Calibration and field verification of semipermeable membrane devices for measuring polycyclic aromatic hydrocarbons in water

The use of semipermeable membrane devices (SPMDs) has become common in environmental sampling of nonpolar organic contaminants, yet few data exist for the uptake or sampling rates of polycyclic aromatic hydrocarbons (PAH). Two separate laboratory calibration experiments were conducted to determine the sampling rates of 28 individual PAH and 19 homologues. PAH with a log Kow > 4.5 remained in the linear uptake phase for 30 days, but PAH with a log Kow < 4.5 began to approach steady state within 15 days. Sampling rates, corrected for dissolved organic carbon, ranged from 2.11 to 6.06 L d(-1). Shear flow across the membrane had no statistically significant effect on rates over the range of 0.01-0.50 cm s(-1). Field verification of these sampling rates yielded agreement within about a factor of 2 for most PAH and a factor of 4 for all PAH. The worst agreement was for the most hydrophobic PAH, where partitioning into dissolved and particulate organic carbon pools are more important and less certain. These SPMD sampling rate data will allow quantitative estimations of freely dissolved concentrations of 47 compounds that are commonly used for PAH and petroleum product source identification and allocation.     

Temperature-dependent uptake rates of nonpolar organic compounds by semipermeable membrane devices and low-density polyethylene membranes

The effect of temperature on sampling rates and sampler-water partition coefficients of semipermeable membrane devices (SPMDs) and low-density polyethylene (LDPE) strips was studied in an experimental setup under controlled flow conditions. Aqueous concentrations of chlorobenzenes, polychlorinated biphenyls (PCBs), and polyaromatic hydrocarbons (PAHs) were maintained by continuous circulation of the water over a generator column. Sampling rates for standard design SPMDs (460 cm2) were in the range of 20-200 L d(-1). No significant differences were observed between sampling rates of SPMDs and LDPE strips, but the latter samplers reached equilibrium faster because of their smaller sorption capacity. Sampling rates at 30 degrees C were higher than at 2 degrees C by a factor of about 3. Sampling rate modeling indicated boundary layer-controlled uptake for compounds with log octanol-water partition coefficients smaller than 4.4 and aqueous boundary-layer controlled uptake for more hydrophobic compounds. SPMD-water partition coefficients did not significantly change with temperature, but LDPE-water partition coefficients were larger at 2 degrees C than at 30 degrees C by a factor of 2. For field application of SPMDs, the results imply that temperature is not a key factor that controls uptake rates unless large geographical and temporal scales are involved. The results confirm that water flow velocity has a profound effect on sampling rates.     

Polycyclic aromatic hydrocarbons in a semiaquatic plant and semipermeable membrane devices exposed to air in Thailand

Semipermeable membrane devices (SPMDs) were deployed at six sites in the Bangkok region, Thailand, to investigate spatial variations in atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs). Sampling sites affected by various levels of traffic intensity were studied. In addition, PAH levels were determined in a common human food plant (water spinach) harvested from canals and ponds in the sampling areas. Significant differences in atmospheric PAH concentrations between sites were found, with 10 times higher PAH levels in the urban areas compared to the rural areas. Increasing concentrations of 1-methylphenanthrene relative to phenanthrene were found in the urban air close to the city center, indicating that traffic probably contributed to the higher PAH concentrations detected. Due to SPMD's passive sampling technique, their long-term operation and high ability to detect spatial differences, they proved to be suitable for semiquantitative field studies of PAHs. The PAH compounds sampled with SPMDs were mainly associated with gaseous PAHs, while both gas phase and particle-bound PAHs were detected in the plant samples. The relative abundance ratios of some PAHs in the plants were not well correlated with the ratios detected in the SPMDs, indicating that gas-phase exposure made low contribution to the PAH concentrations in the plants. However, similarities in the profiles of 3-ring PAHs between the SPMD and plant samples indicate that gas-phase exchange occurs between the atmosphere and the plants.     

Use of passive samplers to mimic uptake of polycyclic aromatic hydrocarbons by benthic polychaetes

Experiments were conducted to test whether passive samplers made of low-density polyethylene (polyethylene devices, or PEDs) can estimate the extent of uptake of polycyclic aromatic hydrocarbons (PAHs) by benthic polychaetes (Nereis virens) in contaminated marine sediments. For a variety of PAHs, PEDs reached 90% equilibrium with sediment PAHs in 60 days or less. Using 60-day sediment bioaccumulation tests, we have demonstrated a significant relationship between PAH concentrations in the polychaetes and the PEDs (R2 = 0.67, p = 0.002), with the PEDs taking up less PAHs than the polychaetes. Because of this relationship, PEDs can potentially be used in a regulatory context to simulate uptake of bioavailable PAHs in contaminated marine sediments. The PED PAH concentrations were also used to calculate porewater PAH concentrations that allowed for the estimation of a linear free-energy relationship between the lipid-water distribution coefficient (Klip) and the octanol-water distribution coefficient (KOW) for PAH uptake in marine polychaetes (R2 = 0.94, p < 0.0001).     

