Revealing the Origin of Polycyclic Aromatic Hydrocarbons in an Urban Snowpack

Polyciclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants in urban atmosphere. Several PAHs are known carcinogens or are the precursors to carcinogenic daughter compounds. Understanding the contributions of various PAH emission sources is critical to appropriately managing PAH levels in the environment. The sources of PAHs to urban snowpack in Shelekhov city, Eastern Siberia, characterized by extremely high levels of PAH accumulation in snow were determined by using end-member mixing approach. The best potential to distinguish PAH emission sources is exhibited by ratios of PAH pairs of the principal mass 228, 252, and 276. The ratios of PAH pairs were used as tracers of end-member PAH sources. The contributions of sources were calculated using systems of linear equations. The results obtained using ratios of PAH pairs were compared with those obtained using molecular diagnostic ratios. It was shown that the results obtained using diagnostic ratios as tracers are less reliable than the results obtained using the ratios of the sums of PAHs.     

Equilibrium and Kinetic Studies on Lithium Adsorption from Geothermal Water by λ-MnO2

The adsorption equilibria of lithium from geothermal water were investigated by using both powdery and granulated forms of λ-MnO₂ derived from spinel-type lithium manganese dioxide. Optimum amounts of adsorbents were 1.0 g adsorbent/L-geothermal water for powdery λ-MnO₂ and 6.0 g adsorbent/L-geothermal water for granulated λ-MnO₂. The adsorbents exhibited the promising adsorption capacities and their adsorption equilibria of lithium agreed well with the Langmuir adsorption isotherm model. The kinetic data of lithium adsorption have been evaluated using pseudo-first-order, pseudo-second-order kinetics models, as well as Elovich kinetic model. In addition, intra-particle diffusion model has been used for evaluating the kinetic data to evaluate the adsorption mechanism. The adsorption kinetic process was attributed to the gradual adsorption stage where intra-particle diffusion was found as the rate-controlling step.     

Removal of polyaromatic hydrocarbons from scrap tires by solvent extraction

This study analyzes polycyclic aromatic hydrocarbon (PAH) compounds released from scrap tires by GC/MS and introduces a simple extraction process at ambient conditions to remove PAHs from scrap tires. The PAH species released from scrap tires included seven PAH compounds with high molecular weight and 4- and 5-aromatic rings and total-PAH content of 159 mg/L. When scrap tires were extracted using hot water (180 °C) for 3 h, the overall removal efficiency was 53%, indicating that PAHs were not adequately removed by this method. However, using organic solvents, the overall PAH removal efficiency improved to 82% for propionic acid and 70% for acetic acid, because the mass transfer of PAHs within scrap tires increases with decreasing dielectric constant. The PAH removal efficiency was dependent on solvent type and temperature.     

New Methodology for Quantifying Polycyclic Aromatic Hydrocarbons (PAHs) Using High-Resolution Aerosol Mass Spectrometry

This article presents a new methodology to potentially quantify polycyclic aromatic hydrocarbon (PAH) isomers using high-resolution time of flight aerosol mass spectrometer (HR-AMS). The fragmentation of PAHs within the HR-AMS is such that significant signal remains at the molecular ion. After quantifying the molecular ion signal and taking into account potential interferences, the amount of the parent PAH in the aerosol may be inferred once its fragmentation pattern is also known. The potential of this approach was evaluated using mixed gasoline and diesel engine exhaust sampled under varying conditions. This dataset led to the identification and quantification within the aerosol mass spectra of the molecular ions associated with 53 PAH isomers, including both unsubstituted and functionalized species. An evaluation of anticipated interferences shows that interferences from larger molecular weight PAHs (i.e., PAH/PAH interferences) could be constrained based on the fragmentation behavior of PAHs from existing HR-AMS laboratory spectra. Other signal interferences for this data set are typically less than 5% of the total signal or, for ¹³C isotopic interferents, are well constrained by measurements of the dominant isotope. The experimental data reveal that the fractional PAH molecular ion signal remained stable despite dramatic temporal variability of the total particulate organic signal. The fractional contributions of the molecular ions for grouped PAH species and even individual compounds were remarkably consistent across experiments. The distribution of PAHs showed no apparent dependence on engine load or exhaust type. Full application of this approach will require a greater number of standard HR-AMS spectra for PAHs, so that the relationship between compounds and their molecular ions may be understood more precisely.

