Quantitative determination of trace concentration of organics in water by solvent extraction and fused silica capillary gas chromatography: aliphatic and polynuclear hydrocarbons

Solvent extraction procedures with six different solvents on aqueous model systems of aliphatic (C12-C22) and polynuclear aromatic hydrocarbons (PAHs: Naphthalene, acenaphtene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene) were studied for the analysis in the trace concentration range (20-50 ng ml-1) by fused silica capillary gas chromatography. Recovery efficiencies, reproducibilities and detection limits for each analyte and procedure are reported. The effect of the PAHs on the extracting rate of the aliphatic hydrocarbons at the trace concentration range is discussed.     

Multivariate calibration applied to synchronous fluorescence spectrometry. Simultaneous determination of polycyclic aromatic hydrocarbons in water samples

Synchronous fluorescence spectra of mixtures containing ten polycyclic aromatic hydrocarbons (anthracene, benz[a]anthracene, benzo[a]pyrene, chrysene, fluoranthene, fluorene, naphthalene, perylene, phenanthrene and pyrene) have been used for the determination of these compounds by Partial Least Squares Regression (PLSR), using both PLS-1 and PLS-2. Different procedures have been used for the pretreatment of the data in order to obtain better models, and the size of the calibration matrix has also been studied. The best models have been used for the determination of the above mentioned PAHs in spiked natural water samples at concentration levels between 4 and 20 ng ml⁻¹. Recoveries ranged from 80 to 120% in most cases, although fluorene gave significantly lower results.     

The development of solid-surface fluorescence characterization of polycyclic aromatic hydrocarbons for potential screening tests in environmental samples

This paper presents the characterization of polycyclic aromatic hydrocarbons (PAHs) in solid-surface fluorescence as the first step for obtaining new optical sensors for PAHs screening. The fluorescence properties of the EPA-PAHs (naphthalene, acenaphthene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo[a]anthracene, benzo[k]fluoranthene, benzo[b]fluoranthene, benzo[a]pyrene, indeno [1,2,3-cd]pyrene, benzo[g,h,i]perylene and dibenzo[a,h]anthracene) on five types of solid-surfaces were evaluated. The experimental variables (pH and percentage of organic solvent in samples) were studied, obtaining different possibilities for making individual sensors for some of these PAHs and the best conditions for developing sensors for PAH screening were also studied.     

Porous metal membranes for solid-phase extraction of polycyclic aromatic hydrocarbons

Solid-phase extraction (SPE) is one of the most important techniques for sample preparation, purification, concentration and cleanup. Membranes made from synthetic organic polymers, cellulose, or glass fibers are used for sample pretreatment. In this work, we report that a porous metal membrane, the metal filter in HPLC, was used as a novel kind of solid-phase extraction adsorbent material. To evaluate the performance of the porous metal membrane for the SPE, naphthalene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, chrysene, perylene and benzo(a)pyrene were selected as analytes. Several parameters that affected the extraction efficiency such as the extraction time, the concentration of NaCl, the extraction temperature and the agitation speed were optimized. The experimental result indicates that the porous metal membrane possesses high adsorption ability to the tested polycyclic aromatic hydrocarbons (PAHs). Under the optimum conditions, the detection limits of the developed method were in the range of 0.03-0.082 μg L(-1) (S/N = 5), and excellent linear correlations between peak area and concentration of PAHs were found over the range of 0.1-60 μg L(-1). The precisions (RSD) for five replicate extractions of the PAHs from sample solutions were in the range of 2.6-5.0%. The recoveries of the PAHs from tap water and river water samples spiked with 9 PAHs (20 μg L(-1) of each individual PAH) ranged from 83.0% to 112.5%. The porous metal membrane is durable, simple, inexpensive, reproducible and has a high adsorption ability for use in SPE of PAHs.     

Resolution of 13 polycyclic aromatic hydrocarbons by constant-wavelength synchronous spectrofluorometry.

A method capable of determining 13 PAHs (acenaphthene, anthracene, benzo[a]anthracene, benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene, chrysene, dibenzo[ah]anthracene, fluoranthene, fluorene, indene[1,2,3-cd]pyrene, phenanthrene and pyrene) in a mixture of 16 EPA PAHs by second derivative synchronous spectrofluorometry in the constant wavelength mode was developed. It has not been possible to determine the following PAHs in the mixture: acenaphthylene, benzo[ghi]perylene and naphthalene. The approach studied allows the sensitive, rapid and inexpensive identification and quantitation of 13 PAHs in a solution of hexane. The detection limits are <1 microg L(-1) (except for chrysene and phenanthrene).     

