Lovisa C. Romanoff

Concentration and profile of 22 urinary polycyclic aromatic hydrocarbon metabolites in the US population

Urinary monohydroxy polycyclic aromatic hydrocarbons (OH-PAHs) are a class of PAH metabolites used as biomarkers for assessing human exposure to PAHs. The Centers for Disease Control and Preventions National Health and Nutrition Examination Survey (NHANES) uses OH-PAHs to establish reference range concentrations for the US population, and to set benchmarks for future epidemiologic and biomonitoring studies. For the years 2001 and 2002, 22 OH-PAH metabolites were measured in urine specimens from 2748 NHANES participants. Percentages of samples with detectable levels ranged from nearly 100% for metabolites of naphthalene, fluorene, phenanthrene, and pyrene, to less than 5% for metabolites from parent compounds with higher molecular weight such as chrysene, benzo[c]phenanthrene, and benz[a]anthracene. The geometric mean for 1-hydroxypyrene (1-PYR)--the most commonly used biomarker for PAH exposure--was 49.6 ng/L urine, or 46.4 ng/g creatinine. Children (ages 6-11) generally had higher levels than did adolescents (ages 12-19) or adults (ages 20 and older). Model-adjusted, least-square geometric means for 1-PYR were 87, 53 and 43 ng/L for children, adolescents (ages 12-19) and adults (ages 20 years and older), respectively. Log-transformed concentrations for major detectable OH-PAHs were significantly correlated with each other. The correlation coefficients between 1-PYR and other metabolites ranging from 0.17 to 0.63 support the use of 1-PYR as a useful surrogate representing PAH exposure.

Excretion Profiles and Half-Lives of Ten Urinary Polycyclic Aromatic Hydrocarbon Metabolites after Dietary Exposure

Human exposure to polycyclic aromatic hydrocarbons (PAHs) can be assessed by biomonitoring of their urinary monohydroxylated metabolites (OH-PAHs). Limited information exists on the human pharmacokinetics of OH-PAHs. This study aimed to investigate the excretion half-life of 1-hydroxypyrene (1-PYR), the most used biomarker for PAH exposure, and 9 other OH-PAHs following a dietary exposure in 9 nonsmoking volunteers with no occupational exposure to PAHs. Each person avoided food with known high PAH-content during the study period, except for a high PAH-containing lunch (barbecued chicken) on the first day. Individual urine samples (n = 217) were collected from 15 h before to 60 h following the dietary exposure. Levels of all OH-PAHs in all subjects increased rapidly by 9-141-fold after the exposure, followed by a decrease consistent with first-order kinetics, and returned to background levels 24-48 h after the exposure. The average time to reach maximal concentration ranged from 3.1 h (1-naphthol) to 5.5 h (1-PYR). Creatinine-adjusted urine concentrations for each metabolite were analyzed using a nonlinear mixed effects model including a term to estimate background exposure. The background-adjusted half-life estimate was 3.9 h for 1-PYR and ranged 2.5-6.1 h for the other 9 OH-PAHs, which in general, were shorter than those previously reported. The maximum concentrations after barbecued chicken consumption were comparable to the levels found in reported occupational settings with known high PAH exposures. It is essential to consider the relatively short half-life, the timing of samples relative to exposures, and the effect of diet when conducting PAH exposure biomonitoring studies.

Evaluation of exposure reduction to indoor air pollution in stove intervention projects in Peru by urinary biomonitoring of polycyclic aromatic hydrocarbon metabolites

Burning biomass fuels such as wood on indoor open-pit stoves is common in developing regions. In such settings, exposure to harmful combustion products such as fine particulate matter (PM(2.5)), carbon monoxide (CO) and polycyclic aromatic hydrocarbons (PAHs) is of concern. We aimed to investigate if the replacement of open pit stoves by improved stoves equipped with a chimney would significantly reduce exposure to PAHs, PM(2.5) and CO. Two stove projects were evaluated in Peru. Program A was part of the Juntos National Program in which households built their own stoves using materials provided. In Program B, Barrick Gold Corporation hired a company to produce and install the stoves locally. A total of 30 and 27 homes participated in Program A and B, respectively. We collected personal and kitchen air samples, as well as morning urine samples from women tasked with cooking in the households before and after the installation of the improved stoves. Median levels of PM(2.5) and CO were significantly reduced in kitchen and personal air samples by 47-74% after the installation of the new stoves, while the median reduction of 10 urinary hydroxylate PAH metabolites (OH-PAHs) was 19%-52%. The observed OH-PAH concentration in this study was comparable or higher than the 95th percentile of the general U.S. population, even after the stove intervention, indicating a high overall exposure in this population.

Variability of urinary concentrations of polycyclic aromatic hydrocarbon metabolite in general population and comparison of spot, first-morning, and 24-h void sampling.

Urinary mono-hydroxy polycyclic aromatic hydrocarbons (OH-PAHs) are commonly used in biomonitoring to assess exposure to polycyclic aromatic hydrocarbons (PAHs). Similar to other biologically non-persistent chemicals, OH-PAHs have relatively short biological half-lives (4.4-35 h). Little information is available on their variability in urinary concentrations over time in non-occupationally exposed subjects. This study was designed to (i) examine the variability of nine urinary OH-PAH metabolite concentrations over time and (ii) calculate sample size requirements for future epidemiological studies on the basis of spot urine, first-morning void, and 24-h void sampling. Individual urine samples (n=427) were collected during 1 week from 8 non-occupationally exposed adults. We recorded the time and volume of each urine excretion, dietary details, and driving activities of the participants. Within subjects, the coefficients of variation (CVs) for the wet-weight concentration of OH-PAHs in all samples ranged from 45% to 297%; creatinine adjustment reduced the CV to 19-288% (P<0.001; paired t-test). The simulated 24-h void concentrations were the least variable measure, with CVs ranging from 13% to 182% for the 9 OH-PAHs. Within-day variability contributed on average 84%, and between-day variability accounted for 16% of the total variance of 1-hydroxypyrene (1-PYR). Intraclass correlation coefficients of 1-PYR levels were 0.55 for spot urine samples, 0.65 [corrected] for first-morning voids, and 0.77 [corrected] for 24-h voids, indicating a high degree of correlation between urine measurements collected from the same subject over time. Sample size calculations were performed to estimate the number of subjects required for detecting differences in the geometric mean at a statistical power of 80% for spot urine, first-morning, and 24-h void sampling. These data will aid in the design of future studies of PAHs and possibly other biologically non-persistent chemicals and in the interpretation of their analytical results.Urinary mono-hydroxy polycyclic aromatic hydrocarbons (OH-PAHs) are commonly used in biomonitoring to assess exposure to polycyclic aromatic hydrocarbons (PAHs). Similar to other biologically non-persistent chemicals, OH-PAHs have relatively short biological half-lives (4.4–35 h). Little information is available on their variability in urinary concentrations over time in non-occupationally exposed subjects. This study was designed to (i) examine the variability of nine urinary OH-PAH metabolite concentrations over time and (ii) calculate sample size requirements for future epidemiological studies on the basis of spot urine, first-morning void, and 24-h void sampling. Individual urine samples (n=427) were collected during 1 week from 8 non-occupationally exposed adults. We recorded the time and volume of each urine excretion, dietary details, and driving activities of the participants. Within subjects, the coefficients of variation (CVs) for the wet-weight concentration of OH-PAHs in all samples ranged from 45% to 297%; creatinine adjustment reduced the CV to 19–288% (P<0.001; paired t-test). The simulated 24-h void concentrations were the least variable measure, with CVs ranging from 13% to 182% for the 9 OH-PAHs. Within-day variability contributed on average 84%, and between-day variability accounted for 16% of the total variance of 1-hydroxypyrene (1-PYR). Intraclass correlation coefficients of 1-PYR levels were 0.55 for spot urine samples, 0.60 for first-morning voids, and 0.76 for 24-h voids, indicating a high degree of correlation between urine measurements collected from the same subject over time. Sample size calculations were performed to estimate the number of subjects required for detecting differences in the geometric mean at a statistical power of 80% for spot urine, first-morning, and 24-h void sampling. These data will aid in the design of future studies of PAHs and possibly other biologically non-persistent chemicals and in the interpretation of their analytical results.

Polycyclic aromatic hydrocarbon metabolite levels and pediatric allergy and asthma in an inner-city cohort

Miller RL, Garfinkel R, Lendor C, Hoepner L, Li Z, Romanoff L, Sjodin A, Needham L, Perera FP, Whyatt RM. Polycyclic aromatic hydrocarbon metabolite levels and pediatric allergy and asthma in an inner‐city cohort. 
Pediatr Allergy Immunol 2010: 21: 260–267.
© 2009 John Wiley & Sons A/S

Impact of the improved patsari biomass stove on urinary polycyclic aromatic hydrocarbon biomarkers and carbon monoxide exposures in rural Mexican women.

