Priority Pollutant List Research Articles

A sensitive liquid chromatography/tandem mass spectrometry method for the determination of natural and synthetic steroid estrogens in seawater and marine biota, with a focus on proposed Water Framework Directive Environmental Quality Standards

Trace levels of natural and synthetic steroid estrogens estrone (E1), 17β-estradiol (E2) and 17α-ethynyl estradiol (EE2) have been demonstrated to exert adverse effects in exposed organisms. E2 and EE2 have been proposed for inclusion in the Water Framework Directive (WFD) list of priority pollutants; however, the detection and accurate quantification of these compounds provide significant challenges, due to the low detection limits required. A sensitive method combining ultrasonication, solid-phase extraction (SPE) and liquid chromatography/tandem mass spectrometry, with electrospray ionisation in negative mode (LC/ESI-MS/MS), capable of determining E1, E2 and EE2 at concentrations between 0.07 and 60 ng/L for seawater and between 0.4 and 200 ng/g wet weight in Mytilus spp. is reported. Recoveries at the limit of quantification (LOQ) ranged from 95 to 102% and 88 to 100% for water and tissue, respectively. Salinity (12 to 35‰) and typical marine particulate matter loadings (between 10 and 100 mg/L) were not found to affect analyte recoveries. The first detection of E1 by LC/MS/MS in Irish marine waters (Dublin Bay, at 0.76 ng/L) is reported. Steroids were not detected in Galway Bay, or in any mussel samples from Dublin, Galway and Clare. The level of E2 detected in the dissolved water phase was below the proposed WFD Environmental Quality Standard (EQS) in other surface waters. The proposed method is suitable for the detection of E1, E2 and EE2 at biologically relevant concentrations and, due to the specificity offered, is not subject to potential interferences from endogenous E1 and E2 which often complicate the interpretation of estrogenic biomarker assays.

Source identification of polycyclic aromatic hydrocarbons in sediments of a creek around a flow station

Sources of the sixteen polycyclic aromatic hydrocarbons (PAHs) in the United States Environmental Protection Agency priority pollutants list were determined in sediments of Kolo Creek using diagnostic ratios of parent PAHs(phenanthrene/phenanthrene ? anthracene; fluoranthene/fluoranthene ? pyrene; benz(a) anthracene/ benz(a) anthracene ? chrysene and indeno(1,2,3-d)pyrene/ indeno(1,2,3-cd)pyrene ? benzo(ghi)pyrelene). The study was conducted over four seasons (dry, late dry, rainy and late rainy seasons). Applying cross plots of the diagnostic ratios revealed that PAHs in Kolo Creek sediment have pyrogenic origins except in the rainy season that had pe- trogenic origins. Comparison of diagnostic ratio values obtained from this study with literature values enabled the further classification into types of pyrogenic and/or petro- genic sources. While the pyrogenic sources of PAHs were mainly as a result of Grass/Wood combustion, the petro- genic PAHs were as result of drained diesel and lubricating oil. The predicted sources corresponded with the prevailing human activities in the vicinity, especially samples col- lected near a petrol station and an abattoir. This study further affirms the simplicity and accuracy of the use of diagnostic ratios for PAHs source prediction.

Numerical Simulation of the Acenaphthylene Compound in an Atmospheric Plasma Reactor to Treat Cooking Fumes

Acenaphthylene (chemical formula of C12H8, Acpy), also known as cyclopenta[de]naphthalene, is a polycyclic aromatic hydrocarbon (PAH) with 3 aromatic rings. The Acpy compound is a PAH on the Environmental Protection Agency's (EPA's) priority pollutant list. This study presents a simulation of an atmospheric plasma reactor (APR) using a method based on computational fluid dynamics (CFD). A commercial CFD tool was used to solve mass, momentum, and energy equations. The commercial FLUENT code was then used to simulate the Acpy compound using a 3D APR to treat the cooking fume exhaust emitted from a restaurant kitchen. The simulations in this study adopted the APR size and operating parameters from a self-designed atmospheric plasma reactor in a previous study (NSC95-2221-E020-021). An in-house reduced chemical mechanism was coupled with the CFD code for improved computational runtime. The reactivity of the system was considered with the RNG k-ε turbulence model and the classical Eddy Dissipation Concept combustion model. The simulation results were compared with the experimental temperature measurement and the removal efficiency of Acpy. The simulated average removal efficiency of Acpy was 61.3%.

