Structural Analysis and Characterization of 4-F-α-PVP Analog 4-F-3-Methyl-α- PVP Hydrochloride / 法医学杂志

OBJECTIVES@#To identify 1-(4-fluorophenyl)-2-(1-pyrrolidinyl) pentan-1-one (4-F-α-PVP) analog 1-(4-fluoro-3-methyl phenyl)-2-(1-pyrrolidinyl) pentan-1-one (4-F-3-Methyl-α-PVP) hydrochloride without reference substance.@*METHODS@#The direct-injection electron ionization-mass spectrometry (EI-MS), GC-MS, electrospray ionization-high resolution mass spectrometry (ESI-HRMS), ultra-high performance liquid chromatography-high resolution tandem mass spectrometry (UPLC-HRMS/MS), nuclear magnetic resonance (NMR), ion chromatography and Fourier transform infrared spectroscopy (FTIR) were integrated utilized to achieve the structural analysis and characterization of the unknown compound in the sample, and the cleavage mechanism of the fragment ions was deduced by EI-MS and UPLC-HRMS/MS.@*RESULTS@#By analyzing the direct-injection EI-MS, GC-MS, ESI-HRMS and UPLC-HRMS/MS of the compound in the samples, it was concluded that the unknown compound was a structural analog of 4-F-α-PVP, possibly with one more methyl group in the benzene ring. According to the analysis results of 1H-NMR and 13C-NMR, it was further proved that the methyl group is located at the 3-position of the benzene ring. Since the actual number of hydrogen in 1H-NMR analysis was one more than 4-F-3-Methyl-α-PVP neutral molecule, it was inferred that the compound existed in the form of salt. Ion chromatography analysis results showed that the compound contained chlorine anion (content 11.14%-11.16%), with the structural analysis of main functional group information by FTIR, the unknown compound was finally determined to be 4-F-3-Methyl-α-PVP hydrochloride.@*CONCLUSIONS@#A comprehensive method using EI-MS, GC-MS, ESI-HRMS, UPLC-HRMS/MS, NMR, ion chromatography and FTIR to identify 4-F-3-Methyl-α-PVP hydrochloride in samples is established, which will be helpful for the forensic science laboratory to identify this compound or other analog compounds.

Caracterização da qualidade do ar atmosférico na Cidade de São Paulo para compostos do grupo BTEX (benzeno, tolueno, etilbenzeno e xilenos), utilizando amostradores passivos / Characterization of atmospheric air quality in the City of São Paulo for compounds of the BTEX group (benzene, toluene, ethylbenzene and xylenes), using passive samplers

A presença de compostos do grupo BTEX, no ar atmosférico de grandes centros urbanos como a cidade de São Paulo é proveniente principalmente de emissões veiculares e demais fontes como as industriais. A exposição a estes compostos, principalmente quando inalados, podem causar sérios efeitos adversos a saúde humana, especialmente o composto benzeno que possui propriedades cancerígenas. Desta forma, a presente pesquisa teve objetivo realizar uma caracterização da qualidade do ar atmosférico na cidade de São Paulo utilizando amostradores passivos para quantificação de compostos do grupo BTEX. Foram selecionadas 5 áreas na cidade conforme dados de tráfego destas regiões e de acordo com o perfil de uso e ocupação do solo. Adicionalmente, foi selecionada uma área como background, com interferência mínima de emissões veiculares ou industriais. Ao todo foram realizadas 3 campanhas de amostragem no entre os anos de 2020 e 2021. O período de coleta de cada campanha foi de 21 dias e na sequência as amostras foram enviadas para análise química em laboratório através do método USEPA-TO17, de 1999 com a utilização de dessorvedor térmico acoplado à um cromatógrafo de gás e um espectrômetro de massas. Foram quantificadas concentrações de BTEX em todas as áreas selecionadas, com destaque para as concentrações de benzeno cuja variação foi de 1,2µg/m3 a 13,5µg/m3, e média de 4,6µg/m3, considerando as 3 campanhas e todas as áreas. Dentro as áreas avaliadas, os pontos localizados no bairro de Santo Amaro apresentaram as maiores concentrações de BTEX, seguido dos pontos no Jaguaré, Mooca, Pinheiros e Paraíso. A campanha realizada no inverno de 2021 apresentou as maiores concentrações tendo influência das condições meteorológicas características desta estação como também influência do aumento do número de veículos circulando na cidade decorrente da diminuição do distanciamento social necessário por conta da pandemia da COVID-19. Os tratamentos estatísticos utilizados nesta pesquisa, especialmente as ferramentas PCA e PMF, concluíram que a principal contribuição para a presença dos BTEX no ar atmosférico são as emissões veiculares, principalmente para os veículos movidos a gasolina.

The presence of compounds from the BTEX group in the atmospheric air of large urban centers such as the city of São Paulo comes mainly from vehicular emissions and other sources such as industrial ones. Exposure to these compounds, especially when inhaled, can cause serious adverse effects on human health, especially the compound benzene, which has carcinogenic properties. Thus, the present research aimed to carry out a characterization of the atmospheric air quality in the city of São Paulo using passive samplers to quantify compounds of the BTEX group. Five areas were selected in the city according to traffic data from these regions and according to the profile of land use and occupation. Additionally, an area was selected as a background, with minimal interference from vehicular or industrial emissions. In all, 3 sampling campaigns were carried out between the years 2020 and 2021. The collection period of each campaign was 21 days and then the samples were sent for chemical analysis in the laboratory using the USEPA-TO17 method, from 1999 with the use of a thermal desorber coupled to a gas chromatograph and a mass spectrometer. BTEX concentrations were quantified in all selected areas, especially benzene concentrations which ranged from 1.2µg/m3 to 13.5µg/m3, and an average of 4.6µg/m3, considering the 3 campaigns and all areas. Within the evaluated areas, the points located in the Santo Amaro neighborhood had the highest concentrations of BTEX, followed by the points in Jaguaré, Mooca, Pinheiros and Paraíso. The campaign carried out in the winter of 2021 showed the highest concentrations influenced by the meteorological conditions characteristic of this season as well as the influence of the increase in the number of vehicles circulating in the city due to the decrease in the social distance necessary due to the COVID-19 pandemic. The statistical treatments used in this research, especially the PCA and PMF tools, concluded that the main contribution to the presence of BTEX in the atmospheric air are vehicular emissions, especially for gasoline-powered vehicles.