Copyright 2015 American Association for Aerosol Research     

活性炭纤维吸附石化废水中苯酚的吸附平衡及动力学

以活性炭纤维(ACF)为吸附剂,研究了ACF对石化废水中苯酚的吸附平衡及动力学。在25、40、55及65℃下测定了吸附平衡等温线,采用Langmuir、Freundlich和Redlich-Peterson等温方程对吸附平衡数据进行了拟合,结果表明吸附平衡数据更符合Langmuir与Redlich-Peterson方程。体系温度从25、40、55升高到65℃时,ACF对模拟废水中苯酚的吸附能力随温度升高而降低,而ACF对石化废水中苯酚的吸附能力并不完全随温度升高而降低。ACF对石化废水与模拟废水中苯酚的吸附过程均符合拟二级动力学方程。颗粒内扩散模型对吸附动力学实验数据的拟合结果表明,吸附初期吸附速率主要受颗粒内扩散控制且石化废水中苯酚吸附的k_id随温度升高而增大,吸附中后期吸附速率除了受颗粒内扩散控制外还受到外扩散的影响。热力学分析表明,石化废水中ACF吸附苯酚过程的ΔG<0,由于石油类物质对苯酚吸附的影响,温度升高ΔG的数值变化不大。     

乳液法制备石墨烯气凝胶及其吸附水中亚甲基蓝

利用乳液法制备多孔石墨烯气凝胶（emGA）,改变乳液油水比制备不同的emGA。扫描电子显微镜（SEM）、傅里叶红外光谱（FTIR）、氮气吸附脱附等表征显示,emGA具有多孔结构,经水热还原后含氧官能团大部分被除去,比表面积为103.3～243.1m²/g。以亚甲基蓝（MB）浓度和温度作为变量,考察emGA对水中MB的吸附效果。结果表明,emGA的比表面积越大,其对MB平衡吸附量越大;当初始浓度越大,温度越高,则吸附有利。吸附动力学数据表明emGA吸附MB符合准二级动力学模型和内扩散模型,吸附过程分为大孔扩散和微孔扩散。吸附等温线数据拟合结果符合Langmuir模型,表明emGA对MB的吸附属于单分子层吸附。Langmuir模型计算出emGA-2饱和吸附量为307.7mg/g,与实验值291.3mg/g较为接近。分析热力学参数发现,emGA吸附MB为自发吸热过程,且吸附过程属于物理吸附。     

Vehicular Tire as Potential Adsorbent for the Removal of Polycyclic Aromatic Hydrocarbons

ABSTRACT

Polycyclic aromatic hydrocarbons (PAHs) are environmental pollutants, entering into various water and wastewater systems through various natural and anthropogenic activities. The aim of the work is to convert vehicular tires, a highly available waste material, into potential adsorbent for the removal of PAHs from aqueous solutions. The BET surface area of the prepared vehicular tire activated carbon is 643.86 m²/g. Removal of PAHs using activated carbons and the effect of various parameters such as contact time, adsorbent dose, temperature, and pH on the adsorption have been evaluated. The data were fitted to Freundlich and Langmuir isotherms and values of various constants were evaluated. In all the cases, Freundlich model was found to be better fitted. The equilibrium time for adsorption of PAHs was 120 min. The values of thermodynamic parameters, such as Gibb's free energy change ΔG°, enthalpy change ΔH°, and entropy change ΔS°, were calculated using adsorption equilibrium constants obtained from Langmuir isotherm. The thermodynamic data for adsorption of PAHs revealed spontaneity and endothermic nature of the adsorption process. The samples were analyzed using a UV–vis spectrophotometer for PAH determination. Mixture of sodium hydroxide and ethanol in different proportions was tried for desorption of PAHs and 50% ethanolic NaOH solution was most effective. The developed activated carbon demonstrates good adsorption and desorption capabilities for PAHs, indicating towards its suitability for use in the treatment processes of various industrial effluents or water streams containing PAHs.     

