Clinimetallomics: Arsenic Speciation in Urine from Patients With Arsenism by HPLC-ICP-MS

Clinimetallomics is proposed as a branch of metallomics that focuses on the study of the metallome in clinical samples of urine, blood, and tissues. As the clinical diagnosis of arsenic poisoning is mainly based on the concentration of total arsenic in urine, the toxicity of arsenic varies greatly in different speciation. Analysis of arsenic speciation with excessive total arsenic in urine can provide a basis for precise treatment. It can also be used to understand the fate of arsenic in the body of patients with arsenic poisoning after treatment with sodium dimercaptopropane sulfonate. In this study, a HPLC-ICP-MS method was established for the determination of arsenic species in urine samples from patients diagnosed with arsenism. Use the established method to detect urine samples, which can be directly assayed after simple sample dilution with 20 mmol/L EDTA-2Na. With the concentration of arsenic speciation in the range of 1.0~100.0 ng/mL, the linear correlation coefficient was higher than 0.99996. The recoveries were between 92.4% and 109.0%. The precision of the concentration and retention time (n = 3) were less than 3.0% and 0.3%, respectively, and the detection limit was between 1.42 ng/mL and 1.86 ng/mL. This method can be applied to arsenic speciation in the urine of healthy people, in patients treated for arsenic poisoning, and in patients diagnosed with arsenism.

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Fast Determination of Arsenic Species and Total Arsenic in Urine by HPLC-ICP-MS: Concentration Ranges for Unexposed German Inhabitants and Clinical Case Studies

Journal of Analytical Toxicology ◽

10.1093/jat/32.4.308 ◽

2008 ◽

Vol 32 (4) ◽

pp. 308-314 ◽

Cited By ~ 34

Author(s):

P. Heitland ◽

H. D. Koster

Keyword(s):

Case Studies ◽

Clinical Case ◽

Arsenic Species ◽

Total Arsenic ◽

Fast Determination ◽

Icp Ms ◽

Clinical Case Studies

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Effect of arsenosugar ingestion on urinary arsenic speciation

Clinical Chemistry ◽

10.1093/clinchem/44.3.539 ◽

1998 ◽

Vol 44 (3) ◽

pp. 539-550 ◽

Cited By ~ 106

Author(s):

Mingsheng Ma ◽

X Chris Le

Keyword(s):

Arsenic Speciation ◽

Inorganic Arsenic ◽

Sample Pretreatment ◽

Arsenic Species ◽

Urine Samples ◽

Standard Reference Materials ◽

Dimethylarsinic Acid ◽

Urinary Arsenic ◽

Biomarkers Of Exposure

Abstract We developed and evaluated a method for the determination of μg/L concentrations of individual arsenic species in urine samples. We have mainly studied arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid (MMAA), and dimethylarsinic acid (DMAA) because these are the most commonly used biomarkers of exposure by the general population to inorganic arsenic and because of concerns over these arsenic species on their toxicity and carcinogenicity. We have also detected five unidentified urinary arsenic species resulting from the metabolism of arsenosugars. We combined ion pair liquid chromatography with on-line hydride generation and subsequent atomic fluorescence detection (HPLC/HGAFS). Detection limits, determined as three times the standard deviation of the baseline noise, are 0.8, 1.2, 0.7, and 1.0 μ/L arsenic for arsenite, arsenate, MMAA, and DMAA, respectively. These correspond to 16, 24, 14, and 20 pg of arsenic, respectively, for a 20-μL sample injected for analysis. The excellent detection limit enabled us to determine trace concentrations of arsenic species in urine samples from healthy subjects who did not have excess exposure to arsenic. There was no need for any sample pretreatment step. We used Standard Reference Materials, containing both normal and increased concentrations of arsenic, to validate the method. Interlaboratory studies with independent techniques also confirmed the results obtained with the HPLC/HGAFS method. We demonstrated an application of the method to the determination of arsenic species in urine samples after the ingestion of seaweed by four volunteers. We observed substantial increases of DMAA concentrations in the samples collected from the volunteers after the consumption of seaweed. The increase of urinary DMAA concentration is due to the metabolism of arsenosugars that are present in the seaweed. Our results suggest that the commonly used biomarkers of exposure to inorganic arsenic, based on the measurement of arsenite, arsenate, MMAA, and DMAA, are not reliable when arsenosugars are ingested from the diet.