Actividades económicas, laborales, ambientales y aditivas con exposición a benceno y el desarrollo de leucemia mieloide aguda / Economic activities, occupational, environmental and additive exposures to benzene and the development of acute myeloid leukemia

Introducción: el benceno es un hidrocarburo aromático obtenido por destilación del alquitrán utilizado en gasolineras y como solvente industrial, clasificado como cancerígeno por exposición ocupacional o ambiental. Está relacionado con el desarrollo de leucemia mieloide aguda (LMA) por su absorción principal por vía inhalatoria, y su metabolismo hepático con producción de benzoquinona de alta liposolubilidad que le permite depositarse en la médula ósea y tejido graso. Objetivo: analizar la asociación de las formas de exposición por actividades económicas, oficios, cargos, exposición ambiental y aditiva con el desarrollo de LMA. Materiales y métodos: revisión sistemática de la literatura en las bases de datos Medline, Embase, Lilacs, Cochrane Library, Toxnet y OpenGrey, en inglés y español con los términos benzene, cancer, leukemia, occupational and enviromental exposition. Resultados: la mayoría de los estudios muestran una relación causal entre la exposición a benceno y el desarrollo de LMA, con predominio en ambientes laborales, seguidos de factores ambientales y aditivos como el humo del cigarrillo. Conclusiones: se encontró evidencia de asociación entre la exposición a benceno ocupacional y/o ambiental con el desarrollo de leucemia mieloide aguda, debido a que altera el estrés oxidativo y la desregulación del aryl hidrocarburo generando efectos citogenéticos, mutación genética y alteraciones epigenéticas que se expresan en hematotoxicidad y desarrollo de leucemia.

Introduction: Benzene is an aromatic hydrocarbon obtained by distillation of tar used in gas stations and as an industrial solvent, classified as a carcinogen by occupational and environmental exposure. It is related with the development of acute myeloid leukemia (AML) mainly due to its absorption by inhalation and hepatic metabolism producing highly-lipid soluble benzoquinone allowing it to deposit in bone marrow and fatty tissue. Objective: to analyze the association of forms of exposure including economic activities, type of workplace, environmental and additive exposure with the development of AML. Material and Methods: systematic review of the literature in Medline, Embase, Lilacs, Cochrane Library, Toxnet and OpenGrey databases in English and Spanish, using the terms benzene, cancer, leukemia, occupational and environmental exposure. Results: most studies show a causal relationship between benzene exposure and AML development, predominantly in work settings, followed by environmental factors including additive sources such as cigarette smoke. Conclusions: we found evidence of an association between occupational and/or environmental exposure to benzene and the development of AML, for it alters oxidative stress and aryl hydrocarbon deregulation inducing cytogenetic aberrations, genetic mutations and epigenetic changes expressed as hematotoxicity and leukemia development.

Effect of occupational exposure on hematological and biochemical parameters in workers at oil and gas companies

Petroleum refineries are largest chemical industries that are responsible for emission of several pollutants into the atmosphere. Benzene and its metabolites are regarded as the most hazardous compounds that are emitted by petroleum refineries. These contribute to toxic oxidants, which cause many serious health risks to petroleum refineries workers. This study was aimed to analyze the effects of chemical exposure on hematological and biochemical parameters among workers at Zawia oil refinery and Mellituh oil and gas refinery companies. A total of 200 workers participated in this study which consisting of two equal groups (each group: n = 100). The first group consists of petroleum refineries workers and the second group consists of non-oil work civil servants serving were recruited as exposed and control subjects, respectively. The results of blood picture, liver enzymes and kidney functions were compared between the groups. Mean white blood cells counts, platelet counts, and hematocrit count were significantly higher, while the mean red blood cells count was insignificantly changed in petroleum refineries workers. While the mean hemoglobin and corpuscular hemoglobin concentration levels were significantly lower, whereas the mean corpuscular volume and mean corpuscular hemoglobin levels were insignificantly changed in petrol refineries workers. Liver enzymes and renal functions were significantly higher in petrol refineries workers. The present findings indicate that occupational exposure to benzene causes significant alterations in hematological and biochemical parameters and workers are at high risk of developing blood, hepatic or renal related disorders. Protection and frequent medical attention should be given to petroleum refineries workers.

Analysis on incidence of occupational diseases in Guangzhou from 2010 to 2020 / 中华劳动卫生职业病杂志

Objective: To analyze the incidence characteristics of occupational diseases in Guangzhou from 2010 to 2020, provide scientific basis for formulating occupational disease prevention and control policies. Methods: In January 2021, based on the data of occupational diseases in Guangzhou reported in the Information Monitoring System of Occupational Diseases and Occupational Health, descriptive epidemiological method was used to analyze the types and characteristics of occupational diseases in Guangzhou from 2010 to 2020. Results: A total of 1341 cases of 38 kinds of occupational diseases in 9 categories were reported in the past 11 years. The incidence of occupational pneumoconiosis, occupational otolaryngology and oral diseases and occupational chemical poisoning ranked the top three, accounting for 38.1% (511/1341) , 30.5% (409/1341) and 16.2% (217/1341) of the total cases respectively. The cases of pneumoconiosis in welders and silicosis accounted for 47.7% (244/511) and 34.4% (176/511) of the cases of occupational pneumoconiosis respectively. The cases of noise deafness accounted for 99.8% (408/409) of occupational otorhinolaryngology oral diseases. Acute occupational chemical poisoning cases accounted for 26.7% (58/217) of the occupational chemical poisoning cases, in which dichloroethane poisoning cases ranked the first, accounting for 79.3% (46/58) . Chronic occupational chemical poisoning cases accounted for 73.3% (159/217) of the occupational poisoning cases, in which benzene and lead poisoning cases ranked the top two, accounting for 79.2% (126/159) and 17.6% (28/159) respectively. Conclusion: Pneumoconiosis, silicosis, noise deafness, benzene poisoning, lead poisoning, dichloroethane poisoning should be supervised and managed as key occupational diseases in Guangzhou.