Particle Associated Polycyclic Aromatic Hydrocarbons (PAHS) in Urban Air of Agra

Total Suspended Particulate Matter (TSPM) samples were collected at Nunhai Agra from April to September 2006. The concentrations of 16 PAHs in aerosols were quantified. The dominated predominant PAHs in TSPM include high molecular weight (HMW) congeners BghiP, DbA, IP and BaP. Nap and Acy were not detected in any of the samples. The sum of 14 priority PAHs ranged from 150 to 480 ng m^?3 with a mean value of 269 ± 121 ng m^?3. The Results indicated that PAH concentrations at Nunhai were higher than in other industrial sites, but are comparable to those measured in several urban Chinese cities, however, and less than the industrial locations of China. Higher HMW PAH concentration were attributable to higher rates of emissions as well as or greater scavenging and adsorption of vapor phase PAH on available TSPM. Potential sources of PAHs in aerosols were identified using the diagnostic ratios between PAHs. Vehicular emissions were the main contributors of particulate-associated PAHs, with minor contribution from stationary combustion sources may also contribute to the particulate PAHs. PAHs in aerosols were predominantly from gasoline and diesel engines.     

Modelling of porous core–shell adsorbent particles with various morphologies suspended in batch adsorber from analytical solutions of diffusion equations

Considering both intra-particle diffusion and film resistance for mass transfer, analytical solutions of transient concentration of adsorbate inside adsorbents with spherical, cylindrical, or slab-type particles were derived for batch adsorbers by solving governing equations using the Laplace transform. Assuming Henry's or rectangular isotherm, the average concentration inside adsorbents as well as transient bulk concentration were also obtained for the particles with or without the inert core. Computations were performed to compare the results according to the shape of adsorbents by adjusting adsorbent loading, Biot number (Bi), and inert core thickness. Regardless of particle morphologies, steady-state bulk concentration was only affected by adsorbent loading and inert core thickness, whereas the effect of Bi was confirmed from the decreasing reduction rate of adsorbate concentration with decreasing Bi. When diffusivity was dependent on time, time-decaying diffusivity caused the increase in steady-state concentration that was predicted by eigenfunction expansion. Experimental results using porous fibres by electrospinning were compared with the mathematical solution of a cylindrical adsorbent for the estimation of intra-particle diffusivity. Using the solutions of the diffusion equation model, novel core–shell cylindrical adsorbents can be designed and synthesized as core–shell fibres by electrospinning with a coaxial nozzle to save the cost of the active shell layer. Such core–shell structured fibres can be adopted as adsorbents for novel batch adsorption processes and the present modelling results can be extended to other processes like fixed bed adsorbers.     

大孔吸附树脂吸附乳酸及乳酸与谷氨酸的分离

通过筛选,得到大孔吸附树脂NKA-II,并用其对乳酸进行分离. 测定了该树脂对乳酸与谷氨酸的吸附选择系数,得到了乳酸在NKA-II上的吸附等温线,并对其吸附动力学和动态吸附进行了研究. 结果表明,NKA-II对乳酸和谷氨酸的吸附选择系数KGL=16.19. 该树脂对乳酸的吸附等温线符合Freundlich方程,在26和48℃下的相关系数R2均大于0.99,方程的特征参数n>1,属"优惠吸附". 吸附动力学研究表明,粒内扩散是吸附过程的主要控制步骤,符合Kannan-Sundaram粒内扩散模型,相关系数R2=0.9906,粒内扩散速率常数kp=6.0129 mg×min0.5/g. 动态吸附实验结果表明,乳酸的穿透体积比谷氨酸大110.6 mL,故该树脂可以成功地应用于乳酸与谷氨酸的分离.     