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Arsenic Speciation Analysis in Human Saliva

Clinical Chemistry ◽

10.1373/clinchem.2007.092189 ◽

2008 ◽

Vol 54 (1) ◽

pp. 163-171 ◽

Cited By ~ 47

Author(s):

Chungang Yuan ◽

Xiufen Lu ◽

Nicole Oro ◽

Zhongwen Wang ◽

Yajuan Xia ◽

...

Keyword(s):

Mass Spectrometry ◽

Drinking Water ◽

Arsenic Speciation ◽

Speciation Analysis ◽

Arsenic Species ◽

Skin Lesions ◽

Human Saliva ◽

Dimethylarsinic Acid ◽

The Mean

Abstract Background: Determination of arsenic species in saliva is potentially useful for biomonitoring of human exposure and studying arsenic metabolism. Arsenic speciation in saliva has not been reported previously. Methods: We separated arsenic species in saliva using liquid chromatography (LC) and quantified them by inductively coupled plasma mass spectrometry. We further confirmed the identities of arsenic species by LC coupled with electrospray ionization tandem mass spectrometry. These methods were successfully applied to the determination of arsenite (AsIII), arsenate (AsV), and their methylation metabolites, monomethylarsonic acid (MMAV), and dimethylarsinic acid (DMAV), in >300 saliva samples collected from people who were exposed to varying concentrations of arsenic. Results: The mean (range) concentrations (μg/L) in the saliva samples from 32 volunteers exposed to background levels of arsenic were AsIII 0.3 [not detectable (ND) to 0.7], AsV 0.3 (ND to 0.5), MMAV 0.1 (ND to 0.2), and DMAV 0.7 (ND to 2.6). Samples from 301 people exposed to increased concentrations of arsenic in drinking water showed detectable AsIII in 99%, AsV in 98%, MMAV in 80%, and DMAV in 68% of samples. The mean (range) concentrations of arsenic species in these saliva samples were (in μg/L) AsIII 2.8 (0.1–38), AsV 8.1 (0.3–120), MMAV 0.8 (0.1–6.0), and DMAV 0.4 (0.1–3.9). Saliva arsenic correlated with drinking water arsenic. Odds ratios for skin lesions increased with saliva arsenic concentrations. The association between saliva arsenic concentrations and the prevalence of skin lesions was statistically significant (P <0.001). Conclusions: Speciation of AsV, AsIII, MMAV, and DMAV in human saliva is a useful method for monitoring arsenic exposure.

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Sample Preparation and Storage Can Change Arsenic Speciation in Human Urine

Clinical Chemistry ◽

10.1093/clinchem/45.11.1988 ◽

1999 ◽

Vol 45 (11) ◽

pp. 1988-1997 ◽

Cited By ~ 75

Author(s):

Jörg Feldmann ◽

Vivian W-M Lai ◽

William R Cullen ◽

Mingsheng Ma ◽

Xiufen Lu ◽

...

Keyword(s):

Human Urine ◽

Arsenic Speciation ◽

Speciation Analysis ◽

Arsenic Species ◽

Urine Samples ◽

Dimethylarsinic Acid ◽

Detection Techniques ◽

Monomethylarsonic Acid ◽

The Stability ◽

And Storage

Abstract Background: Stability of chemical speciation during sample handling and storage is a prerequisite to obtaining reliable results of trace element speciation analysis. There is no comprehensive information on the stability of common arsenic species, such as inorganic arsenite [As(III)], arsenate [As(V)], monomethylarsonic acid, dimethylarsinic acid, and arsenobetaine, in human urine. Methods: We compared the effects of the following storage conditions on the stability of these arsenic species: temperature (25, 4, and −20 °C), storage time (1, 2, 4, and 8 months), and the use of additives (HCl, sodium azide, benzoic acid, benzyltrimethylammonium chloride, and cetylpyridinium chloride). HPLC with both inductively coupled plasma mass spectrometry and hydride generation atomic fluorescence detection techniques were used for the speciation of arsenic. Results: We found that all five of the arsenic species were stable for up to 2 months when urine samples were stored at 4 and −20 °C without any additives. For longer period of storage (4 and 8 months), the stability of arsenic species was dependent on urine matrices. Whereas the arsenic speciation in some urine samples was stable for the entire 8 months at both 4 and −20 °C, other urine samples stored under identical conditions showed substantial changes in the concentration of As(III), As(V), monomethylarsonic acid, and dimethylarsinic acid. The use of additives did not improve the stability of arsenic speciation in urine. The addition of 0.1 mol/L HCl (final concentration) to urine samples produced relative changes in inorganic As(III) and As(V) concentrations. Conclusions: Low temperature (4 and −20 °C) conditions are suitable for the storage of urine samples for up to 2 months. Untreated samples maintain their concentration of arsenic species, and additives have no particular benefit. Strong acidification is not appropriate for speciation analysis.