Analysis on the detection of suspected occupational diseases and occupational contraindications for benzene workers in Tianjin / 中华劳动卫生职业病杂志

Objective: To investigate the detection of suspected occupational diseases and occupational contraindications for benzene workers in Tianjin. Methods: In June 2020, the occupational health inspection data of 16113 benzene workers in 514 enterprises with benzene hazards in 16 municipal districts in Tianjin from January to December 2019 were included in the analysis. Enterprise information included the employer's region, economic type, industry classification and enterprise scale. Occupational health inspection data for benzene workers during their on-the-job period included routine inspection indicators and benzene special inspection indicators. Multivariate unconditional logistic regression was used to analyze the relationship between personal general information, occupational history, enterprise information and suspected benzene poisoning and occupational contraindications of benzene workers. Results: There were 16073 benzene workers in the normal group and 24 in the suspected benzene poisoning group. The detection rate of suspected benzene poisoning in females was higher than that in males (χ(2)=8.26, P=0.004) . There was no significant difference in the detection rates of suspected benzene poisoning among different dimensions such as age, length of service, occupational health inspection institution location, employer location, industry classification, economic type, and enterprise scale (P>0.05) . There were 16073 benzene workers in the normal group and 16 in the benzene contraindication group. The detection rate of benzene contraindications for workers in suburban areas where occupational health inspection institutions were located was higher than that in urban areas (χ(2)=9.71, P=0.002) , and there was no significant difference in the detection rates of contraindications for benzene in other dimensions (P>0.05) . Multivariate logistic regression analysis showed that female benzene workers were more likely to detect suspected benzene poisoning (OR=3.53, 95%CI: 1.57-7.94, P=0.002) ; benzene workers who received physical examination in suburban occupational health inspection institutions (OR=5.81, 95%CI: 1.94-17.42, P=0.002) , the employer's area was in the suburbs (OR=9.68, 95%CI: 1.23-76.07, P=0.031) , and female workers (OR=3.07, 95%CI: 1.13-8.37, P=0.028) , it was easier to detect occupational contraindications. Conclusion: Female benzene workers with employers located in the suburbs have a higher risk of detecting occupational contraindications, and women are more likely to detect suspected benzene poisoning. The management of benzene operations in the production environment of enterprises in the suburbs of Tianjin and the occupational health monitoring of female workers should be strengthened.

Rapid determination of 30 volatile organic compounds in workplace air by gas chromatography / 中华劳动卫生职业病杂志

Objective: To establish a method for rapid detection of DB-WAX capillary column and determination of the workplace air in 30 kinds of volatile organic pollutants. Methods: In August 2020, N-pentane, n-hexane, methylcyclohexane, octane, Acetone, ethyl acetate, butanone, benzene, 3-pentanone, trichloroethylene, tetrachloroethylene, toluene, butyl acetate, 2-hexanone, Isoamyl acetate, ethylbenzene, p-xylene, m-xylene, amyl acetate, o-xylene, chlorobenzene, styrene, cyclohexanone, P-chlorotoluene, bromobenzene, M-dichlorobenzene, p-dichlorobenzene, O-dichlorobenzene, o-Chlorotoluene, 1, 2 , 4-trichlorobenzene of 30 kinds of substances in air were collected by activated carbon tube. After analysis by carbon disulfide, the analytical solution was analyzed by DB-WAX column and determined by FID detector. Results: The above 30 kinds of volatile organic pollutants had good separation effect, the correlation coefficient of the standard curve was above 0.999, the relative standard deviation was 0.1%-3.2%, the desorption efficiency was 77.0%-117.1% , the lower limit of quantitation was 0.33-5.33 μg/ml, and the lowest quantitation concentration was 0.22-3.55 mg/m(3), the recoveries ranged was 95.4%-104.9%. Conclusion: The method can effectively separate and accurately determine 30 volatile organic compounds in these workplaces, and the method is simple and quick.

Analysis of clinical effect of blood purification on acute benzene-based thinner poisoning / 中华劳动卫生职业病杂志

Objective: To investigate the clinical significance of blood purification on changes in serum toxicant concentration and prognosis of acute benzene-based thinner poisoning. Methods: A total of 44 patients with acute benzene-based thinner poisoning admitted to the emergency department of Characteristic Medical Center of Armed Police from August 2013 to August 2020 were collected and divided into a blood purification group (24 cases) and a conventional treatment group (20 cases) , the general data, toxicant concentrations and prognosis of the two groups of patients were analyzed, and logistic regression analysis was performed on the influencing factors of the prognosis to explore the clinical effect of blood purification. Results: The concentration of poisons in the blood purification group at 24 hours after treatment was significantly lower than that in the conventional treatment group (t=6.76, P<0.001) , and the reduction in the concentration of poisons was significantly higher than that in the conventional treatment group (t=3.33, P=0.002) . The overall improvement rate in the blood purification group was 91.7% (22/24) , which was higher than that in the conventional treatment group (60.0%, 12/20) . Logisitic regression analysis showed that blood purification treatment method was the main factor affecting the prognosis of patients (OR=7.605×10(-5), 95%CI: 6.604×10(-8)-0.087, P=0.008) , and the toxic dose was a synergistic effect on the prognosis of patients factor (OR=1.038, 95%CI: 1.008-1.068, P=0.011) . Conclusion: Early blood purification treatment in patients with acute benzene-based thinner poisoning can rapidly reduce blood toxin concentration, avoid disease progression, and ultimately improve patient prognosis.

Investigation and case analysis of an occupational chronic benzene poisoning accident / 中华劳动卫生职业病杂志

This article investigated an occupational chronic benzene poisoning incident that occurred in a sealing material factory in Hebei Province in September 2019, analyzed the clinical data of workers, to explore the causes of occupational chronic benzene poisoning, and summarize the diagnosis and treatment characteristics and treatment outcome. According to GBZ 68-2013 "Diagnosis of Occupational Benzene Poisoning", a total of 12 cases of occupational chronic benzene poisoning were diagnosed among the 20 workers, including 2 cases of occupational chronic mild benzene poisoning, 7 cases of moderate benzene poisoning, and 3 cases of severe benzene poisoning. Both mild and moderate poisoning patients had recovered after treatment. Severely poisoned patients had recovered more slowly, and the white blood cell count was still 2.0×10(9)-3.0×10(9)/L during the 1-year follow-up. This benzene poisoning incident was caused by illegal operations. The responsibility of the employer, the supervision of the administrative agency, and the awareness of personal protection of employees should be strengthened to avoid or reduce the occurrence of poisoning incidents and ensure the health of workers.

