Determination (monitoring) of PAHs in surface waters: why an operationally defined procedure is needed

The results of interlaboratory studies on the determination of selected PAHs in samples of pure water and water containing suspended matter are presented and discussed in this study. Determinations were performed by independent analytical laboratories which used different sample-preparation procedures, i.e. liquid-liquid extraction and solid-phase extraction with columns and speedisks. The study indicates that the results of PAHs determination depend on the type of isolation technique and the final determination procedure used by a given laboratory. Differences among the determined concentrations of specific PAHs reached 700%. In this work it has been shown that modern analysis does not offer isolation techniques for PAHs which would secure their speciation in the aquatic environment.     

Sample preparation and analytical methods for polycyclic aromatic hydrocarbons in sediment

Polycyclic aromatic hydrocarbons (PAHs) are a large category of ubiquitous persistent environmental pollutants, some of them have strong carcinogenicity to human and animals. These pollutants can easily enter the river through multiple ways including rainfall, dry deposition and water washout, and deposit in the sediment. However, it is easy for them to re-enter the river water and pollute water sources, as well as aquatic animals and plants, bringing potential harm to human health. Therefore, it is requisite to accurately analyze the PAHs in sediment. In this review, the analytical methods of PAHs in sediment, focused on the methods of sample extraction, purification, concentration and determination, are summarized.     

The Application of Active Biomonitoring with the Use of Mosses to Identify Polycyclic Aromatic Hydrocarbons in an Atmospheric Aerosol

The use of biological indicators of environmental quality is an alternative method of monitoring ecosystem pollution. Various groups of contaminants, including organic ones, can be measured in environmental samples. Polycyclic aromatic hydrocarbons (PAHs) have not yet been determined by the moss bag technique. This technique uses several moss species simultaneously in urban areas to select the best biomonitoring of these compounds, which are dangerous to humans and the environment. In this research, a gas chromatography coupled with mass spectrometry was used for the determination of selected PAHs in three species of mosses: Pleurozium schreberi, Sphagnum fallax and Dicranum polysetum (active biomonitoring) and for comparison using an air filter reference method for atmospheric aerosol monitoring. The chlorophyll fluorescence of photosystem II (PSII) was also measured to assess changes in moss viability during the study. As a result of the study, the selective accumulation of selected PAHs by mosses was found, with Pleurozium schreberi being the best bioindicator—9 out of 13 PAHs compounds were determined in this species. The photosynthetic yield of photosystem (II) decreased by 81% during the exposure time. The relationship between PAHs concentrations in mosses and the total suspended particles (TSP) on the filter indicated the possibility of using this bioindicator to trace PAHs in urban areas and to apply the moss bag technique as a method supporting classical instrumental air monitoring.     

同步荧光法检测鱼胆汁中的1-羟基芘

建立了和同步荧光法测定鱼胆汁的1－羟基芘（1－HP）的方法。该方法通过直接测定鱼胆汁的多环芳烃（PAHs)的代谢产物之一1－HP，用于判断PAHs生物有效部分对海岸养殖水环境的污染程度。以真鲷（Pargrosomus major，简称Pm），Mian鱼（Niba miichthys，简称Nm）为实验对象，现场实验结果令人满意。     

Determination of polycyclic aromatic hydrocarbons in sediment by liquid chromatography-atmospheric pressure photoionization-mass spectrometry.

We describe a method for the simultaneous determination of 12 kinds of polycyclic aromatic hydrocarbons (PAHs) in sediment based on liquid chromatography-atmospheric pressure photoionization-mass spectrometry (LC/APPI/MS). The method consists of PAH extractions by ultrasonics, clean-up by a solid-phase extraction procedure and determination by LC/APPI/MS. The limits of the determination for PAHs in sediment using the proposed method ranged from 0.06 to 0.9 mg/kg. PAHs were detected by this method in sediment samples on the mg/kg level.     

The effect of adding a standard on the result of determination of polychlorinated biphenyls in bottom sediment samples

Bottom sediments are a very important component of aquatic ecosystems. The sediment matrix is highly diverse and heterogeneous; in consequence, compounds entering the aquatic environment from different sources are considerably enriched at its surface. Bottom sediments are regarded as natural sorbents, since they accumulate many harmful substances, such as heavy metals and stable organic contaminants.Extraction is a key stage in every analytical procedure. It is during this stage that standards are added to samples. Standards are necessary not only for estimating analyte yields but also for validating the whole procedure. The question of the addition of standard substances to sediment samples has not been widely addressed in the subject literature, and yet it is of fundamental importance as regards obtaining reliable results of determinations.This paper describes the results of a study on the effect of standard addition techniques on the results of determination of polychlorinated biphenyls in sediment samples (certified reference material: METRANAL™2—river sediment).     

