Objectives The purpose of this study was to determine a separation method for each arsenic metabolite in urine by using a high performance liquid chromatography (HPLC)-inductively coupled plasma-mass spectrometer (ICP-MS). Methods Separation of the arsenic metabolites was conducted in urine by using a polymeric anion-exchange (Hamilton PRP X-100, $4.6mm{\times}150mm$, $5{\mu}m$) column on Agilent Technologies 1260 Infinity LC system coupled to Agilent Technologies 7700 series ICP/MS equipment using argon as the plasma gas. Results All five important arsenic metabolites in urine were separated within 16 minutes in the order of arsenobetaine, arsenite, dimethylarsinate, monomethylarsonate and arsenate with detection limits ranging from 0.15 to $0.27{\mu}g/L$ ($40{\mu}L$ injection). We used G-EQUAS No. 52, the German external quality assessment scheme and standard reference material 2669, National Institute of Standard and Technology, to validate our analyses. Conclusions The method for separation of arsenic metabolites in urine was established by using HPLC-ICP-MS. This method contributes to the evaluation of arsenic exposure, health effect assessment and other bio-monitoring studies for arsenic exposure in South Korea.
Arsenic (As) is a well-known human carcinogen and its dietary exposure has been found to be the major route of entry into general population. This study was performed to assess the body levels of As and their associated factors in Korean adults by analyzing total As in urine. Urine and blood samples were collected from 580 adults aged 20 years and older, who had not been exposed to As occupationally. Demographic information was collected with the help of a standard questionnaire, including age, smoking, alcohol intake, job profiles, and diet consumed in the last 24 hrs of the study. Total As, sum of As(III), As(V), monomethylarsonic acid (MMA), dimethylarsinic acid (DMA), in urine was determined using atomic absorption spectrometer involving hydride generation method. The geometric mean concentration of total As in urine was $7.10{\mu}g/L$. Urine As was significantly higher in men ($7.63{\mu}g/L$) than in women ($6.75{\mu}g/L$). Age, smoking, alcohol consumption, and job profiles of study subjects did not significantly affect the concentration of As in urine. No significant relationship was observed between body mass index (BMI), Fe, and total cholesterol in serum and urinary As. Urine As level was positively correlated with seaweeds, fishes & shellfishes, and grain intake. A negative correlation between urinary As level and HDL-cholesterol in serum and meat intake was observed. Overall, these results suggest that urinary As concentration could be affected by seafood consumption. Therefore, people who frequently consume seafood and grain need to be monitored for chronic dietary As exposure.
A noble method for pre-concentration and speciation of ultra trace As (III) and As (V) in urine and whole blood samples based on dispersive liquid-liquid microextraction (DLLME) has been developed. In this method, As (III) was complexed with ammonium pyrrolidine dithiocarbamate at pH = 4 and Then, As (III) was extracted into the ionic liquid (IL). Finally, As (III) was back-extracted from the IL with hydrochloric acid (HCl) and its concentration was determined by flow injection coupled with hydride generation atomic absorption spectrometry (FI-HGAAS). Total amount of arsenic was determined by reducing As (V) to As (III) with potassium iodide (KI) and ascorbic acid in HCl solution and then, As (V) was calculated by the subtracting the total arsenic and As (III) content. Under the optimum conditions, for 5-15 mL of blood and urine samples, the detection limit ($3{\sigma}$) and linear range were achieved 5 ng $L^{-1}$ and 0.02-10 ${\mu}g\;L^{-1}$, respectively. The method was applied successfully to the speciation and determination of As (III) and As (V) in biological samples of multiple sclerosis patients with suitable precision results (RSD < 5%). Validation of the methodology was performed by the standard reference material (CRM).