Comparative Bioaccumulation of PAH and BTEX in Malapterurus electricus (Siluriformes: Malapteruridae) and its Enteric Parasite, Electrotaenia malopteruri Sampled from Lekki Lagoon, Lagos, Nigeria / Bioacumulação comparativa de HAP e BTEX em Malapterurus electricus (Siluriformes: Malapteruridae) e seu parasita entérico, Electrotaenia malopteruri, coletado na lagoa Lekki, Lagos, Nigéria

Abstract Contamination of Lekki lagoon by petrogenic chemicals such as polycyclic aromatic hydrocarbons (PAH) and benzene, toluene, ethylbenzene, and xylene (BTEX) has been widely reported. The study was aimed at investigating the bioaccumulation of PAH and BTEX in Malapterurus electricus collected from Lekki lagoon in Lagos, Nigeria. BTEX was analyzed in the intestine, water, and sediment samples using 8260B Agilent 7890B gas chromatograph coupled to a mass spectrometer (GC-MS). While PAHs were tested in the same media using a gas chromatograph coupled to a flame ionization detector (GC-FID). Histopathological analysis of the fish intestine was conducted using haematoxylin and eosin (H&E) stains. Parasite intensity, antioxidant enzymes, and lipid peroxidation activities were investigated in the fish. The parasitic infection detected in Malapterurus electricus was Electrotaenia malopteruri. The parasite showed weak and no depurative capacities for BTEX and PAH respectively. The decrease in superoxide dismutase (SOD), catalase (CAT), and reduced glutathione (GSH) in conjunction with an increase in Malondialdehyde (MDA) characterized relatively higher susceptibility among the male fish. Varieties of tissue injuries increased with the standard length of the fish groups. Results suggest that lengthier and uninfected M. electricus were more susceptible to PAH in Lekki lagoon than the shorter and infected ones. The study demonstrated a promising tendency of the enteric parasite, E. malopteruri to depurate chlorobenzene, ethylbenzene, o-xylene, m+p-xylene, and 1,4-dichlorobenzene from the intestine of its host fish, M. electricus, while PAHs were poorly mediated by the parasite.

Resumo A contaminação da lagoa Lekki por produtos químicos petrogênicos, como hidrocarbonetos aromáticos policíclicos (HAP) e benzeno, tolueno, etilbenzeno e xileno (BTEX), foi amplamente relatada. O estudo teve como objetivo investigar a bioacumulação de HAP e BTEX em Malapterurus electricus, coletados na lagoa Lekki, em Lagos, Nigéria. O BTEX foi analisado no intestino, na água e nas amostras de sedimento usando o cromatógrafo de gás Agilent 7890B 8260B acoplado a um espectrômetro de massa (GC-MS). Já os HAP foram testados no mesmo meio utilizando cromatógrafo gasoso acoplado a detector de ionização de chama (GC-FID). A análise histopatológica do intestino do peixe foi conduzida usando colorações de hematoxilina e eosina (H&E). Intensidade de parasitas, enzimas antioxidantes e atividades de peroxidação lipídica foram investigadas nos peixes. A infecção parasitária detectada em Malapterurus electricus foi Electrotaenia malopteruri. O parasita mostrou fraca e nenhuma capacidade depurativa para BTEX e HAP, respectivamente. A diminuição da superóxido dismutase (SOD), catalase (CAT) e glutationa reduzida (GSH), em conjunto com o aumento do Malondialdeído (MDA), caracterizou a suscetibilidade relativamente maior entre os peixes machos. Variedades de lesões nos tecidos aumentaram com o comprimento padrão dos grupos de peixes. Os resultados sugerem que os M. electricus maiores e não infectados foram mais suscetíveis aos HAP na lagoa Lekki do que os menores e infectados. O estudo demonstrou uma tendência promissora do parasita entérico E. malopteruri de depurar clorobenzeno, etilbenzeno, o-xileno, m + p-xileno e 1,4-diclorobenzeno do intestino de seu peixe hospedeiro, M. electricus, enquanto os HAP foram mal mediados pelo parasita.

Avaliação da exposição a BTEX em postos de revenda de combustíveis no Rio de Janeiro, Brasil, e os riscos à saúde do trabalhador / Assessment of exposure to BTEX in vehicle filling stations in Rio de Janeiro, Brazil, and risks to workers' health / Evaluación de la exposición a BTEX en puestos de reventa de combustibles, en Río de Janeiro, Brasil, y riesgos para la salud del trabajador

A gasolina é uma mistura complexa de substâncias, dentre elas estão hidrocarbonetos como o benzeno, tolueno, etilbenzeno e xilenos (BTEX), sendo esses compostos emitidos para a atmosfera, com destaque ao benzeno, por ser comprovadamente carcinogênico. Objetivamos avaliar as concentrações de BTEX no ar de postos de revenda de combustíveis no Município do Rio de Janeiro, Brasil, e calcular o risco de câncer associado a estas exposições. Foram realizados dois tipos de amostragem (fixa e móvel) adaptadas da metodologia nº 1.501 do Instituto Nacional de Segurança e Saúde Ocupacional (Estados Unidos), em seis postos de revenda de combustíveis na Zona Oeste da cidade. A amostragem fixa foi feita próxima às bombas de combustível, enquanto a móvel foi realizada através da coleta do ar na zona respiratória dos trabalhadores (frentistas), conforme estes se deslocavam pelo posto. As amostras foram analisadas por cromatografia gasosa com detecção por ionização em chama. Com os resultados das amostragens foram feitos os cálculos de risco à saúde, usando os indicadores Quociente de perigo (HQ) e Risco de câncer (CR), para avaliar os possíveis efeitos não-carcinogênicos e carcinogênicos, respectivamente, nos trabalhadores dos postos de revenda de combustíveis. As concentrações ambientais para a maioria dos compostos BTEX foram abaixo dos limites preconizados, menos para o benzeno, um composto carcinogênico, que apresentou concentrações muito acima dos limites, levando a altos valores de risco de câncer. Os resultados demonstraram que há riscos à saúde dos trabalhadores de postos de revenda de combustíveis, principalmente o risco de desenvolver câncer, devido à exposição excessiva ao benzeno.