Background: Cooking with biomass fuels on open fires results in exposure to health-damaging pollutants such as carbon monoxide (CO), polycyclic aromatic hydrocarbons (PAHs), and particulate matter. Objective: We compared CO exposures and urinary PAH biomarkers pre- and postintervention with an improved biomass stove, the Patsari stove. Methods: In a subsample of 63 women participating in a randomized controlled trial in central Mexico, we measured personal CO exposure for 8 hr during the day using continuous monitors and passive samplers. In addition, first-morning urine samples obtained the next day were analyzed for monohydroxylated PAH metabolites by gas chromatography/isotope dilution/high-resolution mass spectrometry. Exposure data were collected during the use of an open fire (preintervention) and after installation of the improved stove (postintervention) for 47 women, enabling paired comparisons. Results: Median pre- and postintervention values were 4 and 1 ppm for continuous personal CO and 3 and 1 ppm for passive sampler CO, respectively. Postintervention measurements indicated an average reduction of 42% for hydroxylated metabolites of naphthalene, fluorene, phenanthrene, and pyrene on a whole-weight concentration basis (micrograms per liter of urine), and a 34% reduction on a creatinine-adjusted basis (micrograms per gram of creatinine). Pre- and postintervention geometric mean values for 1-hydroxypyrene were 3.2 and 2.0 μg/g creatinine, respectively. Conclusion: Use of the Patsari stove significantly reduced CO and PAH exposures in women. However, levels of many PAH biomarkers remained higher than those reported among smokers.

Urinary polycyclic aromatic hydrocarbons as a biomarker of exposure to PAHs in air: A pilot study among pregnant women

Recent studies have linked increased polycyclic aromatic hydrocarbons (PAHs) in air and adverse fetal health outcomes. Urinary PAH metabolites are of interest for exposure assessment if they can predict PAHs in air. We investigated exposure to PAHs by collecting air and urine samples among pregnant women pre-selected as living in “high” (downtown and close to steel mills, n=9) and “low” (suburban, n=10) exposure areas. We analyzed first-morning urine voids from all 3 trimesters of pregnancy for urinary PAH metabolites and compared these to personal air PAH/PM2.5/NO2/NOX samples collected in the 3rd trimester. We also evaluated activities and home characteristics, geographic indicators and outdoor central site PM2.5/NO2/NOX (all trimesters). Personal air exposures to the lighter molecular weight (MW) PAHs were linked to indoor sources (candles and incense), whereas the heavier PAHs were related to outdoor sources. Geometric means of all personal air measurements were higher in the “high” exposure group. We suggest that centrally monitored heavier MW PAHs could be used to predict personal exposures for heavier PAHs only. Urine metabolites were only directly correlated with their parent air PAHs for phenanthrene (Pearsons r=0.31–0.45) and fluorene (r=0.37–0.58). Predictive models suggest that specific metabolites (3-hydroyxyfluorene and 3-hydroxyphenanthrene) may be related to their parent air PAH exposures. The metabolite 2-hydroxynaphthalene was linked to smoking and the metabolite 1-hydroxypyrene was linked to dietary exposures. For researchers interested in predicting exposure to airborne lighter MW PAHs using urinary PAH metabolites, we propose that hydroxyfluorene and hydroxyphenanthrene metabolites be considered.

Biomonitoring of polycyclic aromatic hydrocarbon exposure in pregnant women in Trujillo, Peru — Comparison of different fuel types used for cooking ☆