Calibrating the uptake kinetics of semipermeable membrane devices in water: impact of hydrodynamics

The use of lipid-containing semipermeable membrane devices (SPMDs) is becoming commonplace, but the potential effects of environmental variables affecting the accumulation of contaminants into SPMDs had not been characterized sufficiently, yet. To characterize the effect of hydrodynamic conditions on the contaminant uptake kinetics, accumulation of pentachlorobenzene, hexachlorobenzene, and hexachlorocyclohexane isomers from water into SPMD was studied at various water flow rates. The accumulation kinetics of hydrophobic compounds (log Kow > 4) are governed by the aqueous boundary layer in linear flow velocity range from 0.06 to 0.28 cm s(-1) and sensitive to slight changes in flow rate. The effect of flow velocity on the exchange kinetics increases with increasing hydrophobicity. Under faster, but still laminar flow conditions (0.28-1.14 cm s(-1)), the sensitivity to changes in flow decreases to a nonsignificant level for the substances under consideration. The results of this study confirm that the use of the laboratory-derived calibration data for estimation of analyte concentrations in the ambient environment is limited unless flow-sensitive performance reference compounds are used.     

Calorimetric approach of the interaction and absorption of polycyclic aromatic hydrocarbons with model membranes

The ability of polycyclic aromatic hydrocarbons (PAHs) to interact with cell membranes outer lipid layer and subsequently to penetrate inside cells can be a prerequisite for exhibiting a mutagenic and carcinogenic activity. The effect exerted by pyrene, benzo[a]pyrene, and anthracene, three structurally similar polycyclic aromatic hydrocarbons possessing mutagenic and carcinogenic activity on the thermotropic behavior of model membranes represented by dimyristoylphosphatidylcholine (DMPC) vesicles, was investigated by differential scanning calorimetry (DSC). The examined compounds, when dispersed in liposomes during their preparation, exerted a different action on the gel-to-liquid crystal phase transition of DMPC multilamellar vesicles. Pyrene and benzo[a]pyrene affected the transition temperature (Tm), shifting it toward lower values with a concomitant decrease of the associated enthalpy changes (AM). Anthracene does not significantly affect the thermotropic behavior of lipid vesicles for all tested concentrations. The interaction between PAHs and model membranes was also studied by considering the ability of such compounds as a finely powdered solid or adsorbed on soil surrogate (constituted by silica gel) to migrate through an aqueous medium. This transfer process was compared with the PAHs intermembrane transfer from PAH loaded liposomes to empty membranes. These processes can mimic absorption kinetics mediated by hydrophilic or lipophilic media. No interaction occurred between model membranes and solid PAHs. A very small effect was also observed for PAHs released by silica gel, suggesting that the migration and absorption are hindered by the aqueous layer and that their low hydrophilic character inhibits migration through the aqueous layer surrounding the multilamellar vesicles (MLV). Different behavior was observed by considering the time-dependent studies carried out by contacting, for increasing times, equivalent amounts of empty DMPC vesicles with PAH loaded ones; all compounds were able to migrate between the two different kinds of model membranes. Thus, PAHs are unable to reach and penetrate biological membranes migrating through an aqueous layer but, when dispersed in a lipophilic medium, are able to penetrate and diffuse inside a membrane. The obtained experimental results seem to validate the employment of the DSC technique in order to study the ability of bioactive compounds, not only to interact with biological membranes, but also to be adsorbed inside a cell when dispersed in a lipophilic medium.     

Controlled exposure chamber study of uptake and clearance of airborne polycyclic aromatic hydrocarbons by wheat grain

Polycyclic aromatic hydrocarbons (PAHs) can partition from the atmosphere into agricultural crops, contributing to exposure through the dietary pathway. In this study, controlled environmental chamber experiments were conducted to investigate the transfer of PAHs from air into wheat grain, which is a major food staple. A series of PAHs ranging in size from naphthalene to pyrene were maintained at elevated gas-phase concentrations in the chamber housing mature and dry wheat grain both on the plant and with the husk removed. The PAHs did not achieve equilibrium between the air and grain over the 6.5 month monitoring period used in this study. Therefore, PAH uptake under field conditions is expected to be kinetically limited. A clearance study conducted for the grain showed the half-life of clearance was approximately 20 days for all compounds studied. The results suggest that atmospheric contaminants that partition into grain may remain in the grain long enough to contribute to dietary exposure for humans. Mass transfer across the air/grain interface appeared to be limited by grain-side resistance. The grain may act as a multicompartment system with rapid exchange at the surface followed by slower transfer into the grain. A grain/air concentration relationship was derived for the uptake time that is relevant to field conditions.     