The application of passive sampler (DGT) technology for improved understanding of metal behaviour at a marine disposal site

Metal behaviour and availability at a contaminated dredge material disposal site within UK waters has been investigated using Diffusive Gradient in Thin films (DGT) passive sampling technology. Three stations representing contrasting history and presence of maintenance dredge disposal, including a control station outside the disposal site, have been studied and depth profiles of fluxes of different metals (Fe, Mn, Pb, Cu, Cd, Cr, Ni, Zn) to the binding gel (Chelex 100) have been derived. Higher flux rates and shallower mobilisation of metals (Mn and Fe) to the binding gel were observed at the disposal stations compared to the control station. Here we describe metal mobilization at different depths, linking the remobilization of Fe 2+ and Mn 2+ to the sediment (re)supply of other heavy metals of interest with a focus on Cd, Ni and Pb and as they are on the Water Framework Directive (WFD) list of priority substances and OSPAR list of priority pollutants. Results showed that Cd, Pb and Ni exhibited signs of resupply at the sediment-water interface (SWI). There was a potential increased mobilisation and source to the water column of Pb and Ni at the disposal site stations, but there was no Cd source, despite higher total loadings. This information has the potential to improve our current understanding of metal cycles at disposal sites. This work can be used as an indication of likely metal bioavailability and also assist in determining whether the sites act as sources or sinks of heavy metals. This information could assist disposal site monitoring and dredge material licensing.

Estimation of contamination of atmosphere of Moscow in winter

To establish the priority pollutants in the atmosphere of Moscow in winter 8 snow samples were collected along the perimeter (109 km) of the Moscow Ring Road. Mass spectrometry was used as an analytical tool to identify individual organic compounds (gas chromatography/mass spectrometry) and the most environmentally relevant chemical elements (inductively coupled plasma with mass spectrometric detection). As a result several hundred organic compounds belonging to various classes, including representatives of the list of priority pollutants of the USA Environmental Protection Agency were identified. Their levels as well as the levels of chemical elements were quantified. The importance of accurate mass measurements for the efficient structural elucidation and reliability of quantitative measurements has been demonstrated. The data obtained allow estimating atmospheric pollution in Moscow in the period between December and March and proposing a list of priority pollutants for the atmosphere of Moscow.

Feasibility of the determination of polycyclic aromatic hydrocarbons in edible oils via unfolded partial least-squares/residual bilinearization and parallel factor analysis of fluorescence excitation emission matrices

The possibility of simultaneously determining seven concerned heavy polycyclic aromatic hydrocarbons (PAHs) of the US-EPA priority pollutant list, in extra virgin olive and sunflower oils was examined using unfolded partial least-squares with residual bilinearization (U-PLS/RBL) and parallel factor analysis (PARAFAC). Both of these methods were applied to fluorescence excitation emission matrices. The compounds studied were benzo[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenz[a,h]anthracene, benzo[g,h,i]perylene and indeno[1,2,3-c,d]-pyrene. The analysis was performed using fluorescence spectroscopy after a microwave assisted liquid–liquid extraction and solid-phase extraction on silica. The U-PLS/RBL algorithm exhibited the best performance for resolving the heavy PAH mixture in the presence of both the highly complex oil matrix and other unpredicted PAHs of the US-EPA list. The obtained limit of detection for the proposed method ranged from 0.07 to 2μgkg−1. The predicted U-PLS/RBL concentrations were satisfactorily compared with those obtained using high-performance liquid chromatography with fluorescence detection. A simple analysis with a considerable reduction in time and solvent consumption in comparison with chromatography are the principal advantages of the proposed method.

