1.UPLC-QTOF mass spectrometry detection of four endocrine disrupting chemicals (Methyl Paraben, 2,4-Dichlorophenoxyacetic acid, Monobutyl Phthalate, and Bisphenol A) in urine of Filipino women
Francisco M. Heralde III ; Zaidy T. Martin ; Maria Stephanie Fay S. Cagayan ; Ma. Esterlita V. Uy ; Paulyn Jean R. Ubial ; Michael C. Velarde ; Erlidia F. Llamas-clark
Acta Medica Philippina 2025;59(3):70-79
BACKGROUND AND OBJECTIVE
Endocrine Disrupting Chemicals (EDCs) are ubiquitously found as low-level contaminants and pose serious threat to women’s health. EDCs may result in various reproductive disorders, fetal birth and developmental abnormalities, and endocrine and metabolic disorders. EDCs can be detected in body fluids of exposed individuals including blood and urine. This study aimed to detect four EDCs — Methyl Paraben (MP), 2,4-Dichlorophenoxyacetic acid (2,4-D), Monobutyl Phthalate (MBP), and Bisphenol A (BPA) in urine samples of women using Ultra-Performance Liquid Chromatography – Quadrupole Time-of-Flight (UPLC-QTOF) mass spectrometry.
METHODSSequential steps of enzymatic deconjugation, liquid-liquid extraction, solid phase extraction, and liquid chromatography separation and mass spectrometry detection were optimized in urine samples. The method was used to analyze 70 urine samples from women of reproductive age.
RESULTSThe sample preparation method showed a recovery ranging from 86.6% (MBP) to 100 % (2,4-D). The method demonstrated limits of quantitation ranging from 1.52 ng/m(MP) to 6.46 ng/mL(2,4D). Intra-day precisions expressed as relative standard deviation were all below 15% while accuracy was shown to range from 67.10% (2,4-D) to 102.39% (MBP). MP was detected in nine samples (12.86%) with a geometric mean value of 10.15 ng/ml (range: 3.62-52.39 ng/ml). MBP was detected in 68 samples (97.14%) with a geometric mean value of 97.62 ng/ml (range: 15.32-698.18 ng/ml). BPA was detected only once (9.58 ng/ml) while 2, 4-D was not detected in all samples.
CONCLUSIONA UPLC-QTOF mass spectrometry method to detect four EDCs at parts per billion level (ng/ml) was adapted and applied for analysis of urine samples. This method can find applicability in routine testing of clinical specimens as well as surveillance and other epidemiological studies.
Endocrine Disruptors ; 2,4-dichlorophenoxyacetic Acid ; Bisphenol A
2.Determination of 2, 4-dichlorophenoxyacetic acid in air of workplace by high-performance liquid chromatography.
Yanan WEN ; Zhaohui FU ; Jianning XU ; Shichuan TANG ; Quankai WANG ; Huanhuan LI ; Guangyun XIE ; Yuling ZHU ; Yiting GU ; Feng TAN
Chinese Journal of Industrial Hygiene and Occupational Diseases 2014;32(6):458-459
OBJECTIVETo develop a method for determination of 2, 4-dichlorophenoxyacetic acid (2, 4-D) in the air of workplace by high-performance liquid chromatography.
METHODS2, 4-D was collected by ultrafine glass filters, desorbed by methanol, separated by a C18 column, and detected by a UV detector. Identification and quantification of 2, 4-D were performed by retention time and peak areas, respectively.
RESULTSThe linear range of the test was 2∼200 µg/ml; the elution efficiency was 94.6%- 95.9%; the limit of detection (S/N = 3) was 0.034 µg/ml (injection volume of 20 µl eluant); the lower limit of quantification (S/N = 10) was 0.11 µg/ml; the minimum detectable concentration was 0.011 mg/m(3); the minimum quantifiable concentration was 0.037 mg/m(3) (with sampled air volume of 45 L).
CONCLUSIONThis method is convenient and simple in sample collection and preparation, and satisfies all methodological requirements. Therefore, this method is useful for the determination of 2, 4-D in the air of workplace.
