RESUMEN
Due to growing concern about organic micropollutants and their transformation products (TP) in surface and drinking water, reliable identification of unknowns is required. Here, we demonstrate how non-target liquid chromatography (LC)-high-resolution tandem mass spectrometry (MS/MS) and the feature-based molecular networking (FBMN) workflow provide insight into water samples from four riverbank filtration sites with different redox conditions. First, FBMN prioritized and connected drinking water relevant and seasonally dependent compounds based on a modification-aware MS/MS cosine similarity. Within the resulting molecular networks, forty-three compounds were annotated. Here, carbamazepine, sartans, and their respective TP were investigated exemplarily. With chromatographic information and spectral similarity, four additional TP (dealkylated valsartan, dealkylated irbesartan, two oxygenated irbesartan isomers) and olmesartan were identified and partly verified with an authentic standard. In this study, sartans and TP were investigated and grouped regarding their removal behavior under different redox conditions and seasons for the first time. Antihypertensives were grouped into compounds being well removed during riverbank filtration, those primarily removed under anoxic conditions, and rather persistent compounds. Observed seasonal variations were mainly limited to varying river water concentrations. FBMN is a powerful tool for identifying previously unknown or unexpected compounds and their TP in water samples by non-target analysis.
RESUMEN
Effect-directed analysis (EDA) is a powerful strategy to identify biologically active compounds in environmental samples. However, in current EDA studies, fractionation and handling procedures are laborious, consist of multiple evaporation steps, and thus bear the risk of contamination and decreased recoveries of the target compounds. The low resulting throughput has been one of the major bottlenecks of EDA. Here, we propose a high-throughput EDA (HT-EDA) work-flow combining reversed phase high-performance liquid chromatography fractionation of samples into 96-well microplates, followed by toxicity assessment in the micro-EROD bioassay with the wild-type rat hepatoma H4IIE cells, and chemical analysis of bioactive fractions. The approach was evaluated using single substances, binary mixtures, and extracts of sediment samples collected at the Three Gorges Reservoir, Yangtze River, China, as well as the rivers Rhine and Elbe, Germany. Selected bioactive fractions were analyzed by highly sensitive gas chromatography-atmospheric pressure laser ionization-time-of-flight-mass spectrometry. In addition, we optimized the work-flow by seeding previously adapted suspension-cultured H4IIE cells directly into the microplate used for fractionation, which makes any transfers of fractionated samples unnecessary. The proposed HT-EDA work-flow simplifies the procedure for wider application in ecotoxicology and environmental routine programs.
Asunto(s)
Dioxinas , Sedimentos Geológicos/química , Animales , Bioensayo , Ecotoxicología , Ríos/química , Contaminantes Químicos del AguaRESUMEN
A method has been developed for the sensitive and rapid analysis of polycyclic aromatic hydrocarbons (PAHs) in environmental samples using liquid chromatography time-of-flight mass spectrometry as well as the selective atmospheric pressure laser ionization (APLI) process (LC-APLI-MS). Upon analyzing 34 PAHs, the limits of detection of this method were found to range from 0.008 to 1.824 pg (0.024 pg for benzo[a]pyrene). The method therefore provides 30-fold to 5,400-fold increased sensitivity compared with the established GC-MS technique. This LC-APLI-MS method was optimized for higher molecular weight PAHs (C24-C30 PAHs with 6-8 rings), which are difficult to detect or cannot be detected by GC-MS. Using the LC-APLI-MS method, various 6- to 8-ring PAHs were detected in environmental samples for the first time. After developing the method, it was successfully validated in ruggedness tests. The concentrations determined by the LC-APLI-MS method were in good accord with the certified concentrations in three certified reference materials (contaminated soils and sediments). Upon applying the method to environmental samples, it was found that (1) the presence of dibenzo[a,i]pyrene and dibenzo[a,h]pyrene in urban soil samples could only be detected using LC-APLI-MS (i.e., not GC-MS) due to its high sensitivity, (2) a bituminous coal sample yielded 211 tentative peaks from aromatic compounds in the C24-C30 range, and (3) eleven of those compounds occurred in different environmental samples in similar patterns. Hence, 6- to 8-ring PAHs occur in solid environmental samples in which other 6-ring PAHs such as indeno[1,2,3-cd]pyrene or benzo[ghi]perylene may also be present. Some of these numerous higher molecular weight PAH compounds could have very high carcinogenic potential, which will need to be elucidated to ensure the reliability of PAH risk assessments.
