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Concept: Chrysene

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BACKGROUND: Bronchial asthma is one of the most prevalent diseases in Arab children. Environmental pollution has been suggested to be considered causative of asthma, nasal symptoms and bronchitis in both children and adult. The objectives of this study were to evaluate the association between serum polycyclic aromatic hydrocarbons (PAHs) levels, asthma and allergic outcomes among Saudi children aged up to 15 yrs. We hypothesized that increased serum PAHs are associated with allergy, asthma, or respiratory symptoms. METHODS: A total of 195 Saudi children (98 asthma pediatric patients and 97 healthy controls) were randomly selected from the Riyadh Cohort Study for inclusion. The diagnosis of Asthma was based on established pediatric diagnosis and medications taken. RESULTS: Asthma related markers showed highly significant differences between children with and without asthma. Thus IgE, resistin and IL-4 were significantly increased (p 0.004, 0.001 and 0.003, respectively) in children with asthma compared with non-asthma control subjects. GMCSF, IFN-gamma, IL-5, IL-8 and IL-10, on the other hand, were significantly decreased in children with asthma (p 0.003, 0.03, 0.001, 0.004 and 0.03, respectively). Strong associations between serum PAHs levels and biomarkers of childhood asthma were detected in Arabic children. Data confirmed the role of naphthalene, 4H-cyclobenta[def]phenanthrene, 1,2-benzanthracene, chrysene and benzo(e)acephenanthrylene in childhood asthma; levels of these PAHs were correlated with asthma related biomarkers including IgE, resistin, GMCSF and IFN-gamma as well as IL-4, IL-5, IL-8 and IL-10 cytokines. CONCLUSIONS: This data highlight the pivotal role of specific PAHs in childhood asthma.

Concepts: Asthma, Allergy, Polycyclic aromatic hydrocarbon, Benzene, Hydrocarbon, Aromaticity, Naphthalene, Chrysene

151

The analysis of polycyclic aromatic hydrocarbons (PAH) in ambient air requires the tedious experimental steps of both sampling and pretreatment (e.g., extraction or clean-up). To replace pre-existing conventional methods, a simple, rapid, and novel technique was developed to measure gas-particle fractionation of PAH in ambient air based on ‘sorbent tube-thermal desorption-gas chromatograph-mass spectrometer (ST-TD-GC-MS)’. The separate collection and analysis of ambient PAHs were achieved independently by two serially connected STs. The basic quality assurance confirmed good linearity, precision, and high sensitivity to eliminate the need for complicated pretreatment procedures with the detection limit (16 PAHs: 13.1 ± 7.04 pg). The analysis of real ambient PAH samples showed a clear fractionation between gas (two-three ringed PAHs) and particulate phases (five-six ringed PAHs). In contrast, for intermediate (four ringed) PAHs (fluoranthene, pyrene, benz[a]anthracene, and chrysene), a highly systematic/gradual fractionation was established. It thus suggests a promising role of ST-TD-GC-MS as measurement system in acquiring a reliable database of airborne PAH.

Concepts: Measurement, Polycyclic aromatic hydrocarbon, Benzene, Aromaticity, Naphthalene, Pyrene, Fluoranthene, Chrysene