Distribution, toxicity level, and concentration of polycyclic aromatic hydrocarbons (PAHs) in surface soil and groundwater of Rawalpindi, Pakistan

In this study, the distribution, toxicity level, and relationship of polycyclic aromatic hydrocarbons (PAHs) with total organic content (TOC) have been investigated using surface soil and ground water samples from an area adjacent to petrochemical plant in Pakistan. Six PAHs, naphthalene, acenaphthene, phenanthrene, anthracene, flouranthene, and chrysene, were selected from the 16 Environment Protection Agency priority pollutants list. ΣPAHs range from 2,700 to 4,443 μg/g (average: 3,672 ± 592 μg/g) in soil and 201–1,634 ng/L (average: 763 ± 377 ng/L) in water. The compositional profile of PAHs revealed that low molecular weight 3–4 ring PAHs were predominant. The ratios of phenanthrene/anthracene reflected the pyrogenic origin of PAHs. The relationship of PAHs with TOC has also been investigated and a positive correlation was observed between ΣPAHs and TOC. This indicates that partitioned in organic matter may be the possible source of PAHs in water. An assessment using widely cited guidelines indicates that water samples do not pose biological impact, while soil can pose a threat of lung cancer.

Persistent toxic substances in surface water of Todos Os Santos Bay, Brazil

Persistent toxic substances (PTSs) such as polycyclic aromatic hydrocarbons (PAHs) are of great concern due to their persistence, bioaccumulation and toxic effects. In this work, 14 PAHs included in the US Environmental Protection Agency’s (EPA) priority pollutant list were analysed using gas chromatography–mass spectrometry (GC–MS). Surface water sampling was undertaken in Todos os Santos Bay, northern Brazil. Total PAH concentrations varied from 0.0029 to 0.1079 ng/L in surface waters (main rivers, tributaries, etc.) with mean value of 0.0344 ng/L. Such concentrations can be taken as background values for the studied region and show that PAHs are within or lower than levels reported in certain other areas. The PAH profiles were dominated by high molecular weight PAHs (four- and five-ring components) in surface water samples. It indicated that PAHs in surface water have its origin from oil or sewage contamination (petrogenic input). The collected data, based on indices among phenanthrene versus anthracene, showed that petrogenic input was predominant at almost all the stations investigated. Principal component analysis (PCA), using a correlation matrix, revealed the latent relationships among all the surface water stations investigated and confirmed our analytical results.

A method based on microextraction by packed sorbent-programmed temperature vaporizer–fast gas chromatography–mass spectrometry for the determination of aromatic amines in environmental water samples

We report a sensitive method for the determination of 15 aromatic amines in environmental water samples. They have been included in the list of priority pollutants in surface water by the European Union. The method is based on analyte enrichment using microextraction by packed sorbent (MEPS) and later analysis using programmed temperature vaporizer-gas chromatography-mass spectrometry (PTV-GC-MS). All MEPS steps were carried out manually. The detection limits were of the order of nanograms per liter for most of the compounds. The results were compared with those obtained without MEPS using the method exclusively based on direct injection of the sample into the PTV-GC-MS. External calibration in ultrapure water was used in the determination of the compounds studied in five types of water samples (sea, river, tap, influent, and effluent waste water) since no significant matrix effect was found. The results obtained can be considered highly satisfactory and they revealed the presence of aniline in the sea and the influent and effluent waste water samples.

Determination of Polycyclic Aromatic Hydrocarbons in Industrial Harbor Sediments by GC-MS

Analysis of the 16 polycyclic aromatic hydrocarbons (PAHs) of the US Environmental Protection Agency priority pollutant list was carried out in sediment samples of an industrial port in the southern Kaohsiung Harbor of Taiwan which is supposed to be extensively polluted by industrial wastewater discharges. The determination and quantification of PAHs in sediment samples were performed using gas chromatography coupled to mass spectrometry (GC-MS) with the aid of deuterated PAH internal standards and surrogate standards. The total concentrations of the 16 PAHs varied from 4,425 to 51,261 ng/g dw, with a mean concentration of 13,196 ng/g dw. The PAHs concentration is relatively high in the river mouth region, and gradually diminishes toward the harbor region. Diagnostic ratios showed that the possible source of PAHs in the industrial port area could be coal combustion. As compared with the US Sediment Quality Guidelines (SQGs), the various observed levels of PAHs exceeded the effects range median (ERM), and could thus cause acute biological damages. The results can be used for regular monitoring, and future pollution prevention and management should target the various industries in this region for reducing pollution.