Women and children in developing countries are often exposed to high levels of air pollution including polycyclic aromatic hydrocarbons (PAHs), which may negatively impact their health, due to household combustion of biomass fuel for cooking and heating. We compared creatinine adjusted hydroxy-PAH (OH-PAH) concentrations in pregnant women in Trujillo, Peru who cook with wood to levels measured in those who cook with kerosene, liquefied petroleum gas or a combination of fuels. Seventy-nine women were recruited for the study between May and July 2004 in the first trimester of their pregnancy. Urine samples were collected from the subjects in the first, second and third trimesters for OH-PAH analyses. The concentrations of the OH-PAHs were compared across the type of fuel used for cooking and pregnancy trimesters. The relationships between OH-PAHs levels in the first trimester and concurrently measured personal exposures to PM₂.₅, carbon monoxide and nitrogen dioxide together with their indoor and outdoor air concentrations were also investigated. Women cooking with wood or kerosene had the highest creatinine adjusted OH-PAH concentrations compared with those using gas, coal briquette or a combination of fuels. Concentrations of creatinine adjusted 2-hydroxy-fluorene, 3-hydroxy-fluorene, 1-hydroxy-fluorene, 2-hydroxy-phenanthrene and 4-hydroxy-phenanthrene were significantly higher (p<0.05) in women who used wood or kerosene alone compared with women who used liquefied petroleum gas (LPG), coal briquette or a combination of fuels. An increase in the concentrations of creatinine adjusted 9-hydroxy-fluorene, 1-hydroxy-phenanthrene, 2-hydroxy-phenanthrene, 4-hydroxy-phenanthrene and 1-hydroxy-pyrene in the third trimesters was also observed. Weak positive correlation (Spearman correlation coefficient, ρ<0.4; p<0.05) was observed between all first trimester creatinine adjusted OH-PAHs and indoor (kitchen and living room), and personal 48-h TWA PM₂.₅. Women who cooked exclusively with wood or kerosene had higher creatinine adjusted OH-PAH levels in their urine samples compared to women who cooked with LPG or coal briquette.

Lung function, airway inflammation, and polycyclic aromatic hydrocarbons exposure in mexican schoolchildren: A pilot study

Objective: To determine the association of exposure to polycyclic aromatic hydrocarbons (PAHs) with lung function and pH of exhaled breath condensate (EBC) in Mexican schoolchildren. Methods: A pilot study was performed in a subsample of 64 schoolchildren from Mexico City. Lung function and pH of EBC were measured and metabolites of PAHs in urine samples were determined. The association was analyzed using robust regression models. Results: A 10% increase in the concentrations of 2-hydroxyfluorene was significantly negatively associated with forced expiratory volume in 1 second (−11.2 mL, 95% CI: −22.2 to −0.02), forced vital capacity (−11.6 mL, 95% CI: −22.9 to −0.2), and pH of EBC (−0.035, 95% CI: −0.066 to −0.005). Conclusion: Biomarkers of PAHs exposure were inversely associated with lung function and decrease of ph of EBC as a marker of airway inflammation in Mexican schoolchildren.

Personal Exposure to PM2.5 and Urinary Hydroxy-PAH Levels in Bus Drivers Exposed to Traffic Exhaust, in Trujillo, Peru

Public transport vehicle drivers, especially in highly polluted or trafficked areas, are exposed to high levels of air pollutants. In this study, we assessed the influence of traffic on levels of hydroxy polycyclic aromatic hydrocarbons (OH-PAHs) in commercial bus drivers in Trujillo, Peru, by measuring the within-shift changes in the urinary whole weight and creatinine-corrected concentrations of the PAH metabolites. We measured personal PM2.5 as a proxy of exposure to traffic emission. Urine samples were collected daily from two bus drivers and three minivan drivers in Trujillo, pre-, mid-, post-work shift and on days when the drivers were off work (total n = 144). Ten OH-PAH metabolites were measured in the urine samples. Drivers were also monitored for exposure to PM2.5 (n = 41). Daily work shift (mean = 13.1 ± 1.3 hr) integrated PM2.5 was measured in the breathing zones of the drivers for an average of 10.5 days per driver. The differences across shift in OH-PAH concentrations were not statistically significant except for urinary 2-hydroxyfluorene (2-FLU) (p = 0.04) and 4-hydroxyphenanthrene (4-PHE) (p = 0.01) and creatinine-corrected 4-hydroxyphenanthrene (p = 0.01). Correlation between pairs of hydroxy-PAHs (ρ = 0.50 to 0.93) were highest for mid-shift samples. Concentrations of PM2.5 (geometric mean = 64 μg/m3; 95% confidence limits = 52 μg/m3, 78 μg/m3) is similar to those measured in many other studies of traffic exposure. There was significant change across work shift for concentrations of only two of the OH-PAHs (2-FLU and 4-PHE). Results indicate that the drivers may have had limited time for clearance of PAH exposure from the body between work shifts. Comparisons of the concentrations of creatinine-corrected hydroxy-PAH to those reported in other studies indicate that exposure of public transport drivers to PAH could be similar. By following the subjects over multiple days, this study gives an indication of appropriate exposure situations for the use of hydroxy-PAHs and will be beneficial in designing future occupational studies of PAH exposure.