RESUMEN
Due to several polycyclic aromatic hydrocarbons (PAHs) being highly carcinogenic and at the same time occurring at very low environmental concentrations up to the microgram per kilogram range, highly sensitive chemical analysis in various matrices is needed. Here, for the first time, a method using gas chromatography (GC) and atmospheric pressure laser ionization-mass spectrometry (APLI-MS), which is much more sensitive compared to common GC-MS, proved to produce reliable (certified reference materials) and comparable (GC-MS) results. PAHs and selected isomers of alkyl-PAHs were targeted, whereby 53 analytes could be quantified individually; for one pair, the sum had to be calculated. In combination with the selective and sensitive (1+1)-REMPI process of the APLI, limits of detection (LODs) between 5 and 50 fg/µL could be obtained. To prove the reliability of this method, four certified reference materials (SRM1649b urban dust, SRM 1941b organics in marine sediment, BCR 535 fresh water harbor sediment, and ERM CC013a contaminated soil from a former gas plant site) were analyzed. The results were in good accordance with the certified values. In addition, analytical results of three different environmental matrices (bituminous coal, suspended particulate matter from river and pine needles) were compared to values obtained with well-established GC-EI-MS. The results show that this method presents an excellent tool ready-to-use for the analysis of environmental samples with very low PAH content or very low sample amount.
RESUMEN
The identification of polycyclic aromatic hydrocarbon (PAH) sources in heterogeneous urban soils containing pyrogenic and/or petrogenic anthropogenic substrates is a common task for risk assessment. Here, for the first time, the results of source identification using analysis of 71 PAH, alkylated PAH patterns and PAH Alkylation Index were related to visually identified and quantified anthropogenic substrates in 50 soil samples. Only the combination of chemical methods with visual characterization enabled the deeper understanding of varying alkylated PAH patterns used for source apportionment and their superimposition if multiple sources occur. Pyrogenic substrates show homogenic slope-shape PAH patterns despite large visual variety. Petrogenic substrates (bituminous coals), show prevailingly bell-shape patterns but pyrogenic patterns also occur, probably due to residues from industrial processes and/or sorption of other pyrogenic PAH. Superimposition of both PAH patterns within a sample results in intermediate patterns, which are determined by the abundance of substrates and their individual PAH contents. A discrepancy between the share of petrogenic substrates and petrogenic PAH was observed due to low-medium PAH contents from coals/tailings. This may lead to misinterpretations if only chemical source identification methods are applied. With increasing proportion of petrogenic PAH in the mixture, the intermediate V-shape pattern (later bell-shape) appears in lower molecular weight PAH and moves progressively to higher molecular weight PAH. ∑71 PAH contents vary from 1.77 to 326.5 mg/kg (median 26.5 mg/kg). Non-EPA PAH measured include highly toxic ∑4 dibenzopyrene isomers (0.045-6.23 mg/kg, median 0.79 mg/kg) and 7H-benzo[c]fluorene (0.008-1.57 mg/kg, median 0.12 mg/kg). Most common anthropogenic substrates are bottom ashes, slags, bituminous coals/tailings and coke/coke ash. The PAH Alkylation Index identifies reliably samples dominated by either petrogenic (<0.4) or pyrogenic (>0.9) PAH, independently of the PAH content. Mixed or primarily pyrogenic PAH sources (0.4-0.9) need further investigations, like the presented combination of methods, which enables a reliable source apportionment.
Asunto(s)
Coque , Hidrocarburos Policíclicos Aromáticos , Carbón Mineral/análisis , Coque/análisis , Hidrocarburos Policíclicos Aromáticos/análisis , Suelo/química , Monitoreo del Ambiente/métodosRESUMEN
Standard OECD tests are used to generate data on biodegradation (OECD 307) and sorption (OECD 106) of test chemicals in soil. In such tests, data on abiotic degradation using sterile samples are utilised to investigate any losses due to abiotic processes. The data from sterile samples are also used to interpret results and findings of non-sterile samples, especially in the context of sorption and non-extractable residue (NER) formation. However, to ensure the comparability of the data obtained from sterile and non-sterile experiments, effects of sterilisation on the soil matrix should be minimal. The objective of this study was to investigate the efficiencies of different sterilisation techniques and the impact of the sterilisation on sorption and NER formation in soil. In this study, experiments in accordance with OECD 307 and OECD 106 guidelines were performed with two soils covering wide range of soil characteristics and treated with the three sterilisation techniques autoclaving, gamma(γ)-radiation and adding 1% (w/w) sodium azide. As a test item, 14C-labelled phenanthrene and bromoxynil was used for OECD 307 test, whereas non-labelled phenanthrene and atrazine was used for OECD 106. The sterilisation efficiencies were investigated using traditional viable plate count and molecular approaches (RNA extraction method). The results suggest that none of the tested techniques resulted in completely sterilised soil with autoclaving being the most efficient technique. Adding sodium azide led to most inefficient sterilisation and a significant increase (0.56 units) in soil pH. OECD 307 results showed differences in NER formation of the test chemicals, especially for soil poisoning and γ-radiation, which could be due to inefficient sterilisation and/or change in soil physico-chemical properties. OECD 106 results suggest that none of the sterilisation techniques considerably affected sorption behaviour of the test chemicals. Based on our results, we recommend autoclaving as most suitable sterilisation technique.
