Quantification of 1-hydroxypyrene, 1- and 2-hydroxynaphthalene, 3-hydroxybenzo[a]pyrene and 6-hydroxynitropyrene by HPLC-MS/MS in human urine as exposure biomarkers for environmental and occupational surveys

Raponi, Flavio; Bauleo, Lisa; Ancona, Carla; Forastiére, Francesco; Paci, Enrico; Pigini, Daniela; Tranfo, Giovanna

doi:10.1080/1354750x.2016.1252959

Cited by 17 publications

(16 citation statements)

References 38 publications

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“…Simultaneous quantitation of five urinary monohydroxylated metabolites of four polycyclic aromatic hydrocarbons (PAHs) was carried out using an HPLC-MS/MS analytical method: 1-hydroxypyrene (1-OHPy), 1-hydroxynaphthalene (1-OHNAP), 2-hydroxynaphthalene (2-OHNAP), 3-hydroxybenzo[a]pyrene (3-OHBaPy), 6-hydroxynitropyrene (6-OHNPy) [51]. Results were normalized for the creatininuria.…”

Section: Pahs Biomonitoringmentioning

confidence: 99%

First Results of the “Carbonaceous Aerosol in Rome and Environs (CARE)” Experiment: Beyond Current Standards for PM10

et al. 2017

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In February 2017 the "Carbonaceous Aerosol in Rome and Environs (CARE)" experiment was carried out in downtown Rome to address the following specific questions: what is the color, size, composition, and toxicity of the carbonaceous aerosol in the Mediterranean urban background area of Rome? The motivation of this experiment is the lack of understanding of what aerosol types are responsible for the severe risks to human health posed by particulate matter (PM) pollution, and how carbonaceous aerosols influence radiative balance. Physicochemical properties of the carbonaceous aerosol were characterised, and relevant toxicological variables assessed. The aerosol characterisation includes: (i) measurements with high time resolution (min to 1-2 h) at a fixed location of black carbon (eBC), elemental carbon (EC), organic carbon (OC), particle number size distribution (0.008-10 µm), major non refractory PM 1 components, elemental composition, wavelength-dependent optical properties, and atmospheric turbulence; (ii) 24-h measurements of PM 10 and PM 2.5 mass concentration, water soluble OC and brown carbon (BrC), and levoglucosan; (iii) mobile measurements of eBC and size distribution around the study area, with computational fluid dynamics modeling; (iv) characterisation of road dust emissions and their EC and OC content. The toxicological assessment includes: (i) preliminary evaluation of the potential impact of ultrafine particles on lung epithelia cells (cultured at the air liquid interface and directly exposed to particles); (ii) assessment of the oxidative stress induced by carbonaceous aerosols; (iii) assessment of particle size dependent number doses deposited in different regions of the human body; (iv) PAHs biomonitoring (from the participants into the mobile measurements). The first experimental results of the CARE experiment are presented in this paper. The objective here is to provide baseline levels of carbonaceous aerosols for Rome, and to address future research directions. First, we found that BC and EC mass concentration in Rome are larger than those measured in similar urban areas across Europe (the urban background mass concentration of eBC in Rome in winter being on average 2.6 ± 2.5 µg · m −3 , mean eBC at the peak level hour being 5.2 (95% CI = 5.0-5.5) µg · m −3 ). Then, we discussed significant variations of carbonaceous aerosol properties occurring with time scales of minutes, and questioned on the data averaging period used in current air quality standard for PM 10 (24-h). Third, we showed that the oxidative potential induced by aerosol depends on particle size and composition, the effects of toxicity being higher with lower mass concentrations and smaller particle size. Albeit this is a preliminary analysis, findings reinforce the need for an urgent update of existing air quality standards for PM 10 and PM 2.5 with regard to particle composition and size distribution, and data averaging period. Our results reinforce existing concerns about the toxicity of carbonaceous aerosols, suppo...

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Section: Pahs Biomonitoringmentioning

confidence: 99%

First Results of the “Carbonaceous Aerosol in Rome and Environs (CARE)” Experiment: Beyond Current Standards for PM10

et al. 2017

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“…The use of MS techniques, particularly GC and liquid chromatography (LC), are indispensable tools in metabolomic science owing to their high sensitivity and specificity. Relatively to assessment of B[a]P exposure -the only PAH classified as category 1 by International Agency for Research on Cancerurinary 3-OH-B[a]P determination plays a fundamental role; the hyphenated chromatographic MS procedures proposed for its analysis are based on age-old methodologies resulting in many manual operations with related uncertainty of the determination and higher overall costs of the method [26,27,29,[33][34][35][36]. The use of liquid/liquid extraction (LLE) or SPE with evaporation to dryness of the collect analyte solution followed by reconstitution in a suitable solvent for injection into the chromatographic system -with or o not derivatization -are the typical sequences for monohydroxy PAHs in urine.…”

Section: Resultsmentioning

confidence: 99%

“…Currently four GC methods using N-methyl-N-(trimethylsilyl) trifluoroacetamide (BSTFA) as derivatizing agent previous extraction with hexane or pentane and related analysis by single [27], QpQ [34], or high-resolution [26,35] MS were proposed. Regarding the LC-triple quadrupole analyses, Raponi et al [29] and Zangh et al [36] reported use of SPE, while Luo et al [33] included also the reaction by dansyl chloride (DNS). From the analytical evaluation of the seven above indicated methods we revealed that i) phenolic compounds are susceptible to oxidation with related losses of OH-PAHs and addition of gallic acid (50 µg/mL urine) prior to evaporation and derivatization steps was effective for inhibiting losses (lower than 5%), in according by Jacob et al [9].…”