Gasoline is a complex mixture of substances, including aromatic hydrocarbons such as benzene, toluene, ethylbenzene, and xylenes (BTEX). These compounds are emitted into the air, with the special relevance of benzene since it is provenly carcinogenic. The study aimed to assess BTEX concentrations in filling stations in the city of Rio de Janeiro, Brazil, and to calculate the cancer risk associated with such exposures. Two types of sampling were performed (stationary and mobile), adapted from methodology n. 1,501 (U.S. National Institute for Occupational Safety and Health) for aromatic hydrocarbons, in six filling stations in the West Zone of Rio de Janeiro. Stationary sampling was done near the fuel pumps, while mobile sampling was done in the breathing zone of the workers (station attendants) as they moved around the station. The samples were analyzed with gas chromatography flame ionization detector. The sampling results were used to calculate the health risk, using the indicators Hazard quotient (HQ) and Cancer risk (CR) to assess the possible non-carcinogenic and carcinogenic effects, respectively, in filling station workers. Environmental concentrations for the most of the BTEX compounds were below the recommended limits, except for benzene, a carcinogenic compound, which displayed concentrations far above the limits, leading to high cancer risk values. The results showed that there are health risks for filling station attendants, especially the risk of developing cancer from excessive exposure to benzene.

La gasolina es una mezcla compleja de sustancias, entre ellas existen hidrocarburos como el benceno, tolueno, etilbenceno y xilenos (BTEX), emitiéndose estos compuestos a la atmósfera, donde se destaca el benceno, al tratarse de un carcinogénico comprobado. Los objetivos fueron evaluar las concentraciones de BTEX en el aire de puestos de reventa de combustibles, en el municipio de Río de Janeiro, Brasil, así como calcular el riesgo de cáncer asociado a estas exposiciones. Se realizaron dos tipos de muestra (fija y movible), adaptadas de la metodología nº 1.501 del Instituto Nacional de Seguridad y Salud Laboral (EE.UU.), en seis puestos de reventa de combustibles de la zona oeste de la ciudad. La muestra fija se realizó cerca de las bombas de combustible, mientras que la móvil se hizo mediante tomas de aire en la zona respiratoria de los trabajadores (de la gasolinera), a medida que estos se desplazaban por el lugar de trabajo. Las muestras se analizaron por cromatografía gaseosa con detección por ionización en llama. Junto a los resultados de las muestras, se realizaron cálculos de riesgo para la salud, usando los indicadores Cociente de peligro (HQ) y Riesgo de cáncer (CR), con el fin de evaluar los posibles efectos no-carcinogénicos y carcinogénicos, respectivamente, en los trabajadores de los puestos de reventa de combustibles. Las concentraciones ambientales para la mayoría de los compuestos BTEX estuvieron por debajo de los limites preconizados, menos en el caso del benceno, un compuesto carcinogénico, que presentó concentraciones muy por encima de los límites, llevando a altos valores de riesgo de cáncer. Los resultados demostraron que existen riesgos para la salud de los trabajadores de puestos de reventa de combustibles, principalmente, riesgo de desarrollar cáncer, debido a la exposición excesiva al benceno.

Occupational Health Risk Assessment of Benzene, Toluene, and Xylene in Shanghai / 生物医学与环境科学（英文）

Objective@#This study was designed to conduct a retrospective and systematic occupational health risk assessment (OHRA) of enterprises that used benzene, toluene, and xylene (BTX) in Shanghai, China.@*Methods@#All data for the study were obtained from 1,705 occupational health examination and evaluation reports from 2013 to 2017, and a semiquantitative model following Chinese OHRA guidelines (GBZ/T 298-2017) was applied for the assessment.@*Results@#The selected enterprises using BTX were mainly involved in manufacturing of products. Using the exposure level method, health risk levels associated with exposure to BTX were classified as medium, negligible, or low. However, the risk levels associated with benzene and toluene were significantly different according to job types, with gluers and inkers exhibiting greater health risks. For the same job type, the health risk levels assessed using the comprehensive index method were higher than those using the exposure level method.@*Conclusion@#Our OHRA reveals that workers who are exposed to BTX still face excessive health risk. Additionally, the risk level varied depending on job categories and exposure to specific chemicals. Therefore, additional control measures recommended by OHRA guidelines are essential to reduce worker exposure levels.

Alterações biológicas em operadores de bomba de abastecimento expostos ao benzeno: uma revisão sistemática / Biological changes in benzene-exposed supply pump operators: a systematic review

Introdução: O benzeno é um composto proveniente do petróleo, adicionado à gasolina em pequena quantidade para aumentar a octanagem desse combustível. Esse composto está presente nos veículos, por isso a população está exposta à emissão de vapores de gasolina. Contudo, deve-se ter uma atenção especial aos trabalhadores de postos de gasolina, pois esses são submetidos a níveis altos de benzeno, que pode causar desde sintomas por exposição aguda até o desenvolvimento de leucemia pela cronicidade da exposição. Objetivo: Estudar as alterações biológicas pela exposição ao benzeno em operadores de postos de serviços e bombas de abastecimento inflamáveis, analisar os riscos do hidrocarboneto benzeno ao organismo destes trabalhadores e propor a inserção de análise de um novo perfil hematológico, bioquímico e imunológico no exame médico ocupacional destes trabalhadores. Material e Método: Este trabalho consiste em uma revisão sistemática qualitativa da literatura, fundamentada nas recomendações do PRISMA statement, utilizando-se como frase de busca: ("Hidrocarbon*" OR "Benzen") AND ("hematology*") AND ("filling station"). Resultado: Os achados de seis artigos originais foram apresentados em tabela. Conclusões: Estudos complementares devem ser realizados com a finalidade de detectar marcadores que permitam o diagnóstico precoce dos danos hematológicos, bioquímicos e imunológicos provocados pela exposição ao benzeno.