Asunto(s)
Biodegradación Ambiental , Contaminantes del Suelo , Suelo , Esterilización , Contaminantes del Suelo/química , Contaminantes del Suelo/análisis , Esterilización/métodos , Suelo/química , Adsorción , Rayos gamma , Fenantrenos/químicaAsunto(s)
Contaminantes Atmosféricos/toxicidad , Biomasa , Bronquios/efectos de los fármacos , Células Epiteliales/efectos de los fármacos , Perfilación de la Expresión Génica/métodos , Material Particulado/toxicidad , Madera , Bronquios/metabolismo , Línea Celular , Células Epiteliales/metabolismo , Regulación de la Expresión Génica/efectos de los fármacos , Redes Reguladoras de Genes/efectos de los fármacos , Humanos , Lipopolisacáridos/toxicidad , Análisis de Secuencia por Matrices de Oligonucleótidos , Tamaño de la Partícula , Centrales Eléctricas , ARN Bicatenario/toxicidad , Medición de Riesgo , Transducción de Señal/efectos de los fármacos , Transducción de Señal/genética , Transcriptoma/efectos de los fármacosRESUMEN
Coals contain native polycyclic aromatic compounds (PACs), which include polycyclic aromatic hydrocarbons (PAHs), and heterocyclic aromatic compounds (NSO-PACs) in considerably varying amounts up to 2500 mg/kg. Whereas PAC bioavailability and toxicity from coals are generally considered to be low, few studies have considered potential variations arising from the composition of different coal types including native PAC content. In the present study, fine particles of different coal types exhibiting variable properties were systematically investigated regarding their PAC bioavailability. PAH content reached up to 79 mg/kg EPA-PAH and 865 mg/kg total PAH. Determination of the toxic potential of extracted PACs in bioassays showed inhibition of Caenorhabditis elegans reproduction (up to 94%) and increased mortality of Danio rerio embryos (up to 100%) after exposure to extracts from lignite, sub-bituminous, and bituminous coals. Anthracite extracts showed no effects. Contact assays using whole coal samples revealed no toxicity to D. rerio embryos in any of the coal samples, suggesting low bioavailability of PACs. In contrast, C. elegans reproduction was inhibited by direct coal contact; however, the observed toxicity probably resulted from other coal effects. The results suggest that despite the high toxic potential of PACs present, their bioavailability from different coal types is very limited and independent of coal properties and native PAH content.
Asunto(s)
Carbón Mineral/análisis , Hidrocarburos Policíclicos Aromáticos/toxicidad , Pruebas de Toxicidad Aguda , Contaminantes Químicos del Agua/toxicidad , Animales , Bioensayo , Caenorhabditis elegans/efectos de los fármacos , Caenorhabditis elegans/embriología , Embrión no Mamífero/efectos de los fármacos , Reproducción/efectos de los fármacos , Pez Cebra/embriologíaRESUMEN
The application of polycyclic aromatic hydrocarbon (PAH) analysis by gas chromatography coupled with atmospheric pressure laser ionization and mass spectrometry (GC-APLI-MS) to environmental samples was investigated in the study. The limit of detection for 40 PAH in a standard mixture was 5-100 fg, demonstrating GC-APLI-MS to be a highly sensitive technique and more sensitive by a factor of 100-3,500 compared to GC-MS. Acenaphthylene and cyclopenta[cd]pyrene were not detectable <2,500 fg per injection. To make use of this very high PAH sensitivity, the technique was applied to samples of environmental interest with limited available sample amounts such as particulate matter (PM), soot and a sample from a bioaccumulation test with Lumbriculus variegatus. First, special sample preparation was necessary and ultrasonic extraction proved to be suitable, if a thorough clean-up was performed and plastic materials avoided. By GC-APLI-MS and GC-MS, 224 and 28 single PAH compounds were detected in PM, about 1,000 and 15 in birch soot, and 9 and 2 in worm tissue, respectively, revealing the enormous potential of the method. The selectivity of GC-APLI-MS was shown for a crude oil where >2,200 PAH were detected without any sample preparation.