Comparison of BEA, USY and ZSM-5 for the quantitative extraction of polycyclic aromatic hydrocarbons from water samples

The physicochemical properties of three commercial zeolites – namely BEA, USY and ZSM-5 – are compared for the water removal of 15 PAHs included in the US EPA priority pollutants list. The best percentages of extraction were obtained with BEA and varied from 85.2 ± 1.7% (benzo[ g, h, i]perylene) to 99.6 ± 1.1% (pyrene). The correlation of physicochemical properties to the percentages of extraction suggests that the predominant factor for a successful extracting performance is the adsorption of PAHs to the external surface of the extracting material. This process is facilitated by relatively large total pore volumes, large average pore diameters and a homogeneous distribution of Lewis acid sites. The presence of the latter enhances extraction performance via π-electron interactions with the aromatic rings of the PAH.

Olympic Win: Lower Estimated Cancer Risk with Air Pollution Controls during the 2008 Beijing Games

Polycyclic aromatic hydrocarbons (PAHs) sorbed to fine atmospheric particulate matter (PM2.5) increase inhalation cancer risk in exposed populations. In China each year, an estimated 6.5 people per million develop lung cancer due to PAH inhalation. But stringent air pollution control measures instituted during the 2008 Olympic Games in Beijing, if sustained over a lifetime, could reduce residents’ PAH-related inhalation cancer risk by nearly half [EHP 119(6):815–820; Jia et al.]. Coal combustion and motor vehicle emissions create severe air pollution in Beijing and other major Chinese cities. To improve air quality for the Olympic Games, factories in and around Beijing were moved or closed, vehicular traffic was restricted, and truck traffic was reduced during the period 20 July–20 September 2008. During the games themselves (8–24 August), even stricter controls were imposed. PM2.5 samples were collected at a single representative location in Beijing, and associated concentrations of 17 PAHs were measured and compared for four periods: 1) 28 July–20 September versus 2) 21 September–7 October, and 3) 8–24 August versus 4) 28 July–7 August/25 August–7 October. To enable direct comparison of chemical risks, a benzo[a]pyrene equivalent (BaPeq) concentration was estimated for each PAH by multiplying its concentration by its relative potency factor (RPF). Cancer risk was calculated using the BaPeq values paired with previously established unit risk measures for cancer based on a lifetime (70 years) of BaP exposure at 1 μg/m3 air. Individual BaPeq concentrations were 22–78% lower in period 1 compared with period 2 (i.e., when any pollution controls were in place) and 32–72% lower in period 3 compared with period 4 (i.e., when the strictest controls were in place). Lifetime excess inhalation cancer cases estimated during the period when pollution was controlled ranged from 6.5 to 518 individuals per million compared with a range of 12.2–964 per million after pollution controls ceased—a 46% reduction. PAHs from the U.S. Environmental Protection Agency’s list of priority pollutants made up three of the four largest contributors to total carcinogenicity; however, high-molecular-weight PAHs—a highly carcinogenic group of chemicals that, as a class, haven’t been extensively studied—contributed a considerable 23% of the cancer risk. These top four PAHs are primarily associated with PM2.5, so reducing PM2.5 emissions would also reduce levels of these and other PAHs. Limitations of the study include potential inaccuracies due to its point-estimate approach, which assumes additive cancer risk, and the RPF values, which were based on toxicologic studies with their own uncertainties. However, the study strongly supports the effectiveness of air pollution source control measures and also demonstrated the need to include high-molecular-weight PAHs in future studies.

On-line SPE-HPLC Method using Alumina Filtering to Selectively Extract Phenolic Compounds from Environmental Water

A on-line SPE (solid phase extraction)-HPLC preconcentration method was developed for the determination of phenolic compounds at trace levels in environmental water sample. XAD-4 and Dowex 1-X8 were used as sorbent in the on-line SPE-HPLC method for the selective enrichment of nine phenolic compounds, which are included in the priority pollutants list of the US EPA. Also alumina prefiltering considerably reduced the amount of interfering peaks due to humic substances that could accumulated due to the preconcentration step and prevent quantification of polar phenolic compounds in environmental water samples. This method was used to determine the phenolic compounds in tap and river water and superiority to the US EPA 625 method in its enrichment factor, pretreatment time, recoveries, and detection limit. The limits of detection were in the range of <TEX>$0.3-0.9\;{\mu}g/L$</TEX> in tap water sample.