Section: Resultsmentioning

confidence: 99%

“…Most analytical methods have been published to measure urinary OH-PAHs [12][13][14][15][16][17][18][19][20][21][22][23][24][25] which have two to three benzene rings, and only eleven study [26][27][28][29][30][31][32][33][34][35][36] have considered the determination of OH-PAHs with more than three benzene rings, particularly 3-OH-B[a]P. These existing assays have limitation, namely: their complexity, their use of solvents, and/or the need for clean-up steps to extract and eliminate interfering compounds from the urine, all of which involved lengthy manual operation, bigger costs, uncertainty in the determination analysis and the possible loss of analyte. For these reason, simultaneous and more sensitive assays methods than those available were needed.…”

Section: Introductionmentioning

confidence: 99%

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High-Throughput Analysis of Selected Urinary Hydroxy Polycyclic Aromatic Hydrocarbons by an Innovative Automated Solid-Phase Microextraction

Dugheri

Bonari

Gentili

et al. 2018

Preprint

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High-throughput screening of samples is the strategy of choice to detect occupational exposure biomarkers, yet it requires user-friendly apparatus that gives relatively prompt results while ensuring high degrees of selectivity, precision, accuracy and automation, particularly in preparation processes. In the last 10 years, miniaturization has attracted much attention in analytical chemistry and has driven solvent and sample savings and easier automation, the latter thanks to the introduction on the market of three axis autosampler. In light of the above, this contribution describes a novel user-friendly solid-phase microextraction (SPME) off- and on-line platform coupled with gas chromatography triple quadrupole-mass spectrometry to determine urinary 1- and 2-hydroxy-napthalene, 9-hydroxy-phenantrene, 1-hydroxy-pyrene, 3- and 9-hydroxy-benzoantracene and 3-hydroxy-benzo[a]pyrene, metabolites of the related polycyclic aromatic hydrocarbons. In this new procedure chromatography’s sensitivity is combined with the user-friendliness of N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide on-fiber SPME derivatization previous direct immersion sampling, to which is added the quantitative accuracy afforded using specific isotope-labelled internal standards. The detection limits for the seven OH-PAHs were ranged from 0.28 to 1.87 ng/L. Intra-(from 2.5 to 3.0%) and inter-session (from 2.4 to 3.9%) repeatability was also evaluated. This method serves to identify suitable risk-control strategies for occupational hygiene conservation programs

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“…The development of analytical methods to identify suitable risk-control strategies for occupational hygiene conservation programs have aroused interest in the scientific community. Most analytical methods have been published to measure urinary OH-PAHs [ 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 , 23 , 24 , 25 ], which have two to three benzene rings, and only eleven studies [ 26 , 27 , 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 ] have considered the determination of OH-PAHs with more than three benzene rings, particularly 3-OH-B[a]P.…”

Section: Introductionmentioning

confidence: 99%

High-Throughput Analysis of Selected Urinary Hydroxy Polycyclic Aromatic Hydrocarbons by an Innovative Automated Solid-Phase Microextraction

et al. 2018

View full text Add to dashboard Cite

High-throughput screening of samples is the strategy of choice to detect occupational exposure biomarkers, yet it requires a user-friendly apparatus that gives relatively prompt results while ensuring high degrees of selectivity, precision, accuracy and automation, particularly in the preparation process. Miniaturization has attracted much attention in analytical chemistry and has driven solvent and sample savings as easier automation, the latter thanks to the introduction on the market of the three axis autosampler. In light of the above, this contribution describes a novel user-friendly solid-phase microextraction (SPME) off- and on-line platform coupled with gas chromatography and triple quadrupole-mass spectrometry to determine urinary metabolites of polycyclic aromatic hydrocarbons 1- and 2-hydroxy-naphthalene, 9-hydroxy-phenanthrene, 1-hydroxy-pyrene, 3- and 9-hydroxy-benzoantracene, and 3-hydroxy-benzo[a]pyrene. In this new procedure, chromatography’s sensitivity is combined with the user-friendliness of N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide on-fiber SPME derivatization using direct immersion sampling; moreover, specific isotope-labelled internal standards provide quantitative accuracy. The detection limits for the seven OH-PAHs ranged from 0.25 to 4.52 ng/L. Intra-(from 2.5 to 3.0%) and inter-session (from 2.4 to 3.9%) repeatability was also evaluated. This method serves to identify suitable risk-control strategies for occupational hygiene conservation programs.

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Quantification of 1-hydroxypyrene, 1- and 2-hydroxynaphthalene, 3-hydroxybenzo[a]pyrene and 6-hydroxynitropyrene by HPLC-MS/MS in human urine as exposure biomarkers for environmental and occupational surveys

Abstract: The method is suitable both for occupational and for environmental studies. This is the first paper reporting urinary levels of 6-hydroxynitropyrene in European subjects, nonoccupationally exposed to nitro-PAHs.

Cited by 17 publications

References 38 publications

First Results of the “Carbonaceous Aerosol in Rome and Environs (CARE)” Experiment: Beyond Current Standards for PM10

First Results of the “Carbonaceous Aerosol in Rome and Environs (CARE)” Experiment: Beyond Current Standards for PM10

High-Throughput Analysis of Selected Urinary Hydroxy Polycyclic Aromatic Hydrocarbons by an Innovative Automated Solid-Phase Microextraction

High-Throughput Analysis of Selected Urinary Hydroxy Polycyclic Aromatic Hydrocarbons by an Innovative Automated Solid-Phase Microextraction

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