CARBONIZED FIBROUS RESIN AS A NEW SORBENT FOR SAMPLING POLYCYCLIC AROMATIC HYDROCARBONS （PAHS）IN AMBIENT AIR

A new sampling method of ambient air analysis using carbonized fibrous resin as a sorbent for polycyclic aromatic hydrocarbons(PAHs) was reported.The physical and chemical properties of the carbonized fibrous resins were measured.The sample pretreatment with ultrasonic extraction and subsequent clean-up elution through a silica gel column was optimized.The suitable ultrasonic extraction conditions were selected as follows:resin weight was 1.5g,ultrasonic extraction time 20min,volume of extraction solvent 100 ml and extraction operation times 2-3.The concentrated extractable organic matter was submitted to next step of clean-up procedure of adsorption chromatography on silica gel column/n-hexane and a mixture of dichloromethene:n-hexane solution 2:3(v/v).The PAHs fractions in the real samples from Changzhou,China were particularly analyzed using GC-MS data system and the data of mass spectra,retention times and scan numbers of the real samples were compared with that of the standards of 16 PAHs listed by the US EPA as “priority pollutants” of the environment. The pretreatment of samples of ambient air with carbonized fibrous resin as a sorbent for PAHs is proved to be reliable and might be used for the procedure of the determination of PAHs in atmospheric environment.     

Quantitative determination of 16 polycyclic aromatic hydrocarbons in soil samples using solid‐phase microextraction

A method for the determination of polycyclic aromatic hydrocarbons (PAHs) in soil samples using ultrasonic‐assisted extraction with internal surrogates combined with solid‐phase microextraction and GC‐MS has been developed. Five kinds of commercial solid‐phase microextraction fibers, 100 μm PDMS, 30 μm PDMS, 65 μm PDMS/DVB, 50 μm DVB/CAR/PDMS and 85 μm PA, were compared to choose the optimal SPME fiber for extraction of PAHs. One hundred micrometers of PDMS fiber was found to be more suitable for the determination of PAHs due to its wider linear range, better repeatability, lower detection and more satisfactory efficacy than the other fibers. Under the recommended conditions, 100 μm PDMS fiber could provide low nanogram level detection limits with correlation coefficient greater than 0.98. The method was also applied to determine PAHs in a spiked soil sample, obtaining recoveries higher than 79.3%. A field study with naturally contaminated samples from local contaminated sites was carried out. The proposed method was found to be a reliable, inexpensive and simple preparation method for quantitative determination of 16 PAHs in soil samples.     

Long-term sampling: Suitable monitoring strategy for determination of semi-volatile PAHs at outdoor and indoor sites

Summary A new, molecular diffusion-based, sampling device (Analyst 2) has been used for the determination of semi-volatile PAHs in air. It has been developed from a previous model (Analyst), which is suitable for volatile hydrocarbons. The new model is capable of collecting enough gaseous PAHs for GC-MS analysis of enriched samples after 2 months exposure to both urban and suburban air. The adsorbent material adopted for enriching PAHs from air (Carbopack C) gives good recoveries of analytes from naphthalene to chrysene when a single solvent extraction is run at ambient temperature. The results of an experiment for assessing the internal consistency of this device are presented here. Data collected indicate that the “uptake rate” is constant for a 6-month sampling period. Results are also presented and discussed for indoor and outdoor determination of volatile PAHs, collected at both urban and suburban sites over a 12-month period in 2-monthly steps.     

Improved analysis of Polycyclic Aromatic Hydrocarbons in atmospheric particulate matter by HPLC-fluorescence

An improved method is reported for determination of Polycyclic Aromatic Hydrocarbons (PAHs) in atmospheric particulate matter by HPLC-FLD. The sampling step (air volume collected during each sampling period varies in the range 10/13 m3) is carried out by means of a medium-flow pumping system (15 L min(-1)) on a glass fiber filter (47 mm diameter) placed as collecting substrate in the sampling-cassette. After sampling, the filter is extracted with 3 ml of acetonitrile in an ultrasonic bath for 30 minutes. As for extraction of PAHs from loaded filters a new criterion here is proposed to evaluate the recovery efficiency of PAHs from the sample, instead of the usual spiking method of standard solution. The extract was then reduced to 100 microL and analysed by HPLC-FLD on line spectra system. The method is rapid (about one hour for extraction and analysis), reproducible and enables to measure with good accuracy the atmospheric concentration of benzo(b)fluoranthene (BbF), benzo(k)fluoranthene (BkF), benzo(a)pyrene (BaP), benzo(ghi)perylene (BghiP), carcinogenic compounds always present in the urban airborne particulate matter. So it is useful for routine pollution studies and suitable to substitute the official method used now. Monthly average air concentrations, for the four PAHs above mentioned, measured in Rome from July 2001 to June 2002, are reported.     