Asunto(s)
Monitoreo del Ambiente/métodos , Cromatografía de Gases y Espectrometría de Masas/métodos , Oligoquetos/química , Material Particulado/análisis , Hidrocarburos Policíclicos Aromáticos/análisis , Animales , Presión Atmosférica , Monitoreo del Ambiente/instrumentación , Cromatografía de Gases y Espectrometría de Masas/instrumentación , Rayos Láser , Límite de Detección , Oligoquetos/metabolismo , Hidrocarburos Policíclicos Aromáticos/metabolismoRESUMEN
Medium-sized rivers, which are used for intensive agriculture and urban infrastructure, are subject to manifold hydrochemical stressors. Identifying and monitoring these stressors is important for river basin management and a functioning ecosystem. To understand the spatiotemporal variation of surface water quality in a highly modified lowland river, the Münstersche Aa River (Northwestern Germany) with 62% of land used for agriculture and 26% urban/residential area, was exemplarily studied. A total of 519 samples were collected using two automated high-frequency samplers and five catchment-wide sampling campaigns. They covered the five-year period 2015-2020 and included two extremely dry summers. The Münstersche Aa catchment is dominated by low permeable strata resulting in surface water runoff (Baseflow Index: 0.41) which leads to a high amplitude of discharge variation (mean discharge: 0.7 m3/s) with high flow conditions in winter/spring, and low discharge during summer/fall. In wintertime, maximum nitrate concentrations (up to 73 mg NO3/L) and loads (up to 1300 t NO3/a; up to 98% in winter) correlate with high-flow conditions. δ18O and δ15N isotopic analysis indicated manure from farmland as the major source of nitrate whereas the impact of municipal wastewater treatment plants was neglectable. Increased nitrate concentrations are linked to the higher proportion of farmland in the upper catchment (77%) compared with the lower catchment (47%). In summertime, at extremely low flow conditions, surface water consisted of up to 100% of treated wastewater, resulting in the highest measured chloride, sodium and potassium concentrations. The river is impacted by strongly seasonal and different stressors, which can be expected to intensify with ongoing climate change. Results from this study may help to adapt monitoring schemes for the Münstersche Aa but also for other lowland streams with comparable land-use targeting the goals of the Water Framework Directive.
Asunto(s)
Ríos , Contaminantes Químicos del Agua , Agricultura , Ecosistema , Monitoreo del Ambiente/métodos , Ríos/química , Estaciones del Año , Contaminantes Químicos del Agua/análisis , Calidad del AguaRESUMEN
Urban runoff contains a range of organic micropollutants which, if not removed during wastewater treatment, pose a risk to aquatic environments. These mixtures are complex and often site-specific. Street drains provide an ideal sampling point given they collect the runoff from local and defined catchments. In this study, runoff was collected and sampled in five street drains located in a medium sized town in Germany. A specially constructed trap was used to collect the particulate and total water fractions of the runoff. In addition, passive samplers were deployed to determine the freely dissolved concentrations of selected compounds in the runoff. In sum, 187 polar organic micropollutants could be quantified using LC-HRMS. Thirty of these could only be detected by the use of passive samplers. Traffic derived pollutants such as corrosion inhibitors, rubber- and plastic additives, but also pollutants of industrial origin were strongly represented with sum median concentrations of 100 µg/kg dry weight (DW) in the sediment and 400 ng/L in the water fraction. Several of these substances are of concern due to their environmental persistence and mobility. Perfluorinated compounds and pesticides occurred at lower levels of several µg/kg DW sediment or ng/L water. A number of substances including pharmaceuticals, sweeteners and stimulants indicated domestic wastewater influences. Furthermore, a total of 62 parent and alkylated PAHs were quantified by GC-MS and contributed 30-70% to the sum concentrations of the micropollutants. Non-EPA PAHs dominated the carcinogenic PAH toxicity. The increased PAH alkylation indices (0.7-0.9) showed these primarily came from combustion sources. The runoff particles were additionally microscopically characterized, and correlations were found between the rubber particle counts and the PAH alkylation-index as well as the levels of 2-(methylