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.
BACKGROUND: Sensitization to cockroach is one of the strongest identified risk factors for greater asthma morbidity in low-income urban communities; however, the timing of exposures relevant to the development of sensitization has not been elucidated fully. Furthermore, exposure to combustion byproducts, including polycyclic aromatic hydrocarbons (PAHs), can augment the development of allergic sensitization. OBJECTIVE: We sought to test the hypotheses that domestic cockroach allergen measured prenatally would predict cockroach sensitization in early childhood and that this association would be greater for children exposed to higher PAH concentrations. METHODS: Dominican and African American pregnant women living in New York City were enrolled. In the third trimester expectant mothers wore personal air samplers for measurement of 8 nonvolatile PAHs and the semivolatile PAH pyrene, and dust was collected from homes for allergen measurement. Glutathione-S-transferase μ 1 (GSTM1) gene polymorphisms were measured in children. Allergen-specific IgE levels were measured from the children at ages 2, 3, 5, and 7 years. RESULTS: Bla g 2 in prenatal kitchen dust predicted cockroach sensitization at the ages of 5 to 7 years (adjusted relative risk [RR], 1.15; P = .001; n = 349). The association was observed only among children with greater than (RR, 1.22; P = .001) but not less than (RR, 1.07; P = .24) the median sum of 8 nonvolatile PAH levels. The association was most pronounced among children with higher PAH levels and null for the GSTM1 gene (RR, 1.54; P = .001). CONCLUSIONS: Prenatal exposure to cockroach allergen was associated with a greater risk of allergic sensitization. This risk was increased by exposure to nonvolatile PAHs, with children null for the GSTM1 mutation particularly vulnerable.
- Environmental science and pollution research international
- Published over 7 years ago
Concentrations of 22 polycyclic aromatic hydrocarbons (PAHs) were estimated for individual particle-size distributions at the airport apron of the Taipei International Airport, Taiwan, on 48 days in July, September, October, and December of 2011. In total, 672 integrated air samples were collected using a micro-orifice uniform deposition impactor (MOUDI) and a nano-MOUDI. Particle-bound PAHs (P-PAHs) were analyzed by gas chromatography with mass selective detector (GC/MSD). The five most abundant species of P-PAHs on all sampling days were naphthalene (NaP), phenanthrene (PA), fluoranthene (FL), acenaphthene (AcP), and pyrene (Pyr). Total P-PAHs concentrations were 152.21, 184.83, and 188.94 ng/m(3) in summer, autumn, and winter, respectively. On average, the most abundant fractions of benzo[a]pyrene equivalent concentration (BaPeq) in different molecular weights were high-weight PAHs (79.29 %), followed by medium-weight PAHs (11.57 %) and low-weight PAHs (9.14 %). The mean BaPeq concentrations were 1.25 and 0.94 (ng/m(3)) in ultrafine particles (<0.1 μm) and nano-particles (<0.032 μm), respectively. The percentages of total BaPeq in nano- and ultrafine particulate size ranges were 52.4 % and 70.15 %, respectively.
Cosolubilization of polycyclic aromatic hydrocarbons (PAHs) (naphthalene and pyrene) has been studied in surfactant systems of varying nature of their head-group viz. nonionic: Brij30 and Brij56, cationic: DDEAB and CTAB and anionic: SDS. Solubilization capacity of micelles was quantified in terms of molar solubilization ratio, the micelle-water partition coefficient, the first stepwise association constant and average number of solubilizate molecules per micelle determined by employing spectrophotometric and tensiometric techniques. Solubilization capacity of all the surfactant systems was generally higher for naphthalene than pyrene and followed the order: nonionics>cationics>anionic surfactant. Solubility of naphthalene decreased during cosolubilization in all surfactant systems studied while the solubility of pyrene decreased only in Brij30 and Brij56 surfactant systems due to competitive solubilization of PAHs for the same solubilization site. The solubility of pyrene, however, enhanced in presence of naphthalene in CTAB, DDEAB and SDS surfactant systems owing to increase in core volume of the micelles by the palisade layer solubilization of naphthalene. The results of this study can provide valuable information on the selection of particular surfactant systems for selective separation of naphthalene and pyrene from their mixture relevant to surfactant enhanced remediation (SER) technology at the contaminated sites.
The arenium acid [mesitylene-H]+ has been shown to be an extraordinarily active H/D exchange catalyst for the perdeuteration of polycyclic aromatic hydrocarbons. The reactions take place under ambient conditions in C6D6 as an inexpensive deuterium source. High isolated yields and excellent degrees of deuterium incorporation were achieved using the substrates para-terphenyl, fluoranthene, pyrene, triphenylene, and corannulene.