Adsorption of N-Vinylpyrrolidone from Polyvinylpyrrolidone Solution onto Bamboo-Based Activated Carbon

The adsorption of N-vinylpyrrolidone from aqueous polyvinylpyrrolidone solution using bamboo-based activated carbon was studied. The adsorption isotherms of N-vinylpyrrolidone on the carbon were determined and modeled with the Langmuir, Freundlich, and Temkin models. The Langmuir model provides the best fitting for the equilibrium data and the maximum monolayer adsorption capacity was estimated to be 833.3 mg/g. The kinetics of the adsorption process of N-vinyulpyrrolidone were modeled using various equations including pseudo first-order, pseudo second-order, and intra-particle diffusion equations. The adsorption process follows the pseudo second-order kinetic model, suggesting that the adsorption mechanism is chemisorption. The activation energy for the adsorption is 86.4 kJ/mol. Thermodynamic parameters such as Gibbs free energy, enthalpy, and entropy were determined. The positive value of enthalpy change indicates that the adsorption process is endothermic.     

High-Molecular-Weight Polycyclic Aromatic Hydrocarbons in the Area and Vicinity of the Deza Chemical Plant,Czech Republic

Polycyclic aromatic hydrocarbons (PAHs) with molecular weight exceeding 278 amu were analyzed in air, water, and soils from the area and vicinity of the DEZA Chemical Plant (Vala w ské Mezi q í ) í, Czech Republic). Air and water were sampled using semipermeable membrane devices (SPMDs); grab sampling was applied for soils. Laser desorption/ionization-time-of-flight mass spectrometry (LDI-TOF MS) and liquid chromatography/ion trap mass spectrometry with atmospheric pressure chemical ionization (LC/APCI-ITMS) were employed for the quick assessment of PAH distribution and for the identification and quantification of some high-molecular-weight PAHs. Compounds with molecular mass up to 450 u were found. LDI-TOF mass spectra and selected LC/APCI-ITMS profiles (m/z 303, m/z 327, and m/z 351) were compared to identify potential source of contamination in this locality. High-molecular-weight PAHs were found in all environmental compartments in the area studied; their levels were quite high close to their source and decreased sharply with increasing distance from it.     

Mass transfer kinetics in pressure swing adsorption

Many mass transfer kinetic models are used to study varying pressure steps of a pressure swing adsorption (PSA) cycle, namely pressurization and blowdown steps. It is shown that the choice of an appropriate model to account for intra-particle diffusional limitations is essential to simulate accurately PSA processes. It has been demonstrated that, besides mathematical approximations (parabolic profile within the particle), a very important factor that can affect simulation results remarkably is the correctness of the mass transfer kinetic model when regarded as being a mass balance for the adsorbent particle. In fact, neglecting intra-particle gas phase leads to erroneous simulations. Some models widely used in the literature, such as the classic linear driving force (LDF) and the solid diffusion models prove inadequate. It is recommended to use pore diffusion model as well as a new version of the solid diffusion model to get reliable predictions.     

钢渣对废水中磷的吸附行为

通过批次振荡实验研究了钢渣吸附磷的特性. 结果表明,钢渣对磷的吸附过程符合Langmuir和Freundlich方程,理论饱和吸附量为0.33 g/kg,为优惠型吸附. 吸附动力学过程符合Lagergren准二级动力学方程,平衡吸附量随温度升高而增加,吸附速率主控步骤为液膜扩散和颗粒内扩散同时存在. 吸附热力学参数DH>0, DG<0, DS>0,钢渣对磷的吸附为吸热、自发的物理吸附过程,升高温度有利于吸附进行.     