GC-MS法测定大气样品的前处理研究--碳化纤维树脂捕集大气中痕量多环芳烃

研究了碳化纤维树脂吸附载体采集大气中多环芳烃(PAHs)的性能、样品前处理条件和毛细管气相色谱－质谱联用仪检测PAHs的,地具有代表性的多个采样点进行了实地采样、分析,证明碳化纤维树脂吸附载体是一种性能独特的固相吸附剂,建立的样品前处理方法可行,分析数据可靠,可用于大气中PAHs的检测。     

Quantification of volatile PAHs present at trace levels in air flow by aqueous trapping—SPE and HPLC analysis with fluorimetric detection

In the context of a European project, a new approach of sampling of volatile polycyclic aromatic hydrocarbons (PAHs) from air was developed. In fact, the aim of this project was to test the efficiency of an air cleansing prototype reactor, which was operating by non-thermal plasmolysis. With an eye to model the atmosphere ejected by the prototype, we needed to vaporise the volatile PAHs in an air stream at concentrations as low as those recommended by European Directives (96/62/CE) for PAHs in ambient air (i.e. 1 ng m⁻³). Our strategy was based on the analysis of PAHs trapped in an aqueous medium, in order to avoid important losses of volatile compounds observed during the delicate desorption-concentration step when classical solid supports are used. Then a study was carried out to determine: the design of the collecting part, the flow-rate of the air sampling, the nature and concentration of chemical additives used to enhance PAH solubility in water. The very highly diluted aqueous media obtained after the bubbling step were concentrated by solid-phase extraction (SPE) on hydrophobic cartridges and analysed on-line by reversed-phase HPLC with UV and fluorimetric detections. Lastly, the sampling technique was directly applied to the outlet of the air cleansing prototype and the analysis after 3-6 h of non-thermal plasmolysis showed that the target volatile PAHs were not present in an air stream initially polluted by volatile organic compounds.     

大流量采样高分辨气相色谱/高分辨质谱法测定大气中的多氯联苯和多溴联苯醚

建立了大流量空气采样高分辨气相色谱/高分辨质谱(HRGC/HRMS)同时分析测定大气样品中多氯联苯(PCBs)和多溴联苯醚(PBDEs)的分析方法。结果表明在采样过程中污染物没有发生穿透。通过添加 13C同位素标准物质进行评价,PCBs和PBDEs的加标回收率分别为60.7%～121.4%和69.9%～140.4%,均符合美国环保署相关方法的要求。PCBs和PBDEs的方法检出限分别低于0.019 pg/m3和0.189 pg/m3;色谱分离效果良好,可以满足大气样品中PCBs和PBDEs的监测需要。     

Solid-phase microextraction for determining the distribution of sixteen US Environmental Protection Agency polycyclic aromatic hydrocarbons in water samples

A solid-phase microextraction (SPME) procedure has been developed for the determination of 16 US Environmental Protection Agency promulgated polycyclic aromatic hydrocarbons (PAHs). Five kinds of SPME fibers were used and compared in this study. The extracted sample was analyzed by gas chromatography with flame ionization detection or mass spectrometry. Parameters affecting the sorption of analyte into the fibers, including sampling time, thickness of the fiber coating, and the effect of temperature, have been examined. Moreover, the feasibility of headspace SPME with different working temperatures was evaluated. The method was also applied to real samples. The 85-microm polyacrylate (PA) and 100-microm poly(dimethylsiloxane) (PDMS) fibers were shown to have the highest affinities for the selected PAHs. The PA fiber was more suitable than the PDMS fiber for the determination of low-ring PAHs while high sensitivity of high-ring PAHs was observed when a 100-microm PDMS fiber was used. The method showed good linearity between 0.1 and 100 ng/ml with regression coefficients ranging from 0.94 to 0.999. The reproducibility of the measurements between fibers was found to be very good. The precisions of PA and PDMS fibers were from 3 to 24% and from 3 to 14%, respectively. Headspace SPME is a valid alternative for the determination of two- to five-ring PAHs. A working temperature of 60 degrees C provides significant enhancement in sensitivity of two- to five-ring PAHs having low vapor pressures (>10(-6) mmHg at 25 degrees C) (1 mmHg = 133.3 Pa) and low Henry's constants (>10 atm ml/mol) (1 atm = 1.01 x 10(5) Pa).     