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Determination of Toxic Elements and Arsenic Species in Salted Foods and Sea Salt by ICP–MS and HPLC–ICP–MS

ACS Omega ◽

10.1021/acsomega.1c01273 ◽

2021 ◽

Author(s):

In Min Hwang ◽

Hee Min Lee ◽

Hae-Won Lee ◽

Ji-Hye Jung ◽

Eun Woo Moon ◽

...

Keyword(s):

Toxic Elements ◽

Arsenic Species ◽

Sea Salt ◽

Icp Ms

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Determination of total arsenic and arsenic speciation in tobacco products: from tobacco leaf and cigarette smoke

Journal of Analytical Atomic Spectrometry ◽

10.1039/c0ja00268b ◽

2011 ◽

Vol 26 (8) ◽

pp. 1633 ◽

Cited By ~ 22

Author(s):

Sutthinun Taebunpakul ◽

Chuan Liu ◽

Christopher Wright ◽

Kevin McAdam ◽

Julien Heroult ◽

...

Keyword(s):

Cigarette Smoke ◽

Arsenic Speciation ◽

Total Arsenic ◽

Tobacco Products ◽

Tobacco Leaf

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Contribution of organic arsenic species to total arsenic measurements using ferrihydrite-backed diffusive gradients in thin films (DGT)

Environmental Chemistry ◽

10.1071/en11057 ◽

2012 ◽

Vol 9 (1) ◽

pp. 55 ◽

Cited By ~ 12

Author(s):

Heléne Österlund ◽

Mikko Faarinen ◽

Johan Ingri ◽

Douglas C. Baxter

Keyword(s):

Thin Films ◽

Natural Waters ◽

Arsenic Speciation ◽

Inorganic Arsenic ◽

Speciation Analysis ◽

Arsenic Species ◽

Future Studies ◽

Organic Arsenic ◽

Arsenic Determination ◽

Diffusive Gradients

Environmental contextBoth the mobility and toxicity of arsenic in natural waters are related to the aqueous species distribution. Passive sampling using ferrihydrite-backed diffusive gradients in thin films (DGT) devices has in previous studies been characterised to measure labile inorganic arsenic, and the possible contribution of organic species has been disregarded. This study shows that the two most prevalent organic arsenic species might be included in DGT measurements, which should be taken into consideration when evaluating DGT data in future studies. AbstractIn previous publications discussing arsenic determination using ferrihydrite-backed diffusive gradients in thin films (DGT) devices, organic arsenic forms have been disregarded, even though it is known that the two most prevalent in natural waters, dimethylarsinate (DMA) and monomethylarsonate (MMA), may adsorb to ferrihydrite and thereby be included in the measurement. In this work the accumulation of DMA and MMA, as well as inorganic arsenite and arsenate, to ferrihydrite-backed DGT devices was investigated. It could be demonstrated that MMA, and under acidic conditions also DMA, adsorbed to the binding layer and might therefore contribute to the total mass of measured arsenic. Diffusion coefficients were measured for all four species to enable quantification of DGT-labile concentrations of organic and inorganic arsenic. Elution of the analytes from the ferrihydrite binding layer was performed using 1 mL of 1 M NaOH to facilitate arsenic speciation analysis using chromatographic separation. Average recovery rates were between 87 and 108 %. This study shows that the contribution of DMA and MMA to the total accumulated mass must be taken into consideration when evaluating DGT data in future studies.

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