Optimization of the procedure for the determination of polycyclic aromatic hydrocarbons and their derivatives in fish tissue: Estimation of measurements uncertainty

Three alternative procedures were employed for the isolation of polycyclic aromatic hydrocarbons (PAHs; 15 of 16 US EPA priority pollutants and benzo[e]pyrene), their methyl-derivatives and sulphur analogues from fish tissue: (1) Soxhlet extraction, (2) batch extraction enhanced by sonication, and (3) saponification of the sample followed by re-extraction of analytes into hexane. Soxhlet extraction using hexane-acetone (1:1, v/v) was the most efficient extraction technique, with analyte recoveries in the range 70-108%. Within optimization of the clean-up step, several types of gel permeation chromatography (GPC) systems were tested: two types of polystyrene divinylbenzene copolymer gels (PSDVB), both 'soft' gel type (Bio-Beads S-X3) and 'rigid' gels type (PL gel and Envirogel) in combination with various mobile phases were compared. Bio-Beads S-X3 and mobile phase chloroform were the most appropriate for purifying of crude extracts before the final determinative step. High-performance liquid chromatography with fluorimetric detection (HPLC/FLD) was used for identification and quantification of PAHs in purified fish extracts. The uncertainties of PAHs measurements were estimated by employing two alternative approaches. Both provided similar results: the expanded uncertainties obtained for individual PAHs by the 'top-down' approach were in the range 9-53%, their values resulting from application of the 'bottom-up' approach were in the range 16-52%.     

Comparison of diffusion by anionic surfactants through cellulose acetate and collagen membranes

From a dermatological point of view, it is important to know what is the irritation potential of surfactants on human skin. Recent research trends have been oriented towards the establishment of new ' in vitro ' techniques that will avoid animal experimentation.
In this paper, some results on the rate of diffusion of different anionic surfactants through both cellulose acetate and collagen membranes are described. A correlation between results of diffusion through the protein membrane and results published on the same surfactants and their irritation potential during ' in vivo ' experiments appears possible.     

Survey of polycyclic aromatic hydrocarbons of vegetable oils and oilseeds by GC-MS in China

There is a lack of information regarding the occurrence and content of contamination of polycyclic aromatic hydrocarbon (PAH) in edible vegetable oils and oilseeds used for oil production in China. By combining the advantages of ultrasound-assisted extraction, low temperature separation and silica SPE purification, a method for the determination of the USEPA, 16 PAHs was developed based on GC-MS to fill this gap. The method recoveries for oils and oilseeds were 84.4–113.8% and 84.3–115.3%, respectively. The LODs and LOQs for 16 PAHs were ranged from 0.06–0.17 and 0.19–0.56 μg kg^–1, respectively. Based on the established method, PAH concentrations in 21 edible oils and 17 oilseeds were determined. Almost all the PAHs were found in all the samples tested, especially the light PAHs (LPAHs). Three oil samples exceeded the maximum level of 10 μg kg^–1 for BaP set by China. However, five and six oil samples, respectively, exceeded the maximum limits of 2 and 10 μg kg^–1 set for BaP and PAH4 by the European Union. The concentrations of PAH16 in oilseed samples were 1.5 times higher than corresponding oil samples. The relationships between PAH4 and PAH8, PAH4 and PAH16 as well as PAH8 and PAH16 indicates that PAH4 is a sufficient surrogate for the contamination level of PAHs in edible oils when compared with PAH8.     