大流量采样-GC-NCI-MS测定环境空气中的多溴联苯醚

建立了大流量采样-气相色谱负化学电离质谱法测定环境空气中痕量多溴联苯醚的方法.用PS-1型大流量空气采样器采集环境空气样品,样品经提取、纯化后采用气相色谱负化学电离质谱法测定环境空气中多溴联苯醚.方法的线性范围在5～10000 pg/m3之间,检出限1～50 pg/m3.用于检测2006年5月在广州市采集的环境空气样品,多溴联苯醚组分含量在5.4～4989 pg/m3范围.该方法适合用于监测环境空气中的痕量PBDEs.     

Highly sensitive determination of polycyclic aromatic hydrocarbons in ambient air dust by gas chromatography-mass spectrometry after molecularly imprinted polymer extraction

A method based on solid--phase extraction with a molecularly imprinted polymer (MIP) has been developed to determine five probable human carcinogenic polycyclic aromatic hydrocarbons (PAHs) in ambient air dust by gas chromatography-mass spectrometry (GC-MS). Molecularly imprinted poly(vinylpyridine-co-ethylene glycol dimethacrylate) was chosen as solid-phase extraction (SPE) material for PAHs. The conditions affecting extraction efficiency, for example surface properties, concentration of PAHs, and equilibration times were evaluated and optimized. Under optimum conditions, pre-concentration factors for MIP-SPE ranged between 80 and 93 for 10 mL ambient air dust leachate. PAHs recoveries from MIP-SPE after extraction from air dust were between 85% and 97% and calibration graphs of the PAHs showed a good linearity between 10 and 1000 ng L⁻¹ (r = 0.99). The extraction efficiency of MIP for PAHs was compared with that of commercially available SPE materials—powdered activated carbon (PAC) and polystyrene-divinylbenzene resin (XAD)—and it was shown that the extraction capacity of the MIP was better than that of the other two SPE materials. Organic matter in air dust had no effect on MIP extraction, which produced a clean extract for GC-MS analysis. The detection limit of the method proposed in this article is 0.15 ng L⁻¹ for benzo[a]pyrene, which is a marker molecule of air pollution. The method has been applied to the determination of probable carcinogenic PAHs in air dust of industrial zones and satisfactory results were obtained.     

Solid-phase microextraction and headspace solid-phase microextraction for the determination of high molecular-weight polycyclic aromatic hydrocarbons in water and soil samples

The feasibility of direct-immersion (DI) solid-phase microextraction (SPME) and headspace (HS) SPME for the determination of high-ring polycyclic aromatic hydrocarbons (PAHs) (4- to 6-ring PAHs) in water and soil samples is studied. Three SPME fibers--100- and 30-microm polydimethylsiloxane (PDMS) and 85-microm polyacrylate (PA) fibers-are compared for the effective extraction of PAHs. Parameters affecting the sorption of PAHs into the fiber such as sampling time, sampling volume, and temperature are also evaluated. The extracted amounts of high-ring PAHs decrease with the decreasing of film thickness, and the 100-microm PDMS has the highest extraction efficiency than 85-microm PA and 30-microm PDMS fibers. Also, the extraction efficiency decreases with the increasing molecular weights of PAHs. Of the 10 high-ring PAHs, only fluoranthene and pyrene can reach equilibrium within 120 min at 25 degrees C for DI-SPME in a water sample. Increasing the temperature to 60 degrees C can increase the sensitivity of PAHs and shorten the equilibrium time. A 0.7- to 25-fold increase in peak area is obtained for DI-SPME when the working temperature is increased to 60 degrees C. For HS-SPME, the extraction efficiency of PAHs decrease when the headspace volume of the sampling system increases. All high-ring PAHs can be detected in a water sample by increasing the temperature to 80 degrees C. However, only 4- and 5-ring PAHs can be quantitated in a CRM soil sample when HS-SPME is used. The addition of a surfactant with high hydrophilic property can effectively enhance the sensitivity of high-ring PAHs. HS-SPME as well as DI-SPME with 100-microm PDMS or 85-microm PA fibers are shown to be suitable methods for analyzing high-ring PAHs in a water sample; however, this technique can only apply in a soil sample for PAHs having up to 5 rings.     