Introduction: Benzene is a petroleum compound, that is added to gasoline in small quantities to increase the octane of this fuel. This compound is present in vehicles, so the population as a whole is exposed to the emission of gasoline vapors. However, special attention should be paid to gas station workers, because they are subjected to high levels of benzene, which can cause from acute exposure symptoms to the development of leukemia due to chronic exposure. Objective: To study the biological changes due to benzene exposure in service station and flammable supply pumps operators, to analyze the risks of benzene to the organism of these workers and to propose the insertion of a new hematological, biochemical and immunological profile in the medical examination occupational of workers. Material and Method: This work consists of a qualitative systematic literature review, based on the recommendations of the PRISMA statement, using as search phrase: ("Hydrocarbon *" OR "Benzen") AND ("hematology *") AND ("filling station"). Results: The findings of six original articles were presented in a table. Conclusions: Complementary studies should be performed to detect markers, that allow the early diagnosis of hematological, biochemical and immunological damage, caused by exposure to benzene.

Maternal exposure to benzene and toluene and preterm birth. A longitudinal study

ABSTRACT BACKGROUND: Exposure to air pollutants has several effects on human health, including during pregnancy. OBJECTIVE: To identify whether exposure to benzene and toluene among pregnant women contributes to preterm delivery. DESIGN AND SETTING: Longitudinal study using data on newborns from mothers living in São José dos Campos (SP) in 2016, who had been exposed to benzene and toluene. METHODS: A logistic regression model with three hierarchical levels was constructed using maternal variables relating to newborns, and using benzene and toluene concentrations in quartiles. Occurrences of cesarean births, twins or malformations were excluded. Maternal exposure windows of 5, 10, 15, 30, 60 and 90 days prior to delivery were considered. RESULTS: Out of the 9,562 live births, 3,671 newborns were included and 343 newborns were born at less than 37 weeks of gestation (9.3%). The average birth weight was 3,167.2 g. Exposure to benzene and toluene was significantly associated (P = 0.04) with preterm delivery in the five-day window. There was no association in any of the other exposure windows. CONCLUSIONS: It was possible to identify that maternal exposure to benzene and toluene has an acute effect on preterm delivery.

Environmental exposure to benzene: evaluation of urinary S-PMmorphism (CYP2E1-129A and poly3G>C and NQO1 609C> T) in Campos Elíseos residents, Duque de Caxias, Rio de Janeiro State, Brazil / Exposição ambiental ao benzeno: avaliação do S-PMA urinário e de polimorfismos (CYP2E1-1293G>C e NQO1 609C> T) em residentes de Campos Elíseos, Duque de Caxias, Rio de Janeiro, Brasil / Exposición ambiental al benceno: análisis del S-PMA en la orina y polimorfismo (CYP2E1-1293G>C y NQO1 609C> T) en residentes de Campos Elíseos, Duque de Caxias, Río de Janeiro, Brasil

Benzene is one of the most important substances for assessment, due to its significant use, the environmental contamination resulting from its emission and the effects on human health. It is classified by the International Agency for Research on Cancer (IARC) as a known carcinogen to humans (group 1) and associated with the development of leukemia. In general, the population is exposed to this substance by inhaling contaminated air, which varies according to the location and intensity of its potential sources. The petrochemical industry is one of the most important sources of this compound. The municipality of Duque de Caxias, specifically the Campos Elíseos district, in Rio de Janeiro State, Brazil, houses the Industrial Complex of Campos Elíseos (PICE), a grouping of over 25 industries, which includes the second largest oil refinery in Brazil. Environmental contamination from the PICE has been recognized, but there is a lack of studies concerning its impact on the health of the surrounding population. S-phenylmercapturic acid (S-PMA) concentrations ranging from 0.80 to 8.01μg.g-1 creatinine were observed in the local population, apparently related to hematological changes also observed in exposed population. The quantifiable presence of urinary S-PMA from the benzene metabolism is associated with the fact that 60% of the participants present specific hematological changes, which may be due to the environmental benzene exposure. The allele and genotype frequencies of the CYP2E1 and NQO1 enzymes observed in the study population were similar to those reported in other studies. The presence of the variant allele in the NQO1 genotype may be a risk factor for the observed hematological changes.

O benzeno é uma das substâncias mais importantes para a biomonitorização, em função do uso disseminado, da contaminação ambiental que resulta da emissão e dos efeitos sobre a saúde humana. O benzeno é classificado pela Agência Internacional de Pesquisa em Câncer (IARC) como carcinógeno conhecido em seres humanos (grupo 1) e está associado ao desenvolvimento de leucemias. Em geral, a população fica exposta a essa substância através da inalação do ar contaminado, que varia de acordo com a localização e a intensidade das fontes potenciais. A indústria petroquímica é uma das fontes mais importantes desse composto. O Município de Duque de Caxias, especificamente o Distrito de Campos Elíseos, no Estado do Rio de Janeiro, Brasil, é sede do Polo Industrial de Campos Elíseos (PICE), um conjunto de mais de 25 indústrias que inclui a segunda maior refinaria de petróleo no Brasil. A contaminação ambiental produzida pelo PICE já é conhecida, mas faltam estudos sobre o impacto na saúde da população local. Foram observadas concentrações de ácido S-fenilmercaptúrico (S-PMA) entre 0,80 e 8,01μg.g-1 creatinina na população local, aparentemente implicadas nas alterações hematológicas também observadas na população exposta. A presença quantificável do S-PMA urinário do metabolismo do benzeno está associada ao fato de 60% dos participantes apresentarem alterações hematológicas específicas, o que pode ser devido à exposição ambiental ao benzeno. As frequências alélicas e genotípicas das enzimas CYP2E1 e NQO1, observadas na população do estudo, foram semelhantes àquelas relatadas em outros estudos. A presença da variante alélica do genótipo NQO1 pode ser um fator de risco para as alterações hematológicas observadas.