Lichens as biomonitors for the determination of polycyclic aromatic hydrocarbons (PAHs) in Caracas Valley,Venezuela

Biomonitoring of PAH air pollution using lichens was carried out. Sixteen PAHs were studied in 11 locations along the valley of Caracas (Venezuela). The results of this work indicate that 14 of the 16 analysed PAHs were highly accumulated into the lichen thalli of Pyxine coralligera Malme. PAH levels in the samples revealed that the several volatile PAHs (naphthalene, acenaphtylene, acenaphtene, and fluoranthene) have the highest levels in the majority of the studied locations. The fluoranthene/pyrene and phenantrene/antracene ratios suggested that the major sources of PAHs are anthropogenic, mainly associated with gasoline and diesel combustion (pyrolytic) and unburnt oil derivates (petrogenic). The total PAH concentrations obtained in the present study were in the range of 0.24 to 9.08?µg/g, similar to those reported by other works in European and Asian cities.     

Interpretative optimization and artificial neural network modeling of the gas chromatographic separation of polycyclic aromatic hydrocarbons

An interpretative strategy (factorial design experimentation+total resolution analysis+chromatogram simulation) was employed to optimize the separation of 16 polycyclic aromatic hydrocarbons (PAHs) (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo(a)anthracene, benzo(k)fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, indeno(1,2,3-c,d)pyrene, dibenzo(a,h)anthracene, benzo(g,h,i)perylene) in temperature-programmed gas chromatography (GC). Also, the retention behavior of PAHs in the same GC system was studied by a feed-forward artificial neural network (ANN). GC separation was investigated as a function of one (linear temperature ramp) or two (linear temperature ramp+the final hold temperature) variables. The applied interpretative approach resulted in rather good agreement between the measured and the predicted retention times for PAHs in both one and two variable modeling. The ANN model, strongly affected by the number of input experiments, was shown to be less effective for one variable used, but quite successful when two input variables were used. All PAHs, including difficult to separate peak pairs (benzo(k)fluoranthene/benzo(b)fluoranthene and indeno(1,2,3-c,d)pyrene/dibenzo(a,h)anthracene), were separated in a standard (5% phenyl-95% dimethylpolysiloxane) capillary column at an optimum temperature ramp of 8.0 degrees C/min and final hold temperature in the range of 260-320 degrees C.     

Adsorption kinetics and isotherm parameters of naphthalene onto natural- and chemically modified bentonite from aqueous solutions

Polycyclic aromatic hydrocarbons (PAHs) have widely been studied and a special concern because of their mutagenic and carcinogenic activities. In this study, natural- and chemically modified-bentonite were characterized by means of N₂ adsorption method, XRD, SEM, FT-IR, elemental and thermal analysis and zeta potential techniques and their adsorption behavior were then investigated toward naphthalene, which is the first member of the PAHs. The effects of various experimental parameters such as pH, contact time and temperature on adsorption were tested in the experiments. The optimum pH values for naphthalene adsorption onto natural bentonite (NB) and hexadecyltrimethylammonium bromide modified bentonite (HB) were found to be as 4.00 and 5.97, respectively. The equilibrium contact time was 60 min for both of the adsorbent. A comparison of the linear and nonlinear method of three widely used kinetic models, which are Lagergren-first order, the pseudo-second-order and Elovich kinetics, and the most popular isotherms, which are Langmuir and Freundlich, were examined to the experimental data of the adsorption of naphthalene onto NB and HB. The kinetic results indicated that the pseudo-second-order kinetic model with high correlation coefficients was more suitable than the other kinetic models e.g. Lagergren first-order and Elovich. All results showed that the modified bentonite can be used as an adsorbent to remove PAHs from aqueous solutions by using adsorption method due to its effectiveness, simplicity and low-cost than the other conventional methods.     

Description of adsorption equilibrium of PAHs on hypercrosslinked polymeric adsorbent using Polanyi potential theory

In this research,static adsorption of three polycyclic aromatic hydrocarbons(PAHs),naphthalene,acenaphthene,and fluorene,from aqueous solutions onto hypercrosslinked polymeric adsorbent within the temperature range of 288-308 K is investigated.Several isotherm equations are correlated with the equilibrium data,and the experimental data is found to fit the Polanyi-Dubinin-Manes model best within the entire range of concentrations,providing evidence that pore-filling is the dominating sorption mechanism for PAHs.The study shows that the molecular size of adsorbates has distinct in-fluence on adsorption capacity of hypercrosslinked polymeric adsorbent for the PAHs;the larger the adsorbate molecular size,the lower the adsorption equilibrium capacity.Based on the Polanyi-Dubinin-Manes model,the molecular size of adsorbates was introduced to adjust the adsorbate molar volume.Plots of qv vs.(σε /Vs) are collapsed to a single correlation curve for different adsorbates on hypercrosslinked polymeric resin.     

Solid-surface phosphorescence characterization of polycyclic aromatic hydrocarbons and selective determination of benzo(a)pyrene in water samples

This paper presents the phosphorescence characterization of polycyclic aromatic hydrocarbons (PAHs) on solid-surface for obtaining new flow-through phosphorescence optosensors for PAHs-based on-line, immobilized onto a non-ionic resin solid support coupled to a continuous flow system and the applications for the selective determination of benzo(a)pyrene (BaP). The phosphorescent characterization of 15 PAHs, described as major pollutants by the Environmental Protection Agency (EPA) (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, benzo(a)anthracene, benzo(k)fluoranthene, benzo(b)fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, benzo(g,h,i)perylene and dibenzo(a,h)anthracene) has been carried out. The experimental variables (heavy atom, deoxygenation and organic solvent in samples) for obtaining different possibilities for developing mono and multi-parameter PAH sensors and the conditions for PAH screening have been carefully studied and the experimental conditions to determination of BaP in presence of other PAHs in water samples have been optimized.     

Adsorption preconcentration in the luminescence determination of polycyclic aromatic hydrocarbons

The adsorption of polycyclic aromatic hydrocarbons (PAHs)—pyrene, anthracene, phenanthrene, and fluorene—by a cellulose matrix of micellar media containing sodium dodecyl sulfate and a nonionogenic polymer, namely, polyethylene glycol is studied. Procedures are proposed for the luminescence determination of PAHs in the adsorbent phase.     

Polycyclic aromatic hydrocarbons (PAHs) in edible oils by gas chromatography coupled with mass spectroscopy

The occurrence of polycyclic aromatic hydrocarbons (PAHs) in nine edible oils of three categories of oil samples, such as soy bean oil, mustard oil and coconut oil, has been studied to determine the contamination degree of this type of oil samples. Eight major carcinogenic polycyclic aromatic hydrocarbons (PAHs), such as naphthalene, anthracene, phenanthrene, fluorene, pyrene, crysene, benzo(a)pyrene and benzo(a)anthracene, were identified and quantified in the extract of edible oils collected from Bangladeshi Markets by gas chromatography and mass spectroscopy. All of the carcinogenic PAHs are not present in the edible oils. A few of the carcinogenic PAHs are present in the oils but it is within the permissible limit. The results for the recoveries of naphthalene, fluorene, phenanthrene, anthracene, pyrene, crysene, benzo(a)anthracene and benzo(a)pyrene were in the range of 56–84%. The limit of detection (LOD) of the GC–MS method, established at signals three times that of the noise for naphthalene, fluorene, phenanthrene, anthracene, pyrene, crysene, benzo(a)anthracene and benzo(a)pyrene, was 2.0–2.5 ng, respectively.     

Trap and Desorption Gc/Ms for Detection Polycyclic Aromatic Hydrocarbons in Motorcycles Emission

ABSTRACT

The application of trap and desorption GC/MS to monitoring of sixteen PAHs in the exhaust emissions from motorcycles was investigated. The time of sampling and analysis for one sample is in 40 minutes. The relative standard deviations were estimated from 20% to 34% for monitoring the total concentrations of PAHs from the emissions of motorcycles. The PAH concentrations appeared to show distinct variations with the stroke, engine size and the aging of motorcycles. The predominate of PAHs in the emissions of motorcycle were naphthalene, fluorene, anthracene, fluoranthene and pyrene. Naphthalene exhibited the highest concentration that was obtained over 79% of the total concentration of sixteen PAHs in the emissions of the over nine years old motorcycles.     

Gas chromatographic-mass spectrometric determination of polycyclic aromatic hydrocarbons formed during the pyrolysis of phenylalanine

The formation of polycyclic aromatic hydrocarbons (PAHs) during pyrolysis process of phenylalanine had been studied. Ten PAHs, including fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo[a]anthracene, chrysene, benzo[k]fluoranthene, benzo[e]pyrene, and benzo[a]pyrene were analyzed by gas chromatography-mass spectrometry using selective ion monitoring mode. This technique offers the capability to analyze trace amounts of PAHs in phenylalanine pyrolyzates. The pyrolysis was carried out in a micro-furnace with quartz furnace liner. The injection was conducted with glass pelletizer syringe to avoid metal contamination. Qualitative results were obtained at 900 degrees C and quantitative analysis of 10 PAHs was done for 700 and 900 degrees C.     

超高效合相色谱快速分析塑料制品中的18种多环芳烃

建立了一种超高效合相色谱-二极管阵列检测器快速分析塑料制品中萘、苊烯、苊、芴、菲、蒽、荧蒽、芘、苯并(a)蒽、(屈艹) 、苯并(b)荧蒽、苯并(k)荧蒽、苯并(j)荧蒽、苯并(e)芘、苯并(a)芘、茚并(1,2,3-cd)芘、二苯并(a,h)蒽、苯并(g,h,i)苝(二萘嵌苯)的方法。以甲苯为溶剂,超声萃取实际塑料制品中的多环芳烃,经超高效合相色谱分析。采用Daicel IB-3手性色谱柱,以CO₂为流动相,甲醇/乙腈(25:75, v/v)为流动相助溶剂,在柱温为40 ℃,背压为15.17 MPa的条件下,18种多环芳烃在8.5 min之内实现基线分离。18种多环芳烃的线性范围为0.05~50 mg/L(r≥0.9995),定量限(S/N> 10)为0.05 mg/L。加标回收率为78.3%~117.6%,相对标准偏差(RSD, n=5)小于5%。该方法具有分析速度快、分离效率高、节约有机溶剂的优点。     

Preparation and characterization of DNA films using oleylamine modified Au surfaces

The capacity of a periodic mesoporous organosilica (PMO) to adsorb the aromatic compounds benzene, toluene, o-, and p-xylenes (BTX), which are usually present in produced waters, was investigated under both column and batch processes. The PMO was synthesized by condensation of 1,4 bis(triethoxisilyl)benzene (BTEB) under acidic conditions by using structure-directing agent (SDA) Pluronic P123 in the presence of KCl. Thermogravimetric analysis showed that the presence of the surfactant decreases the thermal stability of the PMO. The small-angle X-ray diffraction pattern, as well as the nitrogen adsorption/desorption isotherm measurements, revealed that the synthesized material has a crystalline structure, with hexagonally-ordered cylindrical mesopores. The adsorption kinetics study indicated an adsorption equilibrium time of 50 min and also showed that the data best fitted the pseudo-first order kinetic model. The intraparticle diffusion model was also tested and pointed to the occurrence of such process in all cases. Both Langmuir and Temkin models best represented the adsorption isotherms of toluene; Langmuir and Redlich-Peterson models best represented the data obtained for the other compounds. Adsorption capacity decreases in the order benzene>o-xylene>p-xylene>toluene. Satisfactory results were observed in the application of the synthesized PMO for the removal of BTX from aqueous solution.     

Determination of polycyclic aromatic hydrocarbons in sediment using solid-phase microextraction with gas chromatography-mass spectrometry

Manual solid-phase microextraction (SPME) coupled with gas chromatography-mass spectrometry (GC-MS) is applied for the determination of polycyclic aromatic hydrocarbons (PAHs) from natural matrix through a distilled water medium. Seven of the 16 PAH standards (naphthalene, acenaphthene, fluorene, anthracene, fluoranthene, pyrene, benzo[a]anthracene) are spiked on a marine muddy sediment. The samples, containing PAHs in the range of 10-20 ppm, are then aged at room temperature more than 10 days before analysis. The influence of the matrix, SPME adsorption time, pH, salt content, and SPME adsorption temperature are investigated. The reproducibility of the technique is less than 13% (RDS) for the first 6 considered PAHs and 28% (RDS) for benzo(a)anthracene with a fiber containing a 100-micron poly dimethylsiloxane coating. Linearity extended in the range of 5-50 picograms for PAHs direct injection, 5-70 picograms for PAHs in water, and 1-170 picograms for PAHs in sediment. The detection limit is estimated less than 1 microgram/kg of dry sample for the first 6 considered PAHs in sediment and 1.5 micrograms/kg of dry sample for benzo(a)anthracene using the selected ion monitoring mode in GC-MS. The recoveries of the considered PAHs are evaluated.     

Adsorption of Cu(II) from aqueous phase by Cedar bark

The capability of Cedar bark (Cedrus atlantica Manetti) (CB) for the adsorption of Cu(II) from aqueous solutions was examined. Adsorption isotherm and kinetics of Cu(II) by CB were investigated through a number of batch adsorption experiments. The effect of experimental parameters such as initial Cu(II) concentration, adsorbent mass, initial pH and ionic strength on the removal of metal ions was examined. Equilibrium data were fitted to the Langmuir, Freundlich and Harkins–Jura isotherm models. Experimental equilibrium data were best represented by the Langmuir and Harkins–Jura isotherms. The findings revealed that the CB has the potential to be used as an adsorbent for the removal of heavy-metal ions from aqueous solutions.