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Laboratory and field studies were carried out to assess the effects of oxidative degradation and volatilization on PM10bound polycyclic aromatic hydrocarbons (PAHs), collected at low volume condition according to the EU sampling reference method EN12341:2014 (flow rate 2.3 m3 h-1), on 47 mm quartz filters. For the laboratory experiments, pairs of twin samples were collected in field and, after treatments favoring decomposition or/and volatilization of PAHs on one sample, the PAH amount was compared with that of the corresponding untreated sample. Ozone exposure caused a general PAHs decay with more marked effects on benzo [a]pyrene, perylene and benz [a]anthracene; these compounds showed, similarly to benzo [ghi]perylene, correlations between ozone dose and losses. Treatments with zero air exhibited losses due to volatilization even for 5-ring PAHs up to benzo [a]pyrene, whereas a linear dependence was observed between filter PAH load and losses for benzo [a]anthracene, chrysene and benzofluoranthenes. Concentrations on samples collected simultaneously over 48, 24, 12 and 6 h were compared. Results confirmed a lack of temporal auto-consistency in the PAHs sampling methodology here adopted. In particular higher atmospheric PAH concentrations were ascertained on samples constituted by cumulative filters exposed over shorter sampling times. When 24-h and 2 × 12-h samples were compared, comparable losses were evaluated in the hot and cold seasons. This finding shows that, although in summer meteorology conditions favor sampling artifacts, the effectiveness of these phenomena continue in the winter, probably due to the larger amount of PAH available on the sampling filter (total PAHs ∼ 10 vs 0.5 ng m-3).

Concepts: Observation, Polycyclic aromatic hydrocarbon, Experiment, Aromaticity, Naphthalene, Perylene, Polycyclic aromatic hydrocarbons, Chrysene

0

Rainfall runoff can remove certain amounts of pollutants from contaminated farmland soil and result in a decline in water quality. However, the leaching behaviors of polycyclic aromatic hydrocarbons (PAHs) with rainfall have been rarely reported due to wide variations in the soil compositions, rainfall conditions, and sources of soil PAHs in complex farmland ecosystems. In this paper, the levels, spatial distributions, and composition profiles of PAHs in 30 farmland soil samples and 49 rainfall-runoff samples from the Tianjin region in 2012 were studied to investigate their leaching behaviors caused by rainfall runoff. The contents of the Σ16PAHs ranged from 58.53 to 3137.90 μg/kg in the soil and 146.58 to 3636.59 μg/L in the runoff. In total, most of the soil sampling sites (23 of 30) were contaminated, and biomass and petroleum combustion were proposed as the main sources of the soil PAHs. Both the spatial distributions of the soil and the runoff PAHs show a decreasing trend moving away from the downtown, which suggested that the leaching behaviors of PAHs in a larger region during rainfall may be mainly affected by the compounds themselves. In addition, 4- and 5-ring PAHs are the dominant components in farmland soil and 3- and 4-ring PAHs dominate the runoff. Comparisons of the PAH pairs and enrichment ratios showed that acenaphthylene, acenaphthene, benzo[a]anthracene, chrysene, and fluoranthene were more easily transferred into water systems from soil than benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[ghi]perylene, and indeno[123-cd]pyrene, which indicated that PAHs with low molecular weight are preferentially dissolved due to their higher solubility compared to those with high molecular weight.

Concepts: Agriculture, Water, Soil, Polycyclic aromatic hydrocarbon, Aromaticity, Polycyclic aromatic hydrocarbons, Pyrene, Chrysene

0

One of the primary sources of polycyclic aromatic hydrocarbons (PAHs) in marine environments is oil. Photochemical oxidation and microbial transformation of PAH-containing oils can result in the formation of oxygenated products. Among the PAHs in crude oil, chrysene is one of the most persistent within the water column and may be transformed to 2- and 6-hydroxychrysene (OHCHR). Both of these compounds have been shown to activate (2-OHCHR) and antagonize (6-OHCHR) the estrogen receptor (ER). Previous studies in our lab have shown that estrogen can significantly alter zebrafish development. However, little is known about the developmental toxicity of hydroxylated PAHs. Zebrafish embryos were exposed to 0.5-10μM of 2- or 6-OHCHR from 2h post-fertilization (hpf) until 76hpf. A significant decrease in survival was observed following exposure to 6-OHCHR - but not 2-OHCHR. Both OHCHRs significantly increased the percentage of overall deformities after treatment. In addition to cardiac malformations, ocular and circulatory defects were also observed in embryos exposed to both compounds, while 2-OHCHR generally resulted in a higher prevalence of effect. Moreover, treatment with 2-OHCHR resulted in a significant decrease in hemoglobin levels. ER nor G-Protein coupled estrogen receptor (GPER) antagonists and agonists did not rescue the observed defects. We also analyzed the expression of cardiac-, eye- and circulation-related genes previously shown to be affected by oil. Rhodopsin mRNA expresssion was significantly decreased by both compounds equally. However, exposure to 2-OHCHR significantly increased the expression of the hematopoietic regulator, runx1 (runt related transcription factor 1). These results indicate the toxicity of oxygenated photoproducts of PAHs and suggest that other targets and signaling pathways may contribute to developmental toxicity of weathered oil. Our findings also demonstrate the regio-selective toxicity of hydroxy-PAHs in the effects on eye and circulatory development and raise the need to identify mechanisms and ecological risks of oxy-PAHs to fish populations.

Concepts: Signal transduction, Developmental biology, Petroleum, Transcription factor, Carbon, Polycyclic aromatic hydrocarbon, Hydrocarbon, Chrysene

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The distribution, sources, and ecological risk of polycyclic aromatic hydrocarbons (PAHs) were investigated in surface sediments from the Haihe River. Total PAH concentrations varied from 171.4 to 9511.2 ng g(-1) with an average of 2125.4 ng g(-1), suggesting serious pollution of the Haihe River in comparison with other reported rivers worldwide. PAH contaminants differed significantly among 17 sampling locations with high values occurring in industrial areas and densely populated areas. The composition of PAHs was characterized by high abundance of 4-ring and 5-ring PAHs, and benzo[a]anthracene, chrysene, and benzo[a]pyrene were the predominant components. Molecular diagnostic ratios have confirmed that PAHs in Haihe River sediments resulted from mixed sources, primarily including various combustion processes. Ecological risk assessment using the Sediments Quality Guidelines indicated that PAHs in sediments could cause certain negative effects on aquatic organisms in most survey regions.

Concepts: Sediment, Polycyclic aromatic hydrocarbon, Population density, Pollution, Aromaticity, Soil contamination, Naphthalene, Chrysene

0

A novel preconcentrator-separator two-in-one online system has been developed for the online analysis of trace amounts of four polycyclic aromatic hydrocarbons (PAHs) in tea samples. A micro-preconcentrator unit of zeolite imidazolate framework-8-poly(vinyl alcohol) cryogel (ZIF-8-PVA cryogel) and a micro-separation unit of multiwalled carbon nanotubes-poly(vinyl alcohol) cryogel (MWCNTs-PVA cryogel) were fabricated onto an acrylic plate. The eluent from this two-in-one system flowed directly to an on-column UV-visible detector. Under optimum conditions, the system provided a wide linear range from 0.10µgL(-1) to 2.00mgL(-1) for benzo(a)anthracene (BaA) and chrysene (Chry), 0.15µgL(-1) to 3.00mgL(-1) for benzo(a)pyrene (BaP) and 0.20µgL(-1) to 5.00mgL(-1) for benzo(b)fluoranthene (BbF). The limits of detection were 0.05µgL(-1) of both BaA and Chry, 0.10µgL(-1) of BaP and 0.20µgL(-1) of BbF. This two-in-one system was cost-effective, easy to prepare, had excellent stability for up to 417 consecutive injection cycles and provided a good system-to-system reproducibility (n=6) with a relative standard deviation of less than 4%. The system was successfully applied to detect PAHs in tea samples. The concentrations of BaA, Chry, BaP and BbF in seven tea samples were found in the range of non-detectable 2.73±0.07mgL(-1) with good recoveries of 83±6 to 108±4%. In addition, it can be easily applied for the detection of other aromatic compounds in contaminated water samples.