Health complaints among vinylhouse workers in Sungjoo county, Kyungpook province led to the investigation of heavy metal levels of air, soil and humans as well as physical conditions of the vinylhouse. The average temperature and humidity inside the vinylhouse were 8 higher and 10% point lower, respectively, as compared to the outside. While discomfort index(D. I.) outside was pleasant level(69.2), D. I. inside was 82 at which point 100% of people feels discomfort. Cadmium concentration of soils inside the vinylhouse(0.116 mg/kg) was 1.8 times higher than the soils outside. Arsenic concentration of soils inside the vinylhouse(4.882 mg/kg) was only slightly higher than the soils outside(4.182 ng/kg). However, both heavy metal concentrations detected in soils inside or outside the vinylhouse were within the normal range. Analysis of 10 air samples taken inside the vinylhouse showed that only one sample had a cadmium concentration above the detectable level and the rest of samples were below the detectable levels. While there were no difference of arsenic concentrations in urine between male and female, cadmium concentrations in urine samples of female (3.31 ug/l) was slightly higher than male(2.38 ug/l). Age-dependent increases of cadmium concentrations in urine samples were also observed. However, there was no concentration difference of these heavy metals in urine between vinylhouse workers and non-vinylhouse workers. Urine concentrations of cadmium and arsenic detected from vinylhouse workers or non-vinylhouse workers were within the normal range. The present study represents a first attempt to evaluate physical and environmental risk factors of the vinylhouse affecting the vinylhouse farmer's health. The study revealed that, while physical conditions of the vinylhouse such as temperature and humidity are the possible factors associated with the farmer's complaints, environmental contamination as judged from heavy metal levels in soil, air and humans is not a risk factor contributing to the vinylhouse farmer's health problem.
The purpose of the present study was to examine the pharmacokinetic characteristics of arsenic hexaoxide($As_4O_6$), a novel anticancer compound, after i.v. bolus and oral administration in rats. We developed an ICP-Mass based method to analyze arsenic hexaoxide levels in plasma, bile, urine, feces, and tissue and validated the method. Arsenic hexaoxide rapidly disappeared from the plasma by 10 min($\alpha$ phase) after i.v. administration, which was followed by the late disappearance in the $\beta$ phase. The mean plasma half-lives($t_{1/2}$) of arsenic hexaoxide at the a and $\beta$ phase when administered at a dose of 5 mg/kg were 1.57 and 29.8 min, respectively. The maximum plasma concentration($C_{max}$) was 230 ng/mL, after oral administration of arsenic hexaoxide at a dose of 50 mg/kg. The bioavailability, which was calculated from the dose-adjusted ratio, of the oral administered arsenic hexaoxide was 1.61%. Of the various tissues tested, arsenic hexaoxide was mainly distributed in the spleen, lung, liver and kidney after oral administration. Arsenic hexaoxide levels in the spleen or lung at 24 hr after oral administration were higher than those of maximum plasma concentration($C_{max}$). The cumulative amounts of arsenic hexaoxide found in the urine by 48 hr after the administration of 50 mg/kg were 5-fold higher than those in the bile. However, the cumulative amounts in the feces were 10-fold higher compared with those of urine, suggesting that arsenic hexaoxide is mostly excreted in the feces. In conclusion, our observations indicated that arsenic hexaoxide was poorly absorbed from the gastro-intestinal tract to the blood circulation and transferred to tissues such as the spleen and lung at 24 hr after oral administration. Moreover, the majority of arsenic hexaoxide appears to be excreted in the feces by 48 hr after oral administration.
This study analyzed the concentration of the heavy metals(Cd, Hg, iAs) of urine(n=576) from May, 2007 to Oct 2007. The subject was residents in G, Y, H industrial area, Jeollanam-do, in which exposure due to the adjacency of the industrial complex. As to the heavy metal concentration in the urine of the residents in the whole exposed region and the comparing region, the content of cadmium, mercury, and inorganic arsenic in the exposed region group were 1.23, 1.85, and 8.80 ${\mu}g$/g_ct respectively, and those of the comparing region group were 1.87, 2.00, and 8.93 ${\mu}g$/g_ct respectively, which indicates that the concentration of the comparing group was higher than that of the exposed group. The heavy metal concentration for each age group increased in proportion to age except those under 10 for some substances(p<0.01). As to geometric mean concentration cadmium and inorganic arsenic in urine according to the smoking history of the subject, the concentration of the smoking group and the non-smoking group were 1.65 ${\mu}g$/g_ct and 9.13 ${\mu}g$/g_ct respectively, while those of the non-smoking group were 1.47 ${\mu}g$/g_ct and 8.91 ${\mu}g$/g_ct respectively, which indicates that the former is higher than the latter. As to the inorganic arsenic concentration in urine according to the food preference, in order of vegetable, fish, and meat showed high concentration (p<0.01). To clarify the factors affecting the heavy metal concentration in urine among the subjects, the multiple regression analysis was conducted. As a result, it turned out that as to cadmium content in urine, gender, age, drinking, and smoking have influence on the subjects, with explanatory adequacy of 37.5 %.