El benceno es una de las sustancias más importantes susceptibles de estudio, debido a su uso significativo, la contaminación ambiental resultante de sus emisiones y sus efectos sobre la salud humana. Está clasificado por el Centro Internacional de Investigaciones sobre el Cáncer (IARC) como un conocido carcinógeno para los humanos (grupo 1) y está asociado con el desarrollo de leucemias. En general, la población está expuesta a esta sustancia por inhalación de aire contaminado, que varía según el lugar y la intensidad de las emisiones. La industria petroquímica es un de las fuentes emisoras más importantes de este compuesto. La municipalidad de Duque de Caxias, específicamente el distrito de Campos Elíseos, en Río de Janeiro, Brasil, alberga el Complejo Industrial de Campos Elíseos (PICE), un conglomerado de más de 25 industrias, que incluye la segunda mayor refinería de petróleo en Brasil. La contaminación ambiental procedente del PICE ya ha sido reconocida, pero es notable la falta de estudios respecto a su impacto en la salud de la población circundante. Se observaron en la población local concentraciones de ácido s-fenilmercaptúrico (SPMA por sus siglas en inglés) que oscilan entre los 0,80 a 8,01μg.g-1 creatinina, aparentemente relacionadas con cambios hematológicos también hallados en la población expuesta. La presencia cuantificable de SPMA en la orina, procedente del metabolismo del benceno, está asociada con el hecho de que un 60% de los participantes presenta cambios específicos hematológicos, los cuales tal vez se deben a la exposición ambiental al benceno. Las frecuencias alélicas y genotípicas del CYP2E1 y enzimas NQO1 observadas en el estudio fueron similares a las reportadas en otros estudios. La presencia de la variante alélica en el genotipo NQO1 podría ser un factor de riesgo para los cambios hematológicos observados.

Os discursos de risco como prática educativa no trabalho: uma análise da campanha operação Caça Benzeno (1991-1994) / Risk speeches as an educational practice at work: an analysis of the campaign Caça Benzeno (1991-1994)

Esta dissertação trata de uma campanha de saúde no mundo do trabalho: a Operação Caça Benzeno. Desenvolvida entre os anos de 1991 e 1994, a campanha fez parte de um projeto de formação em saúde no trabalho, coordenado pela Central Única dos Trabalhadores (CUT) em parceria com algumas organizações nacionais e com a Confederazione Generale Italiana del Lavoro (CGIL), maior entidade sindical da Itália naquela época. Tinha por finalidade instruir os trabalhadores quanto aos cuidados de si considerados prudentes e saudáveis e a exercerem a vigilância em saúde no trabalho. O problema é que os discursos e práticas de saúde podem reforçar os processos de culpabilização destes sujeitos, caso não sejam observados os múltiplos fatores que objetivamente caracterizam os processos de trabalho e subjetivamente são administrados por estes indivíduos nas escolhas para adotar comportamentos e cobrar responsabilidades patronais. A hipótese é que as responsabilidades individuais de risco são dialeticamente construídas entre os discursos e práticas desenvolvidas por sindicatos e órgãos públicos para representar os trabalhadores que atuam na cadeia de produção, processamento, distribuição e comercialização de benzeno e seus derivados no Brasil.

O objetivo desta pesquisa foi compreender como as responsabilidades individuais de risco são construídas através dos discursos de prescrição comportamental das campanhas de promoção da saúde e prevenção de doenças. Observamos como uma cartilha, um jornal e uma revista integraram um conjunto de práticas comunicativas desenvolvidas pela CUT e órgãos públicos para ensinar os trabalhadores a lidar com a epidemia de benzenismo. Verificamos que os gêneros educativos se constituíram entre textos, práticas discursivas e os eventos realizados por estas instituições para abordar o benzenismo como tema de campanha. A convocação feita por sindicatos e órgãos públicos aos trabalhadores na Operação Caça Benzeno nos apontou a proposição de um protagonismo a ser exercido por esses sujeitos para cuidar da própria saúde, mas desconsiderando os recursos e contextos específicos que constituem os processos trabalho e determinam as condições para a tomada de decisões e à adoção de comportamentos no cotidiano laboral. (AU)

Workplace Diesel Exhausts and Gasoline Exposure and Risk of Colorectal Cancer in Four Nordic Countries

BACKGROUND: Evidence on associations between occupational diesel exhaust and gasoline exposure and colorectal cancer is limited. We aimed to assess the effect of workplace exposure to diesel exhaust and gasoline on the risk of colorectal cancer. METHODS: This caseecontrol study included 181,709 colon cancer and 109,227 rectal cancer cases diagnosed between 1961 and 2005 in Finland, Iceland, Norway, and Sweden. Cases and controls were identified from the Nordic Occupational Cancer Study cohort and matched for country, birth year, and sex. Diesel exhaust and gasoline exposure values were assigned by country-specific job-exposure matrices. Odds ratios and 95% confidence intervals were calculated by using conditional logistic regression models. The results were adjusted for physical strain at work and occupational exposure to benzene, formaldehyde, ionizing radiation, chlorinated hydrocarbons, chromium, and wood dust. RESULTS: Diesel exhaust exposure was associated with a small increase in the risk of rectal cancer (odds ratio 1/4 1.05, 95% confidence interval 1.02–1.08). Gasoline exposure was not associated with colorectal cancer risk. CONCLUSION: This study showed a small risk increase for rectal cancer after workplace diesel exhaust exposure. However, this finding could be due to chance, given the limitations of the study.

Insights Into Emissions and Exposures From Use of Industrial-Scale Additive Manufacturing Machines

BACKGROUND: Emerging reports suggest the potential for adverse health effects from exposure to emissions from some additive manufacturing (AM) processes. There is a paucity of real-world data on emissions from AM machines in industrial workplaces and personal exposures among AM operators. METHODS: Airborne particle and organic chemical emissions and personal exposures were characterized using real-time and time-integrated sampling techniques in four manufacturing facilities using industrial-scale material extrusion and material jetting AM processes. RESULTS: Using a condensation nuclei counter, number-based particle emission rates (ERs) (number/min) from material extrusion AM machines ranged from 4.1×1010 (Ultem filament) to 2.2×1011 [acrylonitrile butadiene styrene and polycarbonate filaments). For these same machines, total volatile organic compound ERs (mg/min) ranged from 1.9×104 (acrylonitrile butadiene styrene and polycarbonate) to 9.4×104 (Ultem). For the material jetting machines, the number-based particle ER was higher when the lid was open (2.3×1010 number/min) than when the lid was closed (1.5–5.5×109 number/min); total volatile organic compound ERs were similar regardless of the lid position. Low levels of acetone, benzene, toluene, and m,p-xylene were common to both AM processes. Carbonyl compounds were detected; however, none were specifically attributed to the AM processes. Personal exposures to metals (aluminum and iron) and eight volatile organic compounds were all below National Institute for Occupational Safety and Health (NIOSH)-recommended exposure levels. CONCLUSION: Industrial-scale AM machines using thermoplastics and resins released particles and organic vapors into workplace air. More research is needed to understand factors influencing real-world industrial-scale AM process emissions and exposures.