2,4-Dichlorophenoxyacetic Acid ; analysis ; Air ; analysis ; Air Pollutants, Occupational ; analysis ; Chromatography, High Pressure Liquid ; methods ; Workplace
3.Serum 2,3,7,8-Tetrachlorodibenzo-p-dioxin Levels and Their Association With Age, Body Mass Index, Smoking, Military Record-based Variables, and Estimated Exposure to Agent Orange in Korean Vietnam Veterans.
Sang Wook YI ; Heechoul OHRR ; Jong Uk WON ; Jae Seok SONG ; Jae Seok HONG
Journal of Preventive Medicine and Public Health 2013;46(5):226-236
OBJECTIVES: The aim of this study was to examine the levels of serum 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and evaluate their association with age, body mass index, smoking, military record-based variables, and estimated exposure to Agent Orange in Korean Vietnam veterans. METHODS: Serum levels of TCDD were analyzed in 102 Vietnam veterans. Information on age, body mass index, and smoking status were obtained from a self-reported questionnaire. The perceived exposure was assessed by a 6-item questionnaire. Two proximity-based exposures were constructed by division/brigade level and battalion/company level unit information using the Stellman exposure opportunity index model. RESULTS: The mean and median of serum TCDD levels was 1.2 parts per trillion (ppt) and 0.9 ppt, respectively. Only 2 Vietnam veterans had elevated levels of TCDD (>10 ppt). The levels of TCDD did not tend to increase with the likelihood of exposure to Agent Orange, as estimated from either proximity-based exposure or perceived self-reported exposure. The serum TCDD levels were not significantly different according to military unit, year of first deployment, duration of deployment, military rank, age, body mass index, and smoking status. CONCLUSIONS: The average serum TCDD levels in the Korean Vietnam veterans were lower than those reported for other occupationally or environmentally exposed groups and US Vietnam veterans, and their use as an objective marker of Agent Orange exposure may have some limitations. The unit of deployment, duration of deployment, year of first deployment, military rank, perceived self-reported exposure, and proximity-based exposure to Agent Orange were not associated with TCDD levels in Korean Vietnam veterans. Age, body mass index and smoking also were not associated with TCDD levels.
2,4,5-Trichlorophenoxyacetic Acid/*poisoning
;
2,4-Dichlorophenoxyacetic Acid/*poisoning
;
Adult
;
Age Factors
;
*Body Mass Index
;
Defoliants, Chemical/*poisoning
;
Humans
;
Male
;
Middle Aged
;
Questionnaires
;
Regression Analysis
;
Republic of Korea/epidemiology
;
Self Report
;
Smoking/*blood
;
Tetrachlorodibenzodioxin/*blood/poisoning
;
Time Factors
;
Veterans/*statistics & numerical data
;
Vietnam Conflict
;
Young Adult
4.Agent Orange Exposure and Prevalence of Self-reported Diseases in Korean Vietnam Veterans.
Sang Wook YI ; Heechoul OHRR ; Jae Seok HONG ; Jee Jeon YI
Journal of Preventive Medicine and Public Health 2013;46(5):213-225
OBJECTIVES: The aim of this study was to evaluate the association between Agent Orange exposure and self-reported diseases in Korean Vietnam veterans. METHODS: A postal survey of 114 562 Vietnam veterans was conducted. The perceived exposure to Agent Orange was assessed by a 6-item questionnaire. Two proximity-based Agent Orange exposure indices were constructed using division/brigade-level and battalion/company-level unit information. Adjusted odds ratios (ORs) for age and other confounders were calculated using a logistic regression model. RESULTS: The prevalence of all self-reported diseases showed monotonically increasing trends as the levels of perceived self-reported exposure increased. The ORs for colon cancer (OR, 1.13), leukemia (OR, 1.56), hypertension (OR, 1.03), peripheral vasculopathy (OR, 1.07), enterocolitis (OR, 1.07), peripheral neuropathy (OR, 1.07), multiple nerve palsy (OR, 1.14), multiple sclerosis (OR, 1.24), skin diseases (OR, 1.05), psychotic diseases (OR, 1.07) and lipidemia (OR, 1.05) were significantly elevated for the high exposure group in the division/brigade-level proximity-based exposure analysis, compared to the low exposure group. The ORs for cerebral infarction (OR, 1.08), chronic bronchitis (OR, 1.05), multiple nerve palsy (OR, 1.07), multiple sclerosis (OR, 1.16), skin diseases (OR, 1.05), and lipidemia (OR, 1.05) were significantly elevated for the high exposure group in the battalion/company-level analysis. CONCLUSIONS: Korean Vietnam veterans with high exposure to Agent Orange experienced a higher prevalence of several self-reported chronic diseases compared to those with low exposure by proximity-based exposure assessment. The strong positive associations between perceived self-reported exposure and all self-reported diseases should be evaluated with discretion because the likelihood of reporting diseases was directly related to the perceived intensity of Agent Orange exposure.
