Systematic study of the influence of modifiers on the CO2-supercritical extraction of PAHs in soil

Summary An exhaustive study of the behaviour in supercritical fluid extraction of eight PAHs in real samples of soil compared to spiked samples in silica has been carried out. The presence of a modifier is mandatory for quantitative extraction of the native analytes, but is unnecessary in spiked samples. The type and volume of modifier to be added and the sample-modifier contact time were optimized and the influence of the particle size assessed.     

From S,N‐Heteroacene to Large Discotic Polycyclic Aromatic Hydrocarbons (PAHs): Liquid Crystal versus Plastic Crystalline Materials with Tunable Mechanochromic Fluorescence

A novel type of discotic polycyclic aromatic hydrocarbon (PAH) based on an enlarged dibenzo[a,c]phenazine core has been developed. The large conjugated mesogenic core with increased dipole moment derived from S,N heteroatoms facilitates the formation of highly ordered columnar superstructures both in solution and bulk. Columnar mesophases, including liquid crystal (LC) and plastic crystal (PC) assemblies could form unprecedentedly based on the same PAH core. The cores are delicately modulated by the peripherical alkoxy chains. Both mesogens have mechanochromic fluorescent (MCF) character, which is also structure dependent and correlated with the different mesophase formation. For the first time, MCF properties can be realized in such a large conjugated mesogenic system.     

Bottom‐up Construction of π‐Extended Arenes by a Palladium‐Catalyzed Annulative Dimerization of o‐Iodobiaryl Compounds

A straightforward method was developed for construction of aromatic compounds with a triphenylene core. The method involves Pd‐catalyzed annulative dimerization of o‐iodobiaryl compounds by double C?I and C?H bond cleavage steps. Simple reaction conditions are needed, requiring neither a ligand nor an oxidant, and the reaction tolerates a wide range of coupling partners without compromising efficiency or scalability. Significantly, the tetrachloro‐substituted synthon, 1,6,11‐trichloro‐4‐(4‐chlorophenyl)triphenylene, can be generated and used to prepare a series of fully fused, small graphene nanoribbons by a late‐stage arylation with arylboronic acids and a subsequent Scholl reaction. The synthetic strategy enables bottom‐up access to extended π‐systems in a controlled manner.     

The Regioselective Methylation of Polycyclic Aromatic Hydrocarbons through Tricarbonylchromium Coordination

Deprotonation, methylation, and air oxidation of polycyclic arenes coordinated to chromium(0), (η⁶-arene)Cr(CO)₃, produced ring-methylated products with high selectivity and in good yield. This procedure gave 3-methylbenz[a]anthracene from (η⁶-benz[a]anthracene)Cr(CO)₃, 3-methylphenanthrene from (η⁶-phenanthrene)Cr(CO)₃, 2-acetyl-6-methylphenanthrene from (η^6?2-acetylphenanthrene)Cr(CO)₃, and 3,7,12-trimethylbenz[a]anthracene from (η^6?7,12-dimethylbenz[a]anthracene)Cr(CO)₃.     

铜及氧化铜对煤燃烧过程多环芳烃排放的影响

在实验管式炉上研究了金属铜和氧化铜对烟煤燃烧过程中PAHs生成的影响。采用气相色谱分析PAHs。实验结果表明，铜会促进PAHs的生成，而且主要是促进中高分子量PAHs的生成，这是由于铜为PAHs的合成提供了大量的活性反应中心。另一方面氧化铜对PAHs的合成和裂解具有双重催化效果，从而显著增加了中分子量PAHs的排放。在800 ℃以下，添加铜和氧化铜都减小了PAHs排放的毒性当量。在900 ℃以上，添加铜增大了PAHs排放的毒性当量。添加氧化铜时与添加铜时的规律类似，但是在1100℃以上，PAHs排放的毒性当量要比不添加时小。     

Analysis of BTEX, PAHs and metals in the oilfield produced water in the State of Sergipe, Brazil

During oil and gas exploitation, large amounts of produced water are generated. This water has to be analyzed with relation to the chemical composition to deduce the environmental impact of its discharge after a treatment process. Therefore, a study was carried out to evaluate preliminarily the BTEX (benzene, toluene, ethylbenzene and xylenes), polycyclic aromatic hydrocarbons (PAHs) and metals contents in produced water samples taken from effluents of the Bonsucesso treatment plant located in the city of Carmópolis, the most important oil and gas producer in the State of Sergipe, North-east of Brazil. Three methods were optimized to determine the target compounds. Polycyclic aromatic hydrocarbons were determined by gas chromatography with mass spectrometric detection (GC/MS), volatile aromatic hydrocarbons (BTEX) by gas chromatography with photoionization detector (GC/PID) and metals were analyzed by flame atomic absorption spectrometry (FAAS). The results showed that concentrations of the target compounds in these samples ranged from 96.7 to 1397 μg L^− 1 for BTEX, from 0.9 to 10.3 μg L^− 1 for PAHs and from 0.003 to 4540 mg L^− 1 for metals.     

Identification of Polycyclic Aromatic Hydrocarbons Produced During Combustion of Fuel With Carbon Disulfide as Additive

That polystyrene and benzene as additives to gasoline increase the amount of polycyclic aromatic hydrocarbons (PAHs) has been studied previously in our laboratory. This paper describes the use of carbon disulfide as the solvent instead of benzene brings a marked reduction of the formation of polycyclic aromatic hydrocarbons.     

The niobium and tantalum riddle: gas-phase monocation reactions with pyrene and pyrene-D10

Metal monocation gas-phase reactions with pyrene (Py) have been investigated. Of those cations which bind Py by abstraction of two hydrogen atoms, there are two subgroups of which Nb⁺ and Ta⁺ are the most striking and puzzling representatives. The Ta⁺-like group binds three Py units consecutively, each by expulsion of two hydrogen atoms, whereas the Nb⁺ group binds four Py units; however, in this latter case, the second Py attachment occurs without the expulsion of any hydrogen. When perdeuterated Py-D₁₀ is used, the Ta⁺ group behavior is unaffected, but the Nb⁺ group now exhibits a considerable degree of Py attachment in which no deuterium atoms are lost in the first reaction step. We will attempt to explain this behavior by using the results of reactions of Nb⁺ and Ta⁺ with Py in a Fourier transform mass spectrometer (FTMS).     

Cellulose acetate as stationary phase in microcolumn LC

The retention characteristics of alkylbenzenes and polycyclic aromatic hydrocarbons (PAHs) have been examined in liquid chromatography on a microcapillary column packed with cellulose acetate. Particulate and fibrous cellulose acetate were used as the stationary phase. Fibrous cellulose diacetate was found to be of use as an alternative stationary phase for liquid chromatography, although the separation efficiency was low. The retention characteristics for planar PAHs were linearly correlated with the size of the molecules, but the retention behavior for alkylbenzenes and nonplanar PAHs was affected by exclusion. The retention order was strongly influenced by the addition of dimethylformamide or water to methanol in the mobile phase. The results suggested that the retention behavior is influenced by a slight change in the polymer matrix of cellulose acetate.     

Use of Cyclodextrins as An Environmentally Friendly Extracting Agent in Organic Aged-contaminated Soil Remediation

The removal of Polycyclic Aromatic Hydrocarbons (PAHs) from soil using pure water is quite ineffective due to␣their low aqueous solubility. Most of present processes are based on organic cosolvents or surfactants, leading to potential environmental hazard. Addition of cyclodextrin (CD) in aqueous washing solutions has been shown to␣increase the removal efficiency several times, while being non-toxic agents. Herein are investigated the effectiveness of cyclodextrins to remove PAHs occurring in industrially aged-contaminated soil. β-cyclodextrin (BCD), hydroxypropyl-β-cyclodextrin (HPCD) and methyl-β-cyclodextrin (MCD) solutions were used for soil flushing in column test or batch experiments to evaluate some influent parameters that can significantly increase the removal efficiency. The process parameters chosen were CD concentration, ratio of washing solution volume to soil weight, and temperature of washing solution. These parameters were found to have a significant and almost linear effect on PAHs removal from the contaminated soil, except the temperature where no significant enhancement in PAHs extraction was observed for temperature range from 5 to 35 °C. Removal capacity of HPCD and MCD was higher than BCD one. The PAHs extraction enhancement factor compared to water was about 200.