Evaluation of Hazardous Chemicals with Material Safety Data Sheet and By-products of a Photoresist Used in the Semiconductor-Manufacturing Industry

BACKGROUND: The photolithography process in the semiconductor industry uses various chemicals with little information on their constitution. This study aimed to identify the chemical constituents of photoresist (PR) products and their by-products and to compare these constituents with material safety data sheets (MSDSs) and analytical results. METHODS: A total of 51 PRs with 48 MSDSs were collected. Analysis consisted of two parts: First, the constituents of the chemical products were identified and analyzed using MSDS data; second, for verification of the by-products of PR, volatile organic compounds were analyzed. The chemical constituents were categorized according to hazards. RESULTS: Forty-five of 48 products contained trade secrets in amounts ranging from 1 to 65%. A total of 238 ingredients with multiple counting (35 ingredients without multiple counting) were identified in the MSDS data, and 48.7% of ingredients were labeled as trade secrets under the Korea Occupational Safety and Health Act. The concordance rate between the MSDS data and the analytical result was 41.7%. The by-product analysis identified 129 chemicals classified according to Chemical Abstracts Service No., with 17 chemicals that are carcinogenic, mutagenic, and reprotoxic substances. Formaldehyde was found to be released from 12 of 21 products that use novolak resin. CONCLUSION: We confirmed that several PRs contain carcinogens, and some were not specified in the toxicological information in the MSDS. Hazardous chemicals, including benzene and formaldehyde, are released from PRs products as by-products. Therefore, it is necessary to establish a systematic management system for chemical compounds and the working environment.

Niveles urinarios de ácido trans, trans mucónico y orto cresol en una población infanto-juvenil residente en Ciudad Autónoma de Buenos Aires y Conurbano Bonaerense / Urinary levels of trans, trans muconic and ortho cresol in an infant-juvenile population resident in the Autonomous City of Buenos Aires and the Conurbano of Buenos Aires

Introducción: la exposición crónica al benceno y tolueno produce alteraciones sobre la médula ósea y el sistema nervioso central, entre otros. En orina, el ácido trans, trans mucónico (t, t-MA) es uno de los biomarcadores de exposición al benceno y el o-cresol (oCre) al tolueno. Objetivo: analizar los resultados de los niveles de t, t-MA y oCre urinarios en una población infanto-juvenil residente en Ciudad Autónoma de Buenos Aires y Conurbano Bonaerense potencialmente expuesta a benceno y tolueno ambiental. Materiales y métodos: se realizó un estudio retrospectivo de los resultados de t, t-MA y oCre urinarios. Las muestras de orina ingresaron al laboratorio con solicitud de t, t-MA (n=1519) y oCre (n=1447) durante el período 2011-2017 (rango etario entre 0 a 19 años). El t, t-MA se cuantificó por UFLC con detector de arreglo de diodos y el oCre por CG con detector de ionización por llama. Resultados: la edad promedio de los pacientes fue de 4,8 años y la mediana 4,6 años.Las concentraciones de t, t-MA urinario fueron: menor de 50 μg/l (44,8%); entre 50-500 μg/l (52,1%) y mayores de 500 μg/l (3,1%). Expresadas por gramo de creatinina: entre 15-163 μg/g creatinina (60,4%) y mayores de 163 μg/g creatinina (39,6%). El límite de cuantificación de t, t-MA fue de 50 μg/l. Las concentraciones de oCre urinario fueron: menor de 0,20 mg/l (97,7%) y entre 0,20-0,50 mg/l (2,3%) y mayor de 0,50 mg/l (0%). Expresadas por gramo de creatinina: menor de 0,30 mg/g creatinina en el 0,8% y mayores de 0,30 mg/g creatinina en el 1,5%. El límite de cuantificación de oCre fue de 0,20 mg/l. Conclusiones: los resultados del trabajo podrían indicar una contaminación ambiental persistente, en especial en el Conurbano Bonaerense, donde debería continuarse el monitoreo de algunas zonas. Pero, por otro lado, es de vital importancia tener en cuenta los factores de confusión, tales como la dieta, la exposición al humo de tabaco ambiental (fumador pasivo) y la tasa de excreción renal que llevarían a una sobre-estimación de los resultados y a una incorrecta toma de decisiones.

Introduction: Chronic exposure to benzene and toluene produces alterations in the bone marrow and the central nervous system, among other effects. In urine, trans, trans muconic acid (t, t-MA) is one of the biomarkers of exposure to benzene and o-cresol (oCre), to toluene. Objective: To analyze the results of urinary t, t-MA and oCre levels in an infant-juvenile population resident in the Autonomous City of Buenos Aires and the Conurbano Bonaerense, potentially exposed to environmental benzene and toluene. Materials and methods: A retrospective study of urinary t, t-MA and oCre results was performed. The urine samples entered the laboratory with the request of t, t-MA (n = 1519) and oCre (n = 1447) during the period 2011- 2017. The age range of the population was between 0 and 19 years. The t, t-MA was quantified by UFLC with diode array detector and the oCre by GC with flame ionization detector. Results: The average age of the patients was 4.8 years and the median age was 4.6 years. The urinary concentrations of t, t-MA were: below 50 μg/l (44.8%); between 50-500 μg/l (52.1%) and above 500 μg/l (3.1%). Expressed per gram of creatinine: between 15-163 μg/g creatinine (60.4%) and greater 163 μg/g creatinine (39.6%). The limit of quantification of t, t-MA was 50 μg/l. The urinary oCre concentrations were: less than 0.20 mg/l (97.7%) and between 0.20-0.50 mg/l (2.3%). Expressed per gram of creatinine: less than 0.30 mg/g creatinine in 0.8% and greater than 0.30 mg/g creatinine in 1.5%. The limit of quantification of oCre was 0.20mg/l. Conclusions: The results of the study could indicate persistent environmental contamination, especially in the Conurbano Bonaerense, where monitoring of some areas should be continued. However, it is of vital importance to take into account the confounding factors, such as diet, exposure to environmental tobacco smoke (passive smoking) and the rate of renal excretion, which would lead to an over-estimation of the results and to incorrect decision-making.