Determination of trace PAHs in seawater and sediment pore-water by solid-phase microextraction (SPME) coupled with GC/MS

A fast and reliable method for the determination of trace PAHs (polynuclear aromatic hydrocarbons) in seawater by solid-phase microextraction (SPME) followed by gas chromatographic (GC) analysis has been developed. The SPME operational parameters have been optimized, and the effects of salinity and dissolved organic matter (DOM) on PAHs recoveries have been investigated. SPME measures only the portion of PAHs which are water soluble, and can be used to quantify PAH partition coefficient between water and DOM phases. The detection limits of the overall method for the measurement of sixteen PAHs range from 0.1 to 3.5 ng/g, and the precisions of individual PAH measurements range from 4% to 23% RSD. The average recovery for PAHs is 88.2±20.4%. The method has been applied to the determination of PAHs in seawater and sediment porewater samples collected in Jiaozhou Bay and Laizhou Bay in Shandong Peninsula, China. The overall levels of PAHs in these samples reflect moderate pollution compared to seawater samples reported elsewhere. The PAH distribution pattern shows that the soluble PAHs in seawater and porewater samples are dominated by naphthalenes and 3 ring PAHs. This is in direct contrast to those of the sediment samples reported earlier, in which both light and heavy PAHs are present at comparable concentrations. The absence of heavy PAHs in soluble forms (<0.1-3.5 ng/L) is indicative of the strong binding of these PAHs to the dissolved or solid matters and their low seawater solubility.     

Biomonitoring: an appealing tool for assessment of metal pollution in the aquatic ecosystem

Wide occurrence of aquatic metal pollution has caused much attention. Biomonitoring offers an appealing tool for the assessment of metal pollution in aquatic ecosystem. The bioindicators including algae, macrophyte, zooplankton, insect, bivalve mollusks, gastropod, fish, amphibian and others are enumerated and compared for their advantages and disadvantages in practical biomonitoring of aquatic metal pollution. The common biomonitoring techniques classified as bioaccumulation, biochemical alterations, morphological and behavior observation, population- and community-level approaches and modeling are discussed. The potential applications of biomonitoring are proposed to mainly include evaluation of actual aquatic metal pollution, bioremediation, toxicology prediction and researches on toxicological mechanism. Further perspectives are made for the biomonitoring of metal pollution in aquatic ecosystem.     

Two new marine sediment standard reference materials (SRMs) for the determination of organic contaminants

Two new marine sediment standard reference materials (SRMs), SRM 1941b Organics in Marine Sediment and SRM 1944 New York/New Jersey Waterway Sediment, have been recently issued by the National Institute of Standards and Technology (NIST) for the determination of organic contaminants including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyl (PCB) congeners, and chlorinated pesticides. Both sediment SRMs were analyzed using multiple analytical methods including gas chromatography/mass spectrometry (GC/MS) on columns with different selectivity, reversed-phase liquid chromatography with fluorescence detection (for PAHs only), and GC with electron capture detection (for PCBs and pesticides only). SRM 1941b has certified concentrations for 24 PAHs, 29 PCB congeners, and 7 pesticides, and SRM 1944 has certified concentrations for 24 PAHs, 29 PCB congeners, and 4 pesticides. Reference concentrations are also provided for an additional 58 (SRM 1941b) and 39 (SRM 1944) PAHs, PCB congeners, and pesticides. SRM 1944, which was collected from multiple sites within New York/New Jersey coastal waterways, has contaminant concentrations that are generally a factor of 10–20 greater than SRM 1941b, which was collected in the Baltimore (Maryland) harbor. These two SRMs represent the most extensively characterized marine sediment certified reference materials available for the determination of organic contaminants.Electronic Supplementary Material Supplementary material is available in the online version of this article at . A link in the frame on the left on that page takes you directly to the supplementary material.     

Screening for pharmaceutical transformation products formed in river sediment by combining ultrahigh performance liquid chromatography/high resolution mass spectrometry with a rapid data-processing method

While the occurrence of pharmaceuticals in the aquatic environment has been extensively investigated, their environmental fate is less thoroughly explored. Scarce information on their transformation pathways and transformation products (TPs) limits conventional target analytical approaches. In this study, samples from water/sediment tests were analyzed by ultrahigh performance liquid chromatography interfaced with quadrupole time-of-flight mass spectrometry (UHPLC/QToF-MS). A data processing method based on peak detection, time-trend filtration and structure assignment was established to provide an efficient way for identifying the key TPs in terms of persistence; all software used for the individual steps of this method is freely available. The accurate mass and meaningful time-trends were major contributors in facilitating the isolation of plausible TP peaks. In total, 16 TPs from 9 parent pharmaceuticals were identified. Eleven out of the 16 TPs were confirmed by corresponding reference standards; no standards were available for the remaining TPs. For additional 6 potential TPs, a molecular formula was suggested but no additional structural information could be generated. Among the TPs identified in the water/sediment tests, carbamazepine-10,11-epoxide (parent: carbamazepine), saluamine (parent: furosemide), chlorothiazide and 4-amino-6-chloro-1,3-benzenedisulfonamide (parent of both: hydrochlorothiazide), and 1-naphthol (parent: propranolol) accumulated over the entire incubation period of 35 days.     

Multifactorial optimization approach for the determination of polycyclic aromatic hydrocarbons in river sediments by gas chromatography-quadrupole ion trap selected ion storage mass spectrometry

A procedure for the determination of very low polycyclic aromatic hydrocarbons (PAHs) concentrations in sediment samples has been developed by gas chromatography-quadrupole ion trap mass spectrometry (GC-QIT MS) after extraction with dichloromethane and purification by using silica gel cleanup. Identification and quantification of analytes were based on the selected ion storage (SIS) strategy using deuterated PAHs as internal standards. In order to search out the main factors affecting the SIS mass spectrometry efficiency, four MS parameters, including target total ion count (TTIC), waveform amplitude (WA), transfer line (XLT) and ion trap temperatures (ITT) were subjected to a complete multifactorial design. The most relevant parameters obtained (TTIC and WA) were optimized by a rotatable and orthogonal composite design. Optimum values for these parameters were selected for the development of the method involving PAH determination in sediment samples. The optimized method exhibited a range of 111-760% higher signal-to-noise (S/N) ratios for PAHs in comparison with the method operated by the default conditions, demonstrating that the multifactorial optimization contributed to substantially improve the sensitivity of the GC-QIT MS determination. The accuracy of the method was verified by analyzing NWRI EC-3 certified reference material (Lake Ontario sediment). The selectivity, sensitivity (limits of quantification were in the range of 0.02-11.0 ng g(-1)), accuracy (recoveries >or=77%) and precision (RSD相似文献   

Determination of semi-volatile priority pollutants in landfill leachates and sediments using microwave-assisted headspace solid-phase microextraction

The present work was focused on the development of a simple method aimed at the determination of 12 polycyclic aromatic hydrocarbons (PAHs) and 15 polychlorinated biphenyls (PCBs) in landfill leachates and sediments by adapting a domestic microwave oven to perform microwave-assisted headspace solid-phase microextraction (MA-HS-SPME) followed by gas chromatographic separation and tandem mass spectrometric detection. Good linearity was observed within the concentration range studied; detection limits ranged from 0.1 ng/l to 7 ng/l for PCBs and from 5 ng/l to 926 ng/l for PAHs. Concerning precision, the relative standard deviations obtained were, on average for the leachate and sediment samples analysed, 18% for PCBs and 20% for PAHs. Average recovery values were 37% and 76% for PCBs, and 58% and 48% for PAHs, respectively, for the leachate and reference sediment studied. The method allows the determination of PAHs and PCBs in landfill leachates and sediments, avoiding clean-up steps and the consumption of organic solvents.     

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.     

Determination of polycyclic aromatic hydrocarbons in marine sediments by high-performance liquid chromatography after microwave-assisted extraction with micellar media

A simple and rapid method is developed for extraction and determination of polycyclic aromatic hydrocarbons (PAHs) in marine sediments. The procedure was based on the microwave-assisted extraction of PAHs in marine sediment samples using a micellar medium of Polyoxyethylene 10 lauryl ether as extractant. Two-level factorial designs have been used to optimize the microwave extraction process. The analysis of extracts has been carried out by HPLC with UV detection. Fortified sediments gave an average recovery between 85.70 and 100.73%, with a relative standard deviation of 1.77-7.0% for PAHs with a ring number higher than three.     

Dynamic microwave-assisted extraction coupled on-line with solid-phase extraction: determination of polycyclic aromatic hydrocarbons in sediment and soil

This paper describes a new extraction tool for the determination of polycyclic aromatic hydrocarbons (PAHs) in soil and sediment samples, using dynamic microwave-assisted extraction combined with solid-phase extraction (DMAE-SPE). The critical variables for DMAE-SPE are investigated and optimized in an experimental design. The technique proved to be fast, accurate and able to yield quantitative extraction of PAHs from naturally contaminated sediment and soil samples. The set-up is fully automated and features monitored extraction, which facilitates rapid optimization of the method. In addition, only small quantities of solvent and sample are required.     