Concepts: Scientific method, Carbon, Polycyclic aromatic hydrocarbon, Benzene, Aromatic hydrocarbon, Aromaticity, Naphthalene, Chrysene

0

An accelerated solvent extraction (ASE) procedure for use with gas chromatography-mass spectrometry (GC-MS) was optimized for the determination of eight polycyclic aromatic hydrocarbons (PAHs) in cocoa beans. Plackett-Burman and rotatable central composite design (RCCD) indicated that three variables affected the recoveries of PAHs during the extraction and purification steps: agitation time in the second liquid-liquid partition, weight of silica gel in the column, and volume of hexane for PAH elution from the column. After obtaining the optimal conditions, a single laboratory method validation was performed. Linearity was demonstrated for benzo[a]pyrene in the concentration range from 0.5 to 8.0mgkg(-1) of sample, corresponding to 1.25-20.0μgkg(-1) of cocoa on a fat basis. For the other analytes, linearity was observed from 0.75 to 8.0μgkg(-1) of sample (1.88-20.0μgkg(-1) of cocoa on a fat basis). Significant matrix effects were found for chrysene and benzo[b]fluoranthene. The precision of the method was verified with relative standard deviations (RSDs) ranging from 2.57 to 14.13% and from 4.36 to 19.77% under repeatability and intermediate precision conditions, respectively. The average recoveries of the eight PAHs ranged from 74.99 to 109.73%. These parameters, limits and measurement uncertainties met the performance criteria established by European Union regulations, except for the theoretical limit of detection for chrysene. The method was applied to the analysis of samples of Brazilian cocoa beans, and only one sample was found to have a PAH content above the maximum limit defined by the European Union legislation. This optimized and validated method is intended to be used as part of the official Brazilian monitoring programs investigating contaminants and residues in food.

Concepts: European Union, Polycyclic aromatic hydrocarbon, Benzene, Chromatography, Analytical chemistry, Aromaticity, Naphthalene, Chrysene

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In this study levels of benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene and indeno[1,2,3-c,d]pyrene in 412 food items collected from food service facilities in Korea were analyzed. The concentrations of the 8 polycyclic aromatic hydrocarbons (PAHs) ranged 0.13-0.48 μg/kg. The concentrations of benzo[a]pyrene in all food samples were <1 μg/kg, which is the lowest maximum limit in foods regulated by EU legislation. PAH contents were employed to conduct exposure and risk assessment. The chronic daily intake of PAHs from 412 food samples was 5.48 x 10(-6) to 4.70 x 10(-4) µg-TEQBaP/kg/day with margins of exposure of 1.04 x 10(9) to 1.16 x 10(11).

Concepts: Polycyclic aromatic hydrocarbon, Benzene, Hydrocarbon, Aromatic hydrocarbon, Aromaticity, Naphthalene, Polycyclic aromatic hydrocarbons, Chrysene

0

A total of 13 polycyclic aromatic hydrocarbons (PAHs) were surveyed in dry whole soybeans (Glycine max L.) sold for human consumption. The analysed samples were commercialised in vegetarian shops and food stores in Southern Brazil regions. The determination of PAHs levels was carried out by high performance liquid chromatography (HPLC)with fluorescence detection. PAHs were present in 89.7% of the samples. Chrysene (Chy) and 5 methyl chrysene (5MeChy) were the main PAHs detected (76.9% and 71.8%, respectively) followed by dibenzo(ai)pyrene (DaiP), however in a much less percentage of samples (23.1%). Apart from those PAHs, also benzo(a)antracene (BaA), benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF) and benzo(a)pyrene(BaP) were found. The ΣPAH levels in the positive samples ranged from 0.80 to 38.78 µg kg(-1), with exception of one sample that reached 204.46 µg kg(-1) (ΣPAHs of six compounds). Despite the present contamination there are no maximum limits set for PAHs in soybeans.

Concepts: Polycyclic aromatic hydrocarbon, High performance liquid chromatography, Soybean, Aromatic hydrocarbon, Brazil, Aromaticity, Naphthalene, Chrysene