scholarly journals Effect of arsenosugar ingestion on urinary arsenic speciation

1998 ◽  
Vol 44 (3) ◽  
pp. 539-550 ◽  
Author(s):  
Mingsheng Ma ◽  
X Chris Le

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.

2021 ◽  
Vol 42 (5) ◽  
Author(s):  
Huiling Li

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.


Circulation ◽  
2016 ◽  
Vol 133 (suppl_1) ◽  
Author(s):  
Kalaivani Sivakumar ◽  
Demilade Adedinsewo ◽  
Anekwe Onwuanyi

Background: Heart failure is a major contributor to morbidity and mortality in the United States. Arsenic, a ubiquitous element, found in drinking water, rice, flour and other grains, has been shown to play a role in the development of arrhythmias and coronary heart disease through vascular endothelial dysfunction and free radical injury. Studies have shown that arsenic induces interstitial myocardial fibrosis and we hypothesize that this may contribute to the development of heart failure. Methods: We conducted an analysis of the National Health and Nutrition Examination Survey (NHANES) 2011-2012. Urinary arsenic was evaluated as a combination of inorganic arsenic, and methylated arsenic species (Monomethylarsonic acid and Dimethylarsinic acid) in microgram per gram of urine creatinine. We used a logistic regression model to evaluate the relationship between quartiles of urinary arsenic and heart failure while controlling for confounders. Analyses were conducted using SAS survey procedures and data evaluated at α=0.05. Results: The total number of study participants were 2065 adults with the mean age of 40.2 years, approximately half were male (48.8%) and 64.1% were white. There was no significant association between urinary arsenic measures and incidence of heart failure. Persons with high arsenic levels (>75th percentile) were less likely to develop heart failure after controlling for confounders. Conclusion: Our results show a statistically significant decrease in the odds of developing heart failure among persons with high arsenic levels (>24ug/g). This is in contrast to other studies, which have shown high arsenic levels to have a toxic effect on the heart. Limitations of our study include the inability to determine the chronicity of exposure and exclude persons with increased levels of organic arsenic from seafood, which are nontoxic. Additional observational and prospective studies are needed to further evaluate this association.


1985 ◽  
Vol 4 (2) ◽  
pp. 203-214 ◽  
Author(s):  
M.A. Lovell ◽  
J.G. Farmer

Trends in the urinary concentrations of the four arsenic species, pentavalent [As (V)] and trivalent [As (III)] inorganic arsenic, monomethylarsonic acid (MMAA) and dimethylarsinic acid (DMAA), were followed for several days subsequent to the acute intoxication of two human subjects by arsenic trioxide [As (III)2O3] and sodium orthoarsenate [Na2HAs(V)O4.7H2O], respectively, in unsuccessful suicide attempts. Total arsenic concentrations ranged from 1.6 to 18.7 mg/l. The increasing predominance of the less toxic methylated species, especially DMAA, after 3 or 4 days supports the concept of methylation as a natural detoxification mechanism as part of an overall reduction/methylation sequence involved in the biotransformation of inorganic arsenic by the human body. However, the additional possibility of oxidation of As(III) to As(V) in vivo under extreme immediate postingestion conditions is suggested by initial high urinary As(V) after arsenic trioxide intoxication. Relative proportions of As(V), As(III), MMAA and DMAA in both cases probably reflect species-dependent differences in rates of direct elimination and reactivity with tissues as well as the efficiency of methylation.


2008 ◽  
Vol 54 (1) ◽  
pp. 163-171 ◽  
Author(s):  
Chungang Yuan ◽  
Xiufen Lu ◽  
Nicole Oro ◽  
Zhongwen Wang ◽  
Yajuan Xia ◽  
...  

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.


1999 ◽  
Vol 45 (11) ◽  
pp. 1988-1997 ◽  
Author(s):  
Jörg Feldmann ◽  
Vivian W-M Lai ◽  
William R Cullen ◽  
Mingsheng Ma ◽  
Xiufen Lu ◽  
...  

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.


1999 ◽  
Vol 45 (2) ◽  
pp. 301-306 ◽  
Author(s):  
Larbi Benramdane ◽  
Michele Accominotti ◽  
Laurent Fanton ◽  
Daniel Malicier ◽  
Jean-Jacques Vallon

Abstract The aim of this investigation was to study the distribution of arsenic species in human organs following fatal acute intoxication by arsenic trioxide. The collected autopsy samples of most organs were ground and dried, and the total arsenic was measured by electrothermal atomic absorption spectrometry (ETAAS). The arsenic species—inorganic arsenic, in the form of arsenite [As(III)] and arsenate [As(V)], and its metabolites [monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA)]—were quantified by ETAAS after extraction with methanol/water (1:1, by volume) and separation by HPLC. The results indicate that after acute intoxication, the liver and kidneys show the highest concentrations of total arsenic and that the total concentration in blood is 7- to 350-fold less concentrated than in organs. In all organs, As(III) is the predominant species, and MMA is more concentrated than DMA. MMA and DMA are more prevalent in lipidic organs (49% of total arsenic) compared with other organs (25% of total arsenic). As(V) was found in small quantities in the liver, kidneys, and blood.