Artefacts in semivolatile organic compound sampling with polyurethane foam substrates in high volume cascade impactors

Polyurethane foam (PUF) is known to sorb gas-phase semivolatile organic compounds (SVOCs) from ambient air and is used routinely in conventional high volume filter-sorbent sampling of such pollutants. PUF rings have also been employed as impaction substrates in a high volume cascade impactor (HVCI) used as a sampler for the evaluation of particle toxicity. Though nonvolatile particles (e.g., trace metals, inorganic ions) have been the primary focus, the sampler has also been used to measure particulate SVOC concentrations in ambient air. The aim of this work is to investigate the validity of the latter approach. The results of three sets of experiments conducted in Canada and Denmark are reported herein. Model compounds included native and deuterated polycyclic aromatic hydrocarbons (PAHs). The experiments demonstrated that HVCI PUF substrates sorb gas-phase PAH compounds and that the sorbed mass is subject to mobilization through and out of the sampler. Particulate concentrations of low molecular weight and volatile PAHs are therefore prone to overestimation in samples that have been analyzed after extraction of whole PUF substrates. Sonication of collected particles in water before solvent extraction is effective at dislodging them from the PUF but also acts to redistribute their originally particulate PAH mass back to the PUF and to the sonication water. As a result, the PAH content of particles measured after sonication and subsequent filtration does not accurately represent their true values. These artefacts affect not only measured PAH concentrations but also the results of toxicological assays that are conducted to test the characteristics of particles collected using HVCI PUF samplers.     

Polycyclic aromatic hydrocarbon emissions of non-road diesel engine treated with non-thermal plasma technology

Non-road diesel engines are important polycyclic aromatic hydrocarbon (PAH) sources in the environment due to their high emission concentration compared to on-road diesel engines. Particle- and gas-phase PAH concentrations of a non-road diesel engine were investigated. Non-thermal plasma (NTP) as an effective after-treatment technology was used to reduce PAH emissions. The results showed that particle-phase PAH concentrations were 329.7 µg/m³, 3,206.7 µg/m³, and 1,185.7 µg/m³ without the action of NTP at three different engine loads respectively. Relatively low concentrations were measured for gas-phase PAHs. Excellent linearity was shown for particle-phase with total PAH concentrations both with, and without, NTP. The gas-phase PAH concentrations linearly increased with engine load without NTP. The five most abundant compounds of PAHs were among low molecular weight (LMW) and medium molecular weight (MMW) compounds. Total PAH cleaning efficiency was beyond 50% when treated with NTP at the three different engine loads. We hypothesized that naphthalene (Nap) concentrations increased greatly at 60% and 80% engine loads because it was produced within the plasma zone by decomposition of high molecular weight (HMW) PAHs. The PAHs content of particulate matter (PM) aggregation at 60% load was approximately three times higher than at 40% and 80% loads. High correlation values were observed for MMW PAHs with total PAH concentrations. Correlations of PAH concentration reduction could be important to clarify the PAH reduction mechanism with NTP technology.     

Status of PAHs in Environmental Compartments of South Africa: A Country Report

This article covers the status of PAH concentrations and composition patterns in surface water, air, sediment, and soil samples from South Africa. Despite South Africa being one of the largest economies in Africa, it is only recently that researchers have reported the presence and possible sources of these compounds in various environmental compartments. This article discusses the potential hotspots and possible sources of these compounds. It also compares the total PAH concentrations and percentage composition patterns of the individual PAHs. So far, total concentrations of five PAHs determined in sediment samples from the Johannesburg area, Gauteng Province, gave the highest concentrations ranging from 1233–136,276 μg kg^?1. The total concentration of six PAHs found in runoff water from the Venda region of the Limpopo Province, gave the highest concentration with a range of 28.7–3192.6 μg L^?1. The decreasing order of percentage composition of PAHs in water samples tended to follow 3-ring > 4-ring > 2-ring PAHs. In soil samples the decreasing order of percentage composition followed 4-ring > 3-ring > 5-ring > 2-ring > 6-ring PAHs. The total freely dissolved PAHs followed solubility of the compounds with 2-ring > 3-ring > 4-ring > 5-ring > 6-ring PAHs. Some of the identified sources of PAHs using molecular ratios include petrogenic emissions such as from petroleum combustion from vehicles and pyrolytic sources such as coal combustion by coal powered power stations, as well as iron and steel production industries. Oil spills were also identified as major PAH contributor in runoff water from the Venda region of the Limpopo Province.     