2,4,5-Trichlorophenoxyacetic Acid/*poisoning
;
2,4-Dichlorophenoxyacetic Acid/*poisoning
;
Cardiovascular Diseases/epidemiology/etiology
;
Defoliants, Chemical/*poisoning
;
Endocrine System Diseases/epidemiology/etiology
;
Gastrointestinal Diseases/epidemiology/etiology
;
Humans
;
Logistic Models
;
Male
;
Middle Aged
;
Neoplasms/epidemiology/etiology
;
Neuromuscular Diseases/epidemiology/etiology
;
Odds Ratio
;
Prevalence
;
Republic of Korea/epidemiology
;
Respiratory Tract Diseases/epidemiology/etiology
;
*Self Report
;
Tetrachlorodibenzodioxin/*poisoning
;
*Veterans
;
Vietnam Conflict
5.Induction of adventitious roots of Echinacea pallida and accumulation of caffeic acid derivatives.
Chun-Hua WU ; Tao HUANG ; Xi-Hua CUI ; Keeyoeup PAEK
China Journal of Chinese Materia Medica 2012;37(24):3768-3772
OBJECTIVETo investigate the effect of auxins 2,4-D,IAA,IBA,NAA on induction of adventitious roots as well as that of IBA concentrations on the growth of adventitious roots and the accumulation of caffeic acid derivatives, with test-tube seedling leaves Echinacea pallida as the explant, and cultivate adventitious roots in bioreactors.
RESULT1.0 mg x L(-1) IBA was found the best for the induction of adventitious roots, with the numer of induced adventitious roots up to 22. 5 in each culture dish. Among different concentrations for suspension cultivation of IBA tested, 1.0 mg x L(-1) IBA was found the most suitable for the growth of adventitious roots and the accumulation of caffeic acid derivatives. In a 5 L balloon type bubble bioreactor, 8.98 g x L(-1) dry weight was achieved after one month, which was 2.05 times of 4.38 g x L(-1) dry weight cultivated in a triangular flask. The content of echinacoside cultivated in a bioreactor was 14.08 mg x g(-1) DW, which was 2.4 times of cultivated roots. The contents of chlorogenic acid, chicoric acid and total caffeic acid derivatives were 4.0-25.6 times of ultivated roots.
CONCLUSIONThe study can provide high-quality biomedical drugs containing such caffeic acid derivatives as echinacoside for mass production of Echinacea purpurea medicines.
2,4-Dichlorophenoxyacetic Acid ; pharmacology ; Bioreactors ; Caffeic Acids ; chemistry ; metabolism ; Dose-Response Relationship, Drug ; Echinacea ; drug effects ; growth & development ; metabolism ; Indoleacetic Acids ; pharmacology ; Indoles ; pharmacology ; Naphthaleneacetic Acids ; pharmacology ; Plant Growth Regulators ; pharmacology ; Plant Leaves ; drug effects ; growth & development ; metabolism ; Plant Roots ; drug effects ; growth & development ; metabolism ; Seedlings ; drug effects ; growth & development ; metabolism ; Tissue Culture Techniques ; instrumentation ; methods
6.Effect on different concentrations of exogenous hormones on baicalin in Scutellaria baicalensis callus.
Gui-Xiang WAN ; Lin MA ; Jian ZHANG
China Journal of Chinese Materia Medica 2012;37(24):3799-3802
OBJECTIVETo determine the content of baicalin in Scutellaria baicalensis callus induced by different doncentrations of exogenous hormones.
