pH, thiol-ligand concentration, cotton fibre amount, type of eluents, and flow rate. It was found that As(III) could be efficiently separated from As(V) by using a column containing 0.5 g cotton fibres and 0.1% APDC under pH 2. As(III) was then eluted using 5 mL of mixed solvents of 4 M HNO3, 4 M HCl, and 0.5 M H2O2 (1:1:1 v/v). The method was then used to perform a speciation analysis of arsenic in model solutions with As(III) and As(V) concentrations ranging from 10–1000 μg/L. The results showed good recoveries of both arsenic species at 80–120% with a satisfactory percentage relative standard deviation (%RSD). The developed method was subsequently applied for arsenic speciation analysis in the environmental samples, including natural and wastewater samples.

Spray assisted preconcentration method combined with HPLC – Continuous flow hydride generation – FAAS for inorganic arsenic speciation in olive oil samples

Speciation analysis of arsenic in edible oils is an important topic in terms of the assessment of its risks for human health and the quality of edible oils. In this study, high performance liquid chromatography – continuous flow hydride generation – flame atomic absorption spectrometry (HPLC-CFHG-FAAS) system after vortex assisted reverse phase spray-based fine droplet formation liquid phase microextraction (VA-RP-SFDF-LPME) method was proposed to qualify/quantify arsenite and total arsenic. Limit of detection (LOD) and limit of quantification (LOQ) for arsenite were calculated as 2.86 µg kg–1 (as As) and 9.52 µg kg–1 (as As), respectively. After the extraction/preconcentration process, a prereduction was carried out in the presence of 0.010 mol/L HCl (containing 0.39% L-cysteine) with heat (90 ± 5 oC) for the determination of total arsenic content while arsenite was directly determined via the developed system. Recovery for arsenite and total inorganic arsenic were in the range of 91.5 – 120.4% and 90.0 – 104.4%, respectively. The developed method is proposed for the analysis of olive oil samples containing inorganic arsenic species. This is the first study to carry out the inorganic arsenic speciation in olive oil by HPLC-CFHG-FAAS system after the preconcentration of the species by the VA-RP-SFDF-LPME system. For the matrix including arsenite and arsenate, the developed method can be safely used to find the concentration of both species accurately.

Determination of Arsenic Species in Edible Insects by LC-ICP-MS.

Edible insects may contain arsenic. Analysis of arsenic species is necessary in order to accurately assess arsenic exposure. An analytical method was validated and used to determine and quantitate arsenic species in edible insects. Arsenic species were extracted from edible insects by heating at 100 °C in 0.3 mol/L nitric acid. The concentration of arsenic species was then determined by liquid chromatography inductively coupled plasma mass spectrometry (LC-ICP-MS) using an octadecylsilane (ODS) column with a mobile phase containing an ion-pair reagent. The limit of detection (0.007-0.012 mg/kg), limit of quantitation (0.021-0.038 mg/kg), repeatability (1.2-3.2%), intermediate precision (2.8-4.5%), and trueness (recoveries 97-102% based on spiked samples) of the proposed method were satisfactory for inorganic arsenic, dimethylarsinic acid, and arsenobetaine in edible insects. Total arsenic was detected in all samples obtained in Japan (Asian forest scorpion, diving beetles, giant water bug, grasshoppers, June beetles, mole crickets, male rhino beetle, female rhino beetle, sago worms, and silkworm pupae) and consisted of mostly inorganic arsenic. Beetles in particular showed relatively high levels. Arsenic content varies among edible insect species. Feed control is important, as arsenic concentrations in edible insects may be feed dependent. Arsenic species in edible insects were analyzed by LC-ICP-MS using an ODS column with a mobile phase containing an ion-pair reagent. Inorganic arsenic was detected in most samples, with concentrations ranging from <0.04 to 29.3 mg/kg.

Bioaccumulation and Human Health Risk Assessment of Arsenic and Chromium Species in Water–Soil–Vegetables System in Lephalale, Limpopo Province, South Africa

The accumulation of potentially toxic elements (PTEs) in water, soil and vegetables can pose a severe threat to the respective organisms and lead to human health risks upon exposure. Water, soil and vegetable samples were collected from the Mokolo River and its vicinity. Total concentration quantification and speciation analysis of chromium (Cr) and arsenic (As) were performed using inductively coupled plasma-mass spectrometry (ICP-MS) and high-performance liquid chromatography hyphenated to inductively coupled plasma-mass spectrometry (HPLC-ICP-MS), respectively. The total concentrations of Cr and As were below the maximum permissible levels (MPLs) set by the World Health Organization (WHO) and South Africa’s Department of Water Affairs and Forestry (DWAF) for drinking water. The soil quality guideline value of 64.0 µg/g for Cr was surpassed in most sites and posed a great risk to the vegetables growing in it, whereas the guideline value of 12.0 µg/g for As was surpassed in one sampling site. The observed high concentrations in soil could be linked to the use of fertilizers and atmospheric deposits introduced through coal burning by power stations. In vegetables, the total Cr concentration surpassed the recommended MPL of 0.5 µg/g, rendering the vegetables unsafe for human consumption. Concentrations ranging from 197 to 1180 ng/g and 374 to 17400 ng/g were detected for Cr(VI) and Cr(III), respectively. The consumption of vegetables containing high levels of Cr and As would result in health risks in adults and children as the total hazard quotient (THQ) exceeded 1. The consumption of some vegetables particularly by children could cause serious health risks as the THQ &gt; 10 was observed for some Cr-contaminated vegetables. The incremental lifetime cancer risk (ILCR) threshold of 1 × 10−4 was exceeded, indicating that the overall consumption of vegetables had high cancer risks for adults and children. This study suggests that the consumption of vegetable samples would lead to health risks in the population.

A facile and automated microfluidic electrochemical platform for the in-field speciation analysis of inorganic arsenic

An automated microfluidic electrochemical platform was developed for the rapid in-field analysis of arsenic speciation. Herein, we integrated an electrochemical sensing and microfluidic channel for the simultaneous determination of As(III) and total inorganic As (total iAs) within a single device. The platform was fabricated by assembling a gold nanoparticle-modified screen-printed graphene electrode (AuNP/SPGE) on a hydrophilic polyethylene terephthalate (PET) sheet that was specially designed to enclose a microfluidic channel with dual flow channels for separate determination of the two species. While As(III) can be promptly detected with the AuNP/SPGE on one end, thioglycolic acid stored in glass fiber is employed on the other end to reduce As(V) before being electrochemically analyzed on the AuNP/SPGE as total iAs; the difference represents the amount of As(V). With a wireless potentiostat and a smartphone equipped with Bluetooth technology, the overall procedure can be fully automated and accomplished merely within 9 min. The linear ranges for the determination of As(III) and total iAs were found to be 50–1000 and 100–1500 ng/mL with detection limits of 3.7 and 17 ng/mL, respectively. The proposed method was validated and applied for the inorganic As speciation of various food samples with satisfactory results compared to those obtained with the standard HPLC-ICP‒MS protocol. This novel microfluidic electrochemical platform offers numerous advantages, notably for its simplicity, speed, low cost, and portability for on-site analysis, which conclusively makes it a highly promising analytical device for the speciation of inorganic arsenic.

Association between mediterranean diet and metal(loid) exposure in 4-5-year-old children living in Spain.

Even relatively low levels of metals exposure may impact health, particularly among vulnerable populations such as infants and young children. However, little is known about the interplay between simultaneous metal exposures, common in real-life scenarios, and their association with specific dietary patterns. In this study, we have evaluated the association between adherence to Mediterranean diet (MD) and urinary metal concentrations individually and as an exposure mixture in 713 children aged 4-5-years from the INMA cohort study. We used a validated food frequency questionnaire to calculate two MD indexes scores: aMED and rMED. These indexes gather information on various food groups within the MD and score differently. To measure urinary concentrations of cobalt, copper, zinc, molybdenum, selenium, lead, and cadmium as exposure biomarkers, we used inductively coupled plasma mass spectrometry (ICP-MS), coupled with an ion chromatography (IC) equipment for arsenic speciation analysis. We applied linear regression and quantile g-computation, adjusted for confounders, to analyse the association between MD adherence and exposure to the metal mixture. High adherence to MD such as the quintile (Q) 5 MD was associated with higher urinary arsenobetaine (AsB) levels than Q1, with β values of 0.55 (confidence interval - CI 95% 0.01; 1.09) for aMED and 0.73 (CI 95% 0.13; 1.33) for rMED. Consumption of fish was associated with increased urinary AsB but reduced inorganic arsenic concentrations. In contrast, the aMED vegetables consumption increased urinary inorganic arsenic content. A moderate level of adherence to MD (Q2 and Q3) was associated with lower copper urinary concentrations than Q1, with β values of −0.42 (CI 95% −0.72; −0.11) for Q2 and -0.33 (CI 95% −0.63; −0.02) for Q3, but only with aMED. Our study, conducted in Spain, revealed that adhering to the MD reduces exposure to certain metals while increasing exposure to others. Specifically, we observed increase in exposure to non-toxic AsB, highlighting the significance of consuming fish/seafood. However, it is crucial to emphasize the necessity for additional efforts in reducing early-life exposure to toxic metals, even when adhering to certain food components of the MD.