Adsorption of naphthalene and phenanthrene on dodecylpyridinium-modified bentonite

Eight organoclays were prepared from sodium-rich bentonite and dodecylpyridinium chloride loading levels of 0.25–2.00 times the cation exchange capacity (CEC). The organoclays were characterized by the specific surface area, X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). Adsorption of DPC onto bentonite and of PAHs from the aqueous solution on the organoclays were studied in batch experiments. DPC was adsorbed in excess of the CEC. The adsorption isotherms of PAHs onto the organoclays were linear, indicating partition as the main mechanism of PAH adsorption. As the amount of DPC increased from 0.25 to 1.25 times the CEC, the increased basal spacing and partition medium promoted PAH adsorption. When the amount of DPC was higher than 1.25 times the CEC, PAH adsorption was limited by densely packed dodecylpyridinium chains in the interlayer space.     

Distribution,Sources, and Risk of Polycyclic Aromatic Hydrocarbons in the Core Sediments from Baiyangdian Lake,China

The burial characteristics and risks of 16 polycyclic aromatic hydrocarbons (PAHs) in core sediments from Baiyangdian Lake were investigated through gas-chromato graphy/mass spectrometry. The total concentrations of the 16 PAHs ranged from 39.48–1877.75 ng g^?1. The low-molecular-weight PAHs (two- to three-ring PAHs) were the dominant species, contributing 40.10–92.18% to the total PAHs, with a mean of 71.01%. Based on the observed molecular indices and on principal component analysis, the PAHs inputs were initially dominated by biomass and coal combustion, and atmospheric deposition and surface runoff could be the major transport pathways. The contaminated source characteristics, hydrodynamic condition, and sediment textural composition are the key factors affecting the distribution and source of PAHs. By conducting a risk quotient analysis between specific PAH concentrations and their corresponding sediment quality values, the top layer sediments were found to have a potential biological impact and relatively high toxicity. However, such impact should have no impairment. The toxic potency of PAHs in Baiyangdian Lake could be described by using the toxic equivalent of benzo[a]pyrene.     

PBMA/GMA-SiO2吸附剂的制备及其高效去除铅离子

以甲基丙烯酸丁酯(BMA)和甲基丙烯酸缩水甘油酯(GMA)功能化的纳米SiO2为单体,通过可逆加成-断裂链转移自由基聚合(RAFT)法制备了PBMA/GMA-SiO2有机/无机复合吸附材料,并将其用于吸附含Pb2+的水溶液。考察了吸附时间、温度、pH以及Pb2+初始质量浓度对吸附效果的影响,并对其吸附动力学和热力学特性进行了探讨。结果表明,PBMA/GMA-SiO2对Pb2+具有良好的吸附性能,其对Pb2+的饱和吸附量为423.84mg/g,吸附最佳pH=5~6,平衡时间为1 h,去除率随Pb2+初始质量浓度的减小而增加。优化实验条件下,50 mg吸附剂在298 K时,对pH=6的50 mL 0.02 g/L含Pb2+溶液的去除率高达100%。热力学和动力学过程模拟结果表明,吸附的动力学过程比较符合准二级动力学速率方程,Langmuir等温方程比Freundlich等温方程更适合于描述此吸附行为。颗粒内扩散过程是吸附速率的控制步骤,但不是唯一的速率控制步骤。吸附剂经过5次脱附、吸附后,依然具有较强吸附Pb2+的能力。