METHODHPLC system was adopted to determine baicalin in S. baicalensis callus. Chromatographic conditions: ODS column was adopted, with methanol-water-phosphate (47: 53: 0.2) as the mobile phase. The flow velocity was 1 mL x min(-1), the detective wavelength was 280 nm, and the temperature of column was room temperature.
RESULTS. baicalensis callus induced by 6-BA 1.0 mg x L(-1) + NAA 0.5 mg x L(-1) showed the highest baicalin content, up to 49.78 mg x g(-1).
CONCLUSIONThe experiment is such a simple, rapid and stable method for determining the baicalin content that it can be used for determining the baicalin content in S. baicalensis callus.
2,4-Dichlorophenoxyacetic Acid ; pharmacology ; Benzyl Compounds ; Chromatography, High Pressure Liquid ; Dose-Response Relationship, Drug ; Flavonoids ; metabolism ; Kinetin ; pharmacology ; Naphthaleneacetic Acids ; pharmacology ; Plant Growth Regulators ; pharmacology ; Purines ; Scutellaria baicalensis ; drug effects ; metabolism ; Tissue Culture Techniques ; methods
7.Clinical Outcome of Veterans with Acute Coronary Syndrome Who Had Been Exposed to Agent Orange
Jong Bum KIM ; Won Yu KANG ; Se Gwon MOON ; Hee Jong KIM ; Kyung Hwan KIM ; Yeon Hwa KIM ; Seung Hwan HWANG ; Sun Ho HWANG ; Wan KIM
Chonnam Medical Journal 2012;48(1):47-51
2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD), one of the components of Agent Orange, has been reported to be a deadly poison despite its presence at extremely small doses. TCDD is reported to cause various kinds of cancers and other harmful effects on humans. However, a correlation between exposure to TCDD and acute coronary syndrome (ACS) is not yet proven. Thus, we examined the correlation between exposure to TCDD and ACS through an analysis of coronary angiograms from veterans of the Vietnam War. Two hundred fifty-one consecutive men undergoing coronary angiograms owing to ACS between April 2004 and May 2009 at Gwangju Veterans Hospital were analyzed. Included subjects were between 50 and 70 years of age. The patients were divided into two groups: 121 patients who had been exposed to TCDD (Group I) and 130 patients who had not been exposed to TCDD (Group II). Clinical and coronary angiographic findings were evaluated. Baseline clinical characteristics, inflammatory markers, and echocardiographic parameters were not significantly different between the two groups. The incidence of hypertension (71.1% vs. 60.0%, p=0.039) and hyperlipidemia (27.3% vs. 16.9%, p=0.038) was higher in Group I than in Group II. Total occlusion, stent length, stent use, and coronary lesion characteristics were not significantly different between the two groups. The rate of major adverse cardiovascular events (MACE) had no relationship with exposure to TCDD. Exposure to TCDD might not affect severity or the rate of MACE in persons with ACS.
2,4,5-Trichlorophenoxyacetic Acid
;
2,4-Dichlorophenoxyacetic Acid
;
Acute Coronary Syndrome
;
Angiography
;
Citrus sinensis
;
Hospitals, Veterans
;
Humans
;
Hyperlipidemias
;
Hypertension
;
Incidence
;
Male
;
Stents
;
Tetrachlorodibenzodioxin
;
Veterans
;
Vietnam
8.Defoliant and Skin Diseases.
Korean Journal of Dermatology 2011;49(10):863-871
A defoliant is a toxic chemical agent used to remove leaves. Defoliants are classified into 6 types (purple, pink, green, blue, white and orange). From 1962 to 1971, due to removing leaves and securing their ability to see, the U.S. Army Chemical Corps veterans handled and sprayed defoliant in Vietnam. This resulted in exposure to Agent Orange and its contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD or dioxin). This agent induces many medical problems in humans. Since 1992 in Korea, exposure to defoliants have given rise to several problems. However, there were few reactions due to the lack of data, social apathy, and international relationships. In this article, we review characteristics and diseases related to defoliants.