Environments ◽  
2020 ◽  
Vol 7 (9) ◽  
pp. 68
Author(s):  
Min-hyuk Kim ◽  
Junseob Kim ◽  
Chang-Hyun Noh ◽  
Seogyeong Choi ◽  
Yong-Sung Joo ◽  
...  

Seaweed, a popular seafood in South Korea, has abundant dietary fiber and minerals. The toxicity of arsenic compounds is known to be related to their chemical speciation, and inorganic arsenic (iAs) is more detrimental than other species. Due to the different toxicities of the various chemical forms, speciation analysis is important for evaluating arsenic exposure. In this study, total arsenic (tAs) and six arsenic species (arsenite, arsenate, monomethylarsonic acid, dimethylarsinic acid, arsenobetaine, and arsenocholine) were analyzed in 180 seaweed samples. Although there were differences between seaweed species, the concentration of tAs was detected at levels ranging from 1 to 100 µg/g, and the distribution of six arsenic species differed depending on the seaweed species. No correlation between the concentration of iAs and tAs was found in most seaweed species. Through statistical clustering, hijiki and gulfweed were seen to be the seaweeds with the highest ratios of iAs to tAs. Using the iAs concentration data from the arsenic speciation analysis, a risk assessment of seaweed intake in South Korea was conducted. The margin of exposure values showed no meaningful risk for the general population, but low levels of risk were identified for seaweed consumers, with high intakes of gulfweed and hijiki.


2018 ◽  
Vol 8 (19) ◽  
Author(s):  
Tom Murphy ◽  
Kongkea Phan ◽  
Emmanuel Yumvihoze ◽  
Kim Irvine ◽  
Ken Wilson ◽  
...  

Background. Arsenic bioaccumulation in rice is a global concern affecting food security and public health. Objective. The present study examined arsenic species in rice in Cambodia to characterize health risks with rice consumption and to clarify uncertainties with Codex guidelines. Methods. The present study collected 61 well water samples, 105 rice samples, 70 soil samples, and conducted interviews with 44 families in Preak Russey near the Bassac River and Kandal Province along the Mekong River in Cambodia. Analyses of metals, total arsenic and arsenic species were conducted in laboratories in Canada, Cambodia and Singapore. Results. Unlike in Bangladesh, rice with the highest total arsenic concentrations in Cambodia contains mostly organic arsenic, dimethylarsinic acid (DMA), which is unregulated and much less toxic than inorganic arsenic. The present study found that storing surface runoff in ditches prior to irrigation can significantly reduce the arsenic concentration in rice. It is possible to remove > 95% of arsenic from groundwater prior to irrigation with natural reactions. Conclusions. The provision of high quality drinking water in 2015 to Preak Russey removed about 95% of the dietary inorganic arsenic exposure. The extremes in arsenic toxicity that are still obvious in these farmers should become less common. Rice from the site with the highest documented levels of arsenic in soils and water in Cambodia passes current Codex guidelines for arsenic. Informed Consent. Obtained Competing Interests. The authors declare no competing financial interests.


1994 ◽  
Vol 77 (2) ◽  
pp. 441-445 ◽  
Author(s):  
O Jimenez de Blas ◽  
S Vicente Gonzalez ◽  
R Seisdedos Rodriguez ◽  
J Hernandez Mendez

Abstract A flow injection–hydride generation/atomic absorption spectroscopic method for the measurement of total urinary arsenic and for the selective determination of inorganic arsenic, monomethylarsonic acid (MMAA), and dimethylarsinic acid (DMAA) was developed. Destruction of the organic matrix is necessary to measure total arsenic content of urine samples. Digestion of this matrix with HNO3–H2SO4–H2O2 is described. The separation of inorganic, monomethylated, and dimethylated arsenic compounds in urine was performed with ion-exchange chromatography on AG 50 W-X8 resin. Detection limits of 2 ppb for each arsenic form and of 3 ppb for total arsenic in urine analyzed after mineralization were found. Recoveries in triplicate urine samples spiked with 10 ppb inorganic arsenic, 20 ppb MMAA, and 40 ppb DMAA were 93, 91, and 85%, respectively. The precision (relative standard deviation) of the method obtained in 10 replicate analyses of urine samples spiked with arsenic metabolites varied from 3.2 to 4.6%. This method is applicable to urine samples in studies relating to arsenic exposure and its monitoring.


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