Estimation of atmospheric emissions of six semivolatile polycyclic aromatic hydrocarbons in southern canada and the United States by use of an emissions processing system

Polycyclic aromatic hydrocarbons (PAHs) are toxic compounds that are ubiquitous in the atmospheric environment. The input for an emissions processing system that was originally configured forthe study of criteria air pollutants was updated to calculate emissions of six semivolatile PAHs. The goal of the work was to produce emissions estimates with the spatial and temporal resolution needed to serve as input to a regional air quality model for southern Canada and the U.S. Such modeling is helpful in determining reductions in PAH emissions that may be necessary to protect human and ecosystem health. The total annual emission of the six PAHs (sigma6PAH) for both countries was estimated at 18 273 Mg/year. A total of 90% of these emissions arise from U.S. sources. The top six source types account for 73% of emissions and are related to metal production, open burning, incineration, and forest fires. The emission factors used in this study were derived from published compilations. Although this approach has the advantage of quality control during the compilation process, some compilations include factors from older studies that may overestimate emissions since they do not account for recent improvements in emission control technology. When compared to estimates published in the National Emissions Inventory (NEI) for 2002, the U.S. emissions in this study are higher by a factor of 4 (16 424 vs 4102 Mg/year). The cause of this difference has been investigated, and much of it is likely due to our use of data unavailable in the 2002 NEI but inferred here on the basis of the PAH emissions literature. Augmenting the 2002 NEI with this additional information would bring its reported annual emissions to 8213 Mg/year, which is within a factor of 2 of the estimates herein. The results presented for southern Canada are the first published values for all known PAH sources in that country.     

Assessing sequestration of selected polycyclic aromatic hydrocarbons by use of adsorption modeling and temperature-programmed desorption

Sequestration of phenanthrene and pyrene was investigated in two soils--a sandy soil designated SBS and a silt-loam designated LHS--by combining long-term batch sorption studies with thermal desorption and pyrolysis of amended soil samples. The Polanyi-based adsorption volume and the adsorbed solute mass increased with aging for both soils, thus demonstrating the mechanism for observed sequestration. Despite rigorous thermal analysis, 30-62% (SBS sand) and 8-30% (LHS silt-loam) of phenanthrene could not be recovered after 30-270 days of sorption, with the increase in desorption resistance showing greater significance in SBS sand. For both soils, these values were 20-65% of adsorbed phenanthrene mass. Activation energies estimated from the temperature-programmed desorption (TPD) of sorbed phenanthrene at < or = 375 degrees C were 51-53 kJ/mol, consistent with values derived for desorption of organic compounds from humic materials. The activated first-order model fitting of observed TPD data supports the conclusion that the desorption-resistant fraction of phenanthrene has become sequestered onto condensed organic domains and requires temperatures exceeding 600 degrees C to be released. The work demonstrates the use of thermal analysis in complementing the Polanyi-based adsorption modeling approach for assessing the mechanistic basis for sequestration of organic contaminants in soils.     

Calibration of a passive sampler for both gaseous and particulate phase polycyclic aromatic hydrocarbons

A novel passive air sampler was designed and tested that individually collects the gaseous and particulate phase polycyclic aromatic hydrocarbons (PAHs) in air. The sampler was calibrated against a conventional active sampler in an indoor environment. A PUF (polyurethane foam) disk and a piece of GFF (glass fiber filter) were installed in a sampling shelter for collecting gaseous and particulate phase PAHs, respectively. The passive samplers were deployed in seven indoor locations for 86 days. Six times during this period, 24-h conventional active sampling was conducted for calibration at an average interval of 17-days. Principle component analysis showed that the measured congener profile compositions were totally different between the gaseous and particulate phase PAHs, but similar between the passive and the active samples. This suggested that gaseous and particulate phase PAHs were primarily trapped by the PUF disk and GFF, respectively. Linear relationships between the passively and the actively measured and log-transformed concentrations were derived for calibration of both gaseous and particulate phase PAHs. The uptake rates of the sampler were 0.10 +/- 0.014 m3/d and 0.007 +/- 0.001 m3/d for gaseous and particulate phase PAHs, respectively. The rates were significantly lower than those reported in the literature using similar PUF samplers, mainly because of the special design with limited air circulation.     

GPC结合GC-MS/MS法快速测定植物油中多环芳烃

建立了凝胶渗透色谱（GPC）前处理技术结合气相色谱-串联质谱法（GC-MS/MS）检测植物油中16种多环芳烃含量的方法。结果表明：（1）添加16种多环芳烃的大豆油样品上GPC净化时其流出液采取分段收集的方法进行测定,0～19 min的流出液为油脂类杂质,19～28 min的流出液为前十种小分子量多环芳烃,28～36 min的流出液为后六种大分子量多环芳烃,说明凝胶渗透色谱并不是严格按照分子量大先出峰分子量小后出峰的顺序,在分离多种化合物时应该采用分段收集分段测定的方法才能保证结果的准确性;（2）与GB/T 23213—2008中前处理方法相比,通过将样品量从4 g减少到1 g,使用环己烷乙酸乙酯（1+1）溶解后直接上GPC净化的方法,减少了提取过程,缩短了实验时间,节约了提取试剂,避免了提取过程中可能造成的含量损失;（3）植物油中16种多环芳烃在GC-MS/MS上色谱峰响应值与其质量浓度（10～200ng/mL）之间线性关系良好,相关系数超过0.99,检出限范围是0.02～0.50μg/kg,定量限范围是0.08～1.67μg/kg;(4)在16种多环芳烃标液添加水平为20μL、40μ...     