Solid-phase microextraction under controlled agitation conditions for rapid on-site sampling of organic pollutants in water

An electric drill coupled with a solid-phase microextraction (SPME) polydimethylsiloxane (PDMS) fiber or a PDMS thin film was used for rapid sampling of polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Laboratory experiments demonstrated that the sampling rates of SPME fiber and thin film can be predicted theoretically. Compared with the SPME fiber, the PDMS thin film active sampler exhibited a higher sampling rate and much better sensitivity due to its higher surface-to-volume ratio and its larger extraction phase volume. The amount of the analytes extracted by the thin film was around 100 times higher than those obtained by fiber, for both 5 min rapid sampling and equilibrium extraction. A new thin film active sampler was then developed for rapid on-site water sampling. The sampling kit included a portable electric drill, a copper mesh pocket, a piece of thin film, and a liner. Laboratory experiments indicated that the sampling remained in the linear uptake phase with this sampler to 8 min for the PAHs. Field test illustrated that this novel sampler was excellent for rapid on-site water sampling due to its short sampling period, high sampling efficiency and durability The thin film sampling kit facilitates on-site sampling, sample preparation, storage and transport. This new sampler is more user-friendly and easier to commercialize than previous samplers.     

Determination of polycyclic aromatic hydrocarbons in waste water by off-line coupling of solid-phase microextraction with column liquid chromatography

A new method for the determination of polycyclic aromatic hydrocarbons (PAHs) in waste water using solvent-free solid-phase microextraction (SPME) is described. The PAHs are extracted with a 100 microm polydimethylsiloxane (PDMS) fiber, desorbed in 40 microl acetonitrile and measured with LC and fluorescence detection. The detection limits of this very simple method under the given conditions (extraction from 5 ml sample, extraction time 1 h) are in the range of 1-6 ng l(-1). The standard deviations (n = 6) at a concentration level of 0.8 microg l(-1) are between 1.8 and 14.4%. The procedure was used for the determination of PAHs in contaminated water samples.     

微波消解石墨炉原子吸收法测定环境空气中痕量锡

建立石墨炉原子吸收法测定环境空气中痕量锡的方法。采用混合纤维素微孔滤膜采集环境空气样品,用硝酸–氢氟酸微波消解样品,以5%硝酸镧–10%酒石酸混合液作基体改进剂,石墨炉原子吸收法进行测定。当采样体积为4 800 L,定容体积50 m L时,方法检出限为0.024μg/m~3,样品加标回收率为96.0%~106.0%,测定结果的相对标准偏差为2.74%~5.81%(n=7)。该方法样品处理操作过程简单,酸用量少,可用于环境空气中痕量锡的测定。     

Simultaneous sampling and analysis for vapor mercury in ambient air using needle trap coupled with gas chromatography-mass spectrometry

A needle trap (NT) technique for simultaneous sampling and analysis of vapor and particle mercury in ambient air using gold wire filled in a syringe needle has been developed. This NT technique relies on gold amalgamation rather than adsorption/absorption to traditional solid-phase microextraction. Hg trapped by Au-amalgamation NT is thermally desorbed in a hot injection port of a gas chromatograph; desorbed Hg is then determined by the coupled mass spectrometer. This simultaneous sampling and analysis technique were optimized, tested, and used for the collection and accurate determination of elemental Hg in ambient air. Linear calibration curves were obtained for Hg sampling by NT when mass spectrometry (MS) was used for detection; they spanned over 4 orders of magnitude. MS offered excellent sensitivity and selectivity. Selected ion monitor (SIM) mode was used for the linear calibration curves. The selected quantitation ion was m/z 202, since m/z 202 was the strongest isotope of mercury mass spectrum. The method was verified with HgCl(2) spiked solution samples. An excellent agreement was found between the results obtained for the Hg-saturated air samples and HgCl(2) spiked solution samples. The use of the Au-amalgamation gas-sampling needle trap method, for the measurement of Hg in air and Hg(2+) water samples, is described herein.     

A review of monitoring of airborne polycyclic aromatic hydrocarbons: An African perspective

In this review, we focus on the status of the monitoring of polycyclic aromatic hydrocarbons (PAHs) in ambient air as well as in living (indoor) and working environments in Africa from 2000 to 2018. This is important as PAHs are ubiquitous in the environment and are known to be potentially carcinogenic. Aspects of sampling such as collection media for particle bound and gaseous PAHs are discussed. The efficiency and basic quality assurance data of commonly employed extraction techniques for separating target PAHs from sampling media using conventional solvent-based and emerging solvent-free approaches were also evaluated. Polyurethane foam and quartz fiber filters are generally the most commonly used collection media for gaseous and particle bound PAHs, respectively. A wide range of total PAH concentrations in ambient air has been reported across the continent of Africa, with the highest levels found at sampling sites close to high density traffic and industrial areas. A rapidly increasing population, commercial and industrial development, poor urban transportation infrastructure and the use of low quality oil products were the main causes of high total gas and particulate PAH concentrations (1.6–103 μg/m³) in West African port cities such as Cotonou, Benin. With regards to indoor environments, gas phase PAHs were detected at the highest total concentrations in rural areas ranging from 1 to 43 μg/m³ in Burundi with naphthalene being the most prevalent. Firewood burning was the major emission source in most developing countries and resulted in benzo[a]pyrene concentrations above the European permissible risk level of 1 ng/m³.     