Distribution and sources of polycyclic aromatic hydrocarbons in the aquatic environment: a multivariate analysis

Fourteen polycyclic aromatic hydrocarbons (PAHs) included in the US Environmental Protection Agency's (EPA) priority pollutant list were analyzed using gas chromatography-mass spectrometry (GC--MS). Surface water sampling was undertaken in the Paraguaçu Estuary (Bahia), northern Brazil. Total PAH concentrations varied from 0.0029 to 0.1079 ng/L in the surface waters (main rivers, tributaries) with a mean value of 0.0344 ng/L. Such concentrations can be taken as background values for the studied region. The PAH profiles were dominated by low molecular weight PAHs (two- and three-ring components) in surface water samples. It indicated that PAHs in surface water may have its origin from oil or sewage contamination (petrogenic input). The collected data showed that petrogenic input was predominant at almost all the stations investigated. To discriminate pattern differences and similarities among the samples, a principal component analysis (PCA) was performed using a correlation matrix. PCA revealed the latent relationships among all the surface water from the investigated stations.

Nitroaromatic compounds, from synthesis to biodegradation.

Nitroaromatic compounds are relatively rare in nature and have been introduced into the environment mainly by human activities. This important class of industrial chemicals is widely used in the synthesis of many diverse products, including dyes, polymers, pesticides, and explosives. Unfortunately, their extensive use has led to environmental contamination of soil and groundwater. The nitro group, which provides chemical and functional diversity in these molecules, also contributes to the recalcitrance of these compounds to biodegradation. The electron-withdrawing nature of the nitro group, in concert with the stability of the benzene ring, makes nitroaromatic compounds resistant to oxidative degradation. Recalcitrance is further compounded by their acute toxicity, mutagenicity, and easy reduction into carcinogenic aromatic amines. Nitroaromatic compounds are hazardous to human health and are registered on the U.S. Environmental Protection Agency's list of priority pollutants for environmental remediation. Although the majority of these compounds are synthetic in nature, microorganisms in contaminated environments have rapidly adapted to their presence by evolving new biodegradation pathways that take advantage of them as sources of carbon, nitrogen, and energy. This review provides an overview of the synthesis of both man-made and biogenic nitroaromatic compounds, the bacteria that have been identified to grow on and completely mineralize nitroaromatic compounds, and the pathways that are present in these strains. The possible evolutionary origins of the newly evolved pathways are also discussed.

Theoretical limit of energy consumption for removal of organic contaminants in U.S. EPA Priority Pollutant List by NRTL, UNIQUAC and Wilson models

This paper quantifies the theoretical limit of energy consumption for the removal of 20 representative organic contaminants (9 chlorinated alkyl hydrocarbons, 3 chlorinated alkenes, 3 brominated methanes, 5 aromatic hydrocarbons and their derivatives) in the United States Environmental Protection Agency (U.S. EPA) Priority Pollutant List by physical procedures. The general rules of the theoretical limit of energy consumption with different initial concentrations at 298.15 K and 1.01325 × 10 5 Pa by NRTL, UNIQUAC and Wilson models are obtained from the thermodynamic analysis with our previously established method based on the thermodynamic first and second law. The results show that the waste treatment process needs a high energy consumption and the theoretical limit of energy consumption for organic contaminant removal increases with decreasing initial concentrations in aqueous solutions. The theoretical limit of energy consumption decreases with the more C–H bonds being replaced by C–Cl or C–Br bonds in chlorinated methanes, ethanes, ethenes or brominated methanes except for 1,1,2,2-tetrachloroethane, and the energy consumption for the removal of chlorinated methanes is higher than that of chlorinated ethanes with the same C–H bonds being replaced by C–Cl bonds. For the removal of chlorinated ethenes, brominated methanes and benzene and its derivatives studied, the energy consumption has corresponding relationship with solubility and the energy consumption is higher for the removal of organics with higher solubility.