气相色谱-质谱法测定肉松、鱼干中的多环芳烃

采用正己烷-二氯甲烷(v正己烷:v二氯甲烷=1:1)索氏提取、硅胶柱净化技术,用气相色谱-质谱(GC/MS)的分段选择性离子监测(SIM)对肉松、鱼干中多环芳烃(PAHs)进行定性定量分析.通过优化19种PAHs的分离条件,采用SIM法可实现肉松、鱼干中19种PAHs的同时测定,19种多环芳烃的检出限为0.02～1.28 ng/mL.该法灵敏准确,适合于肉松、鱼干等食品中多环芳烃含量的测定.     

Removal of polycyclic aromatic hydrocarbons by low density polyethylene from liquid model and roasted meat

Low density polyethylene (LDPE) was used to remove polycyclic aromatic hydrocarbons (PAHs) from liquid media and roasted meat by sorption. Three liquid models and five carcinogenic PAHs were employed to monitor the sorption process, and amounts of chemicals were determined by GC-FID. More than 50% of the total adsorption occurred within 24 h for the selected PAHs in the three model systems. The water–oil system yielded the highest PAHs removal by LDPE; and the system containing phospholipid resisted the diffusion and resulted in the least adsorption among three models. Certain residual PAHs in the LDPE were significantly decreased to a range of 70.8–84.0% after 3 h of UV radiation, and benzo(a)pyrene was the most sensitive to UV among these PAHs. Removal of PAHs in roasted meat packaged under vacuum was achieved, and potent contamination by the PAHs in the LDPE may be avoided by subsequent UV irradiation.     

Demonstration of a method for the direct determination of polycyclic aromatic hydrocarbons in submerged sediments

We describe the development of a novel method for real-time in situ characterization of polycyclic aromatic hydrocarbons (PAHs) in submerged freshwater sediments. Laser-induced fluorescence (LIF) spectroscopy, a mature technique for PAH characterization in terrestrial sediments, was adapted for shipboard use. A cone penetrometer-type apparatus was designed for probe penetration at a constant rate (1 cm/s) to a depth of 3 m. A field-portable LIF system was used for in situ measurements in which the output of a pulsed excimer laser was transmitted by optical fiber to a sapphire window (6.4-mm o.d.) in the probe wall; fluorescent emission was collected by a separate optical fiber for transmission to the spectrometer on deck. Four wavelengths (340, 390, 440, 490 nm) were selected via optical delay lines, and multiple-wavelength waveforms were created. These multiple-wavelength waveforms contain information on the fluorescence frequency, intensity, and emission decay rate. Field testing was conducted at 10 sites in Milwaukee Harbor (total PAH concentrations ranged from approximately 10 to 650 microg/g); conventional sediment core samples were collected concurrently. The core samples were analyzed by EPA methods 3545 (pressurized fluid extraction, PFE) and 8270C (gas chromatography-mass spectrometry, GC-MS) for PAHs. A partial least-squares regression (PLSR) model wasthen created based on laboratory LIF measurements and PFE-GC-MS of the core samples. The PLSR model was applied to the in situ field test data, and 13 of the 16 EPA-regulated PAHs were quantified with a relative error of <30% overall (the remaining three PAHs were found at levels insufficient to quantify). We additionally describe preliminary source apportionment relationships that were revealed by the PLSR model for the in situ LIF measurements.     

Review of the quantification techniques for polycyclic aromatic hydrocarbons (PAHs) in food products

There is a growing need for accurate detection of trace-level PAHs in food products due to the numerous detrimental effects caused by their contamination (e.g., toxicity, carcinogenicity, and teratogenicity). This review aims to discuss the up-to-date knowledge on the measurement techniques available for PAHs contained in food or its related products. This article aims to provide a comprehensive outline on the measurement techniques of PAHs in food to help reduce their deleterious impacts on human health based on the accurate quantification. The main part of this review is dedicated to the opportunities and practical options for the treatment of various food samples and for accurate quantification of PAHs contained in those samples. Basic information regarding all available analytical measurement techniques for PAHs in food samples is also evaluated with respect to their performance in terms of quality assurance.