Arsenic poisoning has three types of poisoning. First, acute arsenic poisoning is usually caused by oral intake of large amount of arsenic compound with purpose of homicide or suicide. Second, chronic arsenic poisoning is caused by inhalation of arsenic in the occupational setting or by long-term oral intake of arsenic-contaminated well water. Third, arsine poisoning occurs acutely when impurities of arsenic in non-ferrous metal react with acid. Clinical manifestation of acute arsenic poisoning is mainly gastrointestinal symptoms and cardiovascular collapse. Those of chronic poisoning are skin disorder and cancer. Arsine poisoning shows massive intravascular hemolysis and hemoglobinuria with acute renal failure. Exposure evaluation is done by analysis of arsenic in urine, blood, hair and nail. Species analysis of arsenic is very important to evaluate inorganic arsenic acid and mono methyl arsenic acid (MMA) separated from dimethyl arsenic acid (DMA) and trimethyl arsenic acid (TMA) which originate from sea weed and sea food. Treatment with dimercaprol (BAL) is effective in acute arsenic poisoning only.
The simultaneous determination of As(III), As(V), and DMA has been performed by ion chromatography (IC) coupled with inductively coupled plasma-mass spectrometry (ICP-MS). The separation of the three arsenic species was achieved by an anionic separator column (AS 7) with an isocratic elution system. The separated species were directly detected by ICP-MS as an element-selective detection method. The IC-ICP-MS technique was applied for the determination of arsenic species in a NIST SRM 1643d water sample. An As(III) only was detected in the sample. The detection limits of As(III), As(V) and DMA were 0.31, 0.45, and 2.09 ng/mL, respectively. It was also applied for the determination of arsenic species in a human urine obtained by a volunteer, and three arsenic species were identified. The determination of total As in human urines that were obtained from 25 volunteers at the different age was also carried out by ICP-MS.
Objectives: The purpose of this study was to evaluate the relationship between residential surroundings, such as a power plant, steel mill and petrochemical facilities, and urinary arsenic concentrations in Chungcheongnam-do Province, Korea. Methods: Stratified by fish consumption and residential district, median and maximum block sampling was applied. A total of 346 spot urine samples were speciated for $As^{5+}$, $As^{3+}$, monomethylarsonic acid(MMA), dimethylarsonic acid (DMA) and arsenobetaine (AsB). Exposure assessment was based on questionnaires including data on sex, age, current tobacco use, fish consumption, type of water consumed, and occupational category. Results: Urinary $As^{5+}+As^{3+}+MMA+DMA$ concentrations of people living in the vicinity of a power plant ($GM=50.39{\mu}g/g$) were 61% higher than those of people living in the inland area according to median block sampling. Urinary $As^{5+}+As^{3+}+MMA+DMA+AsB$ concentrations of people living in the vicinity of industrial complex area were higher than those of people living in the inland area according to block sampling by median and maximum. Conclusion: Urinary arsenic concentrations of people living in vulnerable areas such as around industrial complexes, especially power plants, were higher than those of people living in an inland area.
Objectives: The main purpose of this study is to produce background data which can be compared with data on vulnerable areas such as industrial complexes in Ulsan, SihwaBanwol, Gwangyang, Yeosu, Pohang, Cheongju and Daesan in Korea. Methods: This study was performed on 1,007 local residents in Gangneung using personal questionnaires and medical check-up. Environmental pollutants including heavy metals in blood and urine were analyzed and the results are as follows. Results: According to the results of medical check-up, 705 subjects were "Normal (A and B)", 232 subjects were "Disease doubtful (R1)" and 70 subjects were "High blood pressure or Diabetes doubtful (R2)". Regarding geometric mean concentration, blood lead was 1.57 ${\mu}g/dL$, urine cadmium was 0.82 ${\mu}g/g-cr$, urine mercury was 0.98 ${\mu}g/g-cr$ and urine arsenic was 15.78 ${\mu}g/g-cr$. In the analysis of 11 kinds of VOCs in blood, vinyl chloride, 1,3-butadiene and dichloroethylene were not detected, while the detection rate of other chemicals was above 70% except chloroform(49.7%) and trichloroethylene(19.0%). In analysis of 16 kinds of PAHs in blood, 10 kinds showed more than 80% in detection rate. Also, detection rate of 4 kinds of PCBs in blood ranged 52 to 78%. Conclusions: Compared with industrial compelxes, the concentration of blood lead was lower, while urine cadmium and mercury levels were similar. Also, urine arsenic ranged at a significant level. Further study is required to find the cause of regional differences in concentrations of environmental pollutants.
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