Quality assessment of river waters using risk indexes for substances and sites, based on the COMMPS procedure

The well established risk assessment COMMPS methodology (Fraunhofer Institut, Schmallenberg, Germany) developed at a European basin scale to identify priority pollutants based on their exposure and effects, has been applied at a local scale along a double step process: (a) first, the corresponding adapted list of priority pollutants has been obtained from monitoring data at a regional scale; (b) second, a new site pollution risk index has been developed for the relative comparison of the chemical pollution status of the investigated geographical region. As a case study, representative of the Mediterranean area, the process has been applied to 17 Catalan rivers (NE Spain), using the monitoring data collected between 1997 and 2006 in 207 different sampling sites. After an appropriate selection procedure, 52 parameters were finally used for the calculation of the local priority substance and site risk indexes. From the exposure point of view the most relevant substances at the Catalan scale were volatile organohalogen compounds (VOX) and volatile aromatic hydrocarbons (toluene and xylene), whereas the priority substance risk index points to dibromomethane (volatile organohalogen compound) and benzo-a-anthracene (PAH) as the most concerning compounds. The local and European priority substance indexes have been compared, showing minor differences. Finally, site risk indexes have been calculated and utilized for comparison of the chemical status of different sites. They can be conveniently displayed in quality geographical maps and are considered a valuable tool for the environmental management and risk assessment of the region under study.

Validation of a Method for the Analysis of PAHs in Bulk Lake Sediments Using GC-MS

This work presents the validation procedures of an analytical method to determine the 16 PAHs from the US EPA's priority pollutants list in sediment samples using ultrasonic extraction coupled to gas chromatography-mass spectrometry. The extraction techniques are altered by the construction of an extraction flask adapted to the ultrasonic bath that greatly reduces losses and increases extraction efficiency of the volatile compounds, especially naphthalene. Cleanup procedures are also altered to change the polarity of the solvent mixture that contributes to reducing the elution of undesirable compounds. The PAH spiked sediment at 100 microg/kg level shows recovery rate of 68% to 108%. A certified reference material has been analyzed for those compounds showing results conforming to certified values. The optimized procedure is applied to sediment samples from different areas across Southeast Brazil and presents the results from the Ibirité Reservoir (MG, Brazil), a eutrophic water body. The total PAH concentration in these sediment samples varies between 103.96 and 180.87 microg/kg (dry weight). As the detected concentrations are relatively low, the acute toxicity detected in sediment and its pore water is not due to these compounds, but to high concentrations of ammonia, copper, and nickel according to TIE procedures.

Occurrence and distribution of polycyclic aromatic hydrocarbons in the Egyptian aquatic environment

Persistent organic pollutants (POPs) such as polycyclic aromatic hydrocarbons (PAHs) are of great concern due to their persistence, bioaccumulation and toxic effects. In this study, water samples were collected during 2007–2008 from two catchment areas that represent two different models of the aquatic environment in Egypt (Rosetta branch as fresh water and El-Moheet drain as untreated/treated waste water). The distribution of 16 PAHs included in the US Environmental Protection Agency's (EPA) priority pollutant list was analyzed by gas chromatography/mass spectrometry (GC/MS). Total PAH concentrations varied from 242 to 732 ng/L in fresh water from the Rosetta branch with a mean value of 408 ng/L; and for waste water the concentrations were in the range 894 to 1979 ng/L with a mean value of 1476 ng/L. The PAH profiles were dominated by low molecular weight PAHs (two- and three-ring components) in all collected water samples. The origin of PAHs in both waste water and fresh water in these study areas may be from oil or sewage contamination. The total PAHs concentrations of untreated waste water decreased along the treatment process by about 30% at the Zenein waste water treatment plant. The levels of PAHs in waste water are relatively high, although lower than locations with known problems.

Comparison of Two Extraction Methods for the Determination of Polycyclic Aromatic Hydrocarbons in Surface Soils Using Headspace SPME with GC-FID

Two simple methods using headspace solid-phase microextraction (HS-SPME) coupled to a gas chromatograph with a flame ionization detector were compared for the determination of polycyclic aromatic hydrocarbons (PAH) in soils. These compounds were included in the US Environmental Protection Agency's Priority Pollutants list. Direct hot water HS-SPME extraction and sonication organic extraction followed by HS-SPME were optimized using experimental designs. The first method was chosen for PAH determination. The validation of the proposed method was carried out by analyzing PAHs in the certified soil reference material RTC-CRM 123. The accuracy obtained for the PAHs was shown to be inside the prediction interval with the certified material. The optimized method was applied to the analysis of several superficial soils from Gipuzkoa (Basque Country, North Spain).