2,4,5-Trichlorophenoxyacetic Acid
;
2,4-Dichlorophenoxyacetic Acid
;
Apathy
;
Citrus sinensis
;
European Continental Ancestry Group
;
Humans
;
Korea
;
Skin
;
Skin Diseases
;
Tetrachlorodibenzodioxin
;
Veterans
;
Vietnam
9.Multiple Merkel Cell Carcinoma in a Vietnam Veteran Exposed to Agent Orange.
Gyo Shin KANG ; Sung Min HWANG ; Dong Min KIM ; Moo Kyu SUH ; Jae Hong KIM ; Tae Jung JANG
Korean Journal of Dermatology 2011;49(2):191-194
Merkel cell carcinoma is a rare aggressive primary skin cancer which mostly occurs in the elderly on sun-exposed skin. It usually presents as a solitary dome-shaped red or purple nodule on the head, neck and extremities. The mortality rate is higher than the rate for malignant melanoma because its local recurrence is common. Agent Orange, an herbicide widely used as a defoliant in the Vietnam War, contains dioxin contaminants and can cause several dermatoses and skin cancers. We report a case of multiple Merkel cell carcinoma in a 65-year-old male with lesions on the head and neck, who had been exposed to Agent Orange during Vietnam War.
2,4,5-Trichlorophenoxyacetic Acid
;
2,4-Dichlorophenoxyacetic Acid
;
Aged
;
Carcinoma, Merkel Cell
;
Citrus sinensis
;
Extremities
;
Head
;
Humans
;
Male
;
Melanoma
;
Neck
;
Recurrence
;
Skin
;
Skin Diseases
;
Skin Neoplasms
;
Tetrachlorodibenzodioxin
;
Veterans
;
Vietnam
10.A Clinical Study of Self-Inflicted Dermatosis.
Hak Ju KIM ; Yoo Soo KO ; Jae Seung LEE ; Ok Ja JOH
Korean Journal of Dermatology 2009;47(3):259-267
BACKGROUND: Self-inflicted dermatosis is a kind of self-inflicted skin disease. Most Vietnam veterans from Korea have visited the Veterans Hospitals for dermatological examination to determine the relationship between their skin diseases and Agent Orange. We were suspicious of the possibility that several Vietnam veterans intentionally produced their own skin lesions. OBJECTIVE: We conducted this study to determine the clinical characteristics of self-inflicted dermatoses of Korean Vietnam veterans. METHODS: From January, 1999 to December, 2007, a total 24 Vietnam veterans who were diagnosed as having self-inflicted dermatoses during their dermatological examinations at our hospital were included in this study. We investigated their clinical presentation, the laboratory examinations, the pathologic examinations, the medical records and the associated diseases. RESULTS: Itching was the most common subjective complaint and the duration of the itching was as follows; 20 to 30 yrs (50.0%), 1 to 10 yrs (25.0%), 10 to 20 yrs (20.8%) etc. The skin lesions were all multiple, and the involved area was as follows; upper extremities (83.3%), trunk (75.0%), lower extremities (70.8%) etc. There were two categories of clinical skin presentation. The first was the cases with lesion that were thought to be made by physical trauma such as stinging or excoriation, and the second more common cases had lesions that were thought to be made by chemical agents (70.8%). These cases resembled allergic or toxic irritant dermatitis and the lesions were composed of vesicles, erosions, ulcers and crusts that were within an arm's reach. Only 4 cases admitted to intentionally inflicting their skin lesions because of intense itching, and the others denied that they made the skin lesions by themselves. Skin biopsies were carried out in 19 of the total 24 cases, and the most common finding was spongiotic dermatitis (57.8%). CONCLUSION: This study showed the distribution and characteristics of self-inflicted dermatoses, and the study provides fundamental data for dermatologists to assess patients with self-inflicted dermatoses.
2,4,5-Trichlorophenoxyacetic Acid
;
2,4-Dichlorophenoxyacetic Acid
;
Biopsy
;
Bites and Stings
;
Citrus sinensis
;
Dermatitis
;
Dermatitis, Irritant
;
Hospitals, Veterans
;
Humans
;
Intention
;
Korea
;
Lower Extremity
;
Medical Records
;
Pruritus
;
Skin
;
Skin Diseases
;
Tetrachlorodibenzodioxin
;
Ulcer
;
Upper Extremity
;
Veterans
;
Vietnam


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