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。     

Shpol'skii spectrometry, a distinct method in environmental analysis

Whereas common fluorescence and phosphorescence spectra of organic molecules in solutions show little details, Shpol'skii spectra exhibit completely resolved vibronic transitions, enabling the analytical distinction between isomeric compounds. In a simplified qualification, the Shpol'skii technique combines the sensitivity inherent to luminescence spectroscopy with the selectivity of infrared spectra. There are however two main limitations as far as its applicability is concerned: (i) cryogenic temperature conditions are required and (ii) the analytes should be compatible with the solvent matrix, typically an-alkane.The present paper is focused on the potential and achievements of Shpol'skii spectrometry in environmental analysis. After a discussion of the fundamental aspects of spectral line-broadenings and the approaches to accomplish high-resolution, special attention is paid to experimental and instrumental aspects. Recent instrumental developments have made Shpol'skii spectroscopy not only attractive for qualitative but also for quantitative purposes.The main part of the review is devoted to recent applications, for instance the determination of parent polycyclic aromatic hydrocarbons (PAHs) in complex environmental samples as crude oils, sediments, soils and biota. The special features of large PAHs, i.e. PAHs with seven or more hexagonal aromatic rings are considered separately. The analysis of PAH-metabolites in samples like fish bile and human urine is extensively discussed. Subsequently the applicability of Shpol'skii spectroscopy to both in-ring and atring substituted polycyclic aromatics is concerned, including amino- and nitro-substituted PAHs and nitrogen-, oxygen- and sulphur-heterocyclic compounds. The review ends with an interesting new development i.e. the Shpol'skii spectra of fullerenes, the soccerball and rugbyball shaped molecules C₆₀ and C₇₀, compounds receiving wide attention in physics and chemistry.     

Gas chromatography–tandem mass spectrometry analysis of 52 monohydroxylated metabolites of polycyclic aromatic hydrocarbons in hairs of rats after controlled exposure

A method based on gas chromatography–tandem mass spectrometry after derivatization with N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide was developed for the analysis of monohydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) in hair. The method focused on 52 target compounds corresponding to two- to six-ring monohydroxylated metabolites of polycyclic aromatic hydrocarbons (PAHs). The limits of quantification ranged from 0.2 to 50 pg mg^?1. The method was then applied to the analysis of hair samples collected from rats exposed to 12 PAHs at 0.01, 0.1, and 1 mg kg^?1, by intraperitoneal injection, for 28 days. The results of this study confirm that these metabolites can be incorporated in hair after intraperitoneal administration of the corresponding parent compound. Only 20 of the 52 metabolites were actually detected in hair samples and corresponded to nine parent PAHs. The mean concentrations of OH-PAHs in rat hair samples exposed to PAHs at 1 mg kg^?1 ranged from 0.6?±?0.2 pg mg^?1 for 8-hydroxybenzo[b]fluoranthene to 6.7?±?1.0 pg mg^?1 for 1-hydroxypyrene. The results also demonstrated that hair pigmentation has no influence on the concentration of most OH-PAHs. This animal experiment confirmed the incorporation of PAH metabolites in hair and demonstrated that the method was sufficiently sensitive to detect low levels of exposure to PAHs. These results confirmed the usefulness of hair analysis in the biomonitoring of human exposure to PAHs.

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.     

Identification of Phototoxic Polycyclic Aromatic Hydrocarbons in Sediments Through Sample Fractionation and QSAR Analysis

Abstract

The toxicity of certain polycyclic aromatic hydrocarbons (PAHs) can be greatly increased by simultaneous exposure of test organisms to ultraviolet (UV) wavelengths present in sunlight. This phenomenon, commonly termed photoinduced toxicity, had been evaluated extensively in laboratory settings where only one chemical of concern was present. However, more recent studies have demonstrated that complex mixtures of PAHs present, for example in sediments, also can cause phototoxicity to a variety of aquatic species when the samples are tested in simulated sunlight. Unfortunately, because these types of samples can contain thousands of substituted and unsubstituted PAHs it is difficult, if not impossible, to use conventional analytical techniques to identify those responsible for photoinduced toxicity. The objective of the present study was to link two powerful ecotoxicology tools, toxicity-based fractionation techniques and QSAR models, to identify phototoxic chemicals in a sediment contaminated with PAHs emanating from an oil refinery. Extensive chromatographic fractionation of pore water from the sediment, in conjunction with toxicity testing, yielded a simplified set of sample fractions containing 12 PAHs that were identified via mass spectroscopy. Evaluation of these compounds using a recently developed QSAR model revealed that, based upon their HOMO-LUMO gap energies, about half were capable of producing photoinduced toxicity. We further evaluated the phototoxic potential of the reduced set of PAHs by determining their propensity to bioaccumulate in test organisms, through calculation of octanol-water partition coefficients for the chemicals. These studies represent a novel linkage of sample fractionation methods with QSAR models for conducting an ecological risk assessment.