Degradation of polycyclic aromatic hydrocarbons in soil by a tolerant strain of Trichoderma asperellum
- Environmental science and pollution research international
- Published over 5 years ago
Trichoderma asperellum H15, a previously isolated strain characterized by its high tolerance to low (LMW) and high molecular weight (HMW) PAHs, was tested for its ability to degrade 3-5 ring PAHs (phenanthrene, pyrene, and benzo[a]pyrene) in soil microcosms along with a biostimulation treatment with sugarcane bagasse. T. asperellum H15 rapidly adapted to PAH-contaminated soils, producing more CO2 than uncontaminated microcosms and achieving up to 78 % of phenanthrene degradation in soils contaminated with 1,000 mg Kg(-1) after 14 days. In soils contaminated with 1,000 mg Kg(-1) of a three-PAH mixture, strain H15 was shown to degrade 74 % phenanthrene, 63 % pyrene, and 81 % of benzo[a]pyrene. Fungal catechol 1,2 dioxygenase, laccase, and peroxidase enzyme activities were found to be involved in the degradation of PAHs by T. asperellum. The results demonstrated the potential of T. asperellum H15 to be used in a bioremediation process. This is the first report describing the involvement of T. asperellum in LMW and HMW-PAH degradation in soils. These findings, along with the ability to remove large amounts of PAHs in soil found in the present work provide enough evidence to consider T. asperellum as a promising and efficient PAH-degrading microorganism.
Rhamnolipid was applied to degrade anthracene and pyrene in reversed micelles. The parameters in degradation were optimized for the purpose of improving degradation rates. The proper amount of rhamnolipid (RL) used for degrading anthracene was 0.065 mM, while 0.075 mM for pyrene. However, reaction time for degrading both anthracene and pyrene was 48 h. The optimum water content, pH, laccase concentration, polycyclic aromatic hydrocarbon (PAH) initial concentration, and volume ratio of n-hexanol to isooctane for both were found out. The highest degradation rates of anthracene and pyrene were 37.52 and 25.58 %, respectively. Although the degradation rates were not higher than the results previous literatures reported, this method was of novelty and provided guidance in application in degrading PAHs by reversed micellar system, especially for biosurfactant-based reversed micelles.
Hydrophobic organic compounds (HOCs) tend to be associated with suspended particles in surface aquatic systems, however, the bioavailability of HOCs on suspended particles to fish is not well understood. In this study, a passive dosing device was used to control the freely dissolved concentrations (Cfree) of polycyclic aromatic hydrocarbons (PAHs) including fluoranthene and pyrene, and the influence of particle-associated PAHs on their bioaccumulation by zebrafish was investigated. The results showed that, when the Cfreeof PAHs were kept constant, the presence of suspended particles did not significantly affect the steady state of PAH bioaccumulation in zebrafish tissues excluding head and digestive tracts, suggesting that the bioaccumulation steady state was controlled by the freely dissolved concentrations of PAHs. However, suspended particles promoted the uptake and elimination rate constants of PAHs in zebrafish body excluding head and digestive tracts. The uptake rate constants with 0.5 g/L suspended particles were approximately twice of those without suspended particles, and the body burden in zebrafish increased by 16.4% - 109.3% for pyrene and 21.8% - 490.4% for fluoranthene during the first 8-d exposure. This was due to the reasons that suspended particles could be ingested, and part of PAHs associated with them could be desorbed in digestive tract and absorbed by the zebfrafish, leading to the enhancement of uptake rates of PAHs in zebfrafish. The findings obtained from this study indicate that PAHs on suspended particles are partly bioavailable to zebrafish and particle ingestion is an important route in PAH bioaccumulation. Therefore, it is important to consider the bioavailability of HOCs on suspended particles to improve ecological risk assessment.
A hard cap espresso machine has been used in combination with liquid chromatography with molecular fluorescence detection for the determination of polycyclic aromatic hydrocarbons (PAHs) from contaminated soils and sediments providing appropriate extraction efficiencies and quantitative results. Naphthalene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, chrysene, benz[b]fluoranthene, benz[k]fluoranthene, benz[a]pyrene, dibenz[a,h]anthracene, benz[ghi]perylene, and indeno[1,2,3-cd]pyrene were used as target compounds. It should be mentioned that the pairs benz[a]anthracene-chrysene and dibenz[a,h]anthracene-benz[ghi]perylene peaks coelute under the employed chromatographic conditions; thus, those compounds were determined together. PAHs were extracted from 5.0 g of soil, previously homogenized, freeze-dried, and sieved to 250 μm, with 50 mL of 40 % (v/v) acetonitrile in water at a temperature of 72 ± 3 ⁰C. The proposed procedure is really fast, with an extraction time of 11 seconds, and it reduces the required amount of organic solvent to do the sample preparation. The obtained limit of detection for the evaluated PAHs was from 1 to 38 µg kg-1. Recoveries were calculated using clean soils spiked with 100, 500, 1000, and 2000 µg kg-1 PAHs with values ranging from 81 to 121%, and good precision with relative standard deviation values lower than 30%. The method was validated using soil and sediment certified reference materials, and also using real samples by comparison with ultrasound-assisted extraction, as reference methodology, obtaining statistically comparable results. Thus, the use of hard cap espresso machines in the analytical laboratories offers tremendous possibilities as low cost extraction units for the extraction of solid samples.
A simple yet effective method for the formation of thiophene-fused π-systems is reported. When arylethynyl-substituted polycyclic arenes were heated in DMF in the presence of elemental sulfur, the corresponding thiophene-fused polycyclic arenes were obtained via cleavage of the ortho-C-H bond. Thus, arylethynylated naphthalenes, fluoranthenes, pyrenes, corannulenes, chrysenes, and benzo[c]naphtho[2,1-p]chrysenes were effectively converted into the corresponding thiophene-fused π-systems. Apart from polycyclic hydrocarbons, thiophene derivatives are also susceptible to this reaction. The practical utility of this reaction is demonstrated by preparations on the decagram scale, one-pot two-step reaction sequences, and multiple thiophene annulations.