Dynamic non-equilibrium SPME combined with GC, PICI, and ion trap MS for determination of organophosphate esters in air

Methodology for time-weighted average (TWA) air measurements of semivolatile organophosphate triesters, widely used flame-retardants and plasticizers, and common indoor pollutants is presented. Dynamic non-equilibrium solid-phase microextraction (SPME) for air sampling, in combination with GC/PICI and ion trap tandem MS, yields a fast, almost solvent-free method with low detection limits. Methanol was used as reagent gas for PICI, yielding stable protonated molecules and few fragments. A field sampler, in which a pumped airflow over three polydimethylsiloxane (PDMS) 100-μm fibers in series was applied, was constructed, evaluated, and used for the measurements. The method LODs were in the range 2–26 ng m⁻³ for a sampling period of 2 h. The uptake on the SPME fibers was shown to be about five times faster for triphenyl phosphate compared to the other investigated organophosphate esters, most likely due to more lipophilic properties of the aromatic compound. The boundary layer for triphenyl phosphate when using a 100-μm PDMS sorbent was determined to 0.08 mm at a linear air velocity of 34 cm s⁻¹. Five different organophosphate triesters were detected in air from a laboratory and a lecture hall, at concentrations ranging from 7 ng m⁻³ up to 2.8 μg m⁻³.     

A new method for the measurement of trace amounts of HONO in the atmosphere using an air-dragged aqua-membrane-type denuder and fluorescence detection

A new method for the measurement of trace amounts of HONO has been developed. Nitrous acid in the ambient air is absorbed in an aqueous solution by an air-dragged aqua-membrane-type denuder. The absorbed nitrite is reacted with 2,3-diaminonaphthalene, and the formed 1-naphthotriazol is measured using a fluorescence method. The calibration curve of HONO shows a straight line from 0 to 4000 ppt, and the detection limit is estimated to be 8.1 ppt calculated as being three times of the base line noise. The time resolution, which is defined as the time required to become a constant value by changing from 0 to ca. 1000 ppt was 2 min. The present method is not affected by NO(2), NO, SO(2), O(3) NH(3) or mixtures of these gases and organic nitrate, organic carboxylic acids, alcohols and aldehydes. The determination results of HONO concentrations in the ambient air by the present method are in good agreement with those by the annular denuder system and the differential optical absorption method.     

Screening direct analysis of PAHS in atmospheric particulate matter with SPME

A direct headspace SPME method with PDMS fiber was developed for the determination of polynuclear aromatic hydrocarbons (PAHs) in atmospheric particulate matter collected in HiVol filter. The recovery obtained for PAHs lower than four congeners with the proposed method falls in the range 50-125% and DL was around 5-20 pg. The results obtained with standard reference materials (SRM 1649 and SRM 1650) for determination of PAHs showed acceptable agreement with the declared or certificated values.     

Determination of particle-associated hydroxynitropyrenes with correction for chemical degradation on a quartz fibre filter during high volume air sampling

A correction method for the determination of atmospheric monohydroxylated derivatives of 1-nitropyrene (hydroxy-1-nitropyrenes, OHNPs) based on their degradation rates during high volume air sampling was established. OHNPs adsorbed directly on a quartz fibre filter (QFF) or on airborne particles collected on a QFF were exposed to ambient air passively or actively in a high volume air sampling system. The influence of ozone flux and exposure time on the degree of degradation of OHNPs was investigated. Up to 50% of OHNPs degraded over 1 h of exposure to ambient air containing ～60 ppbv of ozone in the active system. The degradation rate constants of OHNPs were found to correlate with the number of ozone molecules passing through the QFF in a unit time (N_O3) during high volume air sampling. The chemical loss of OHNPs under high volume air sampling conditions was successfully evaluated by the exposure time and the pseudo-first-order rate constant for OHNP degradation estimated from the correlation with N_O3. Concentrations of 3-, 6-, and 8-hydroxy-1-nitropyrenes in airborne particles collected in Osaka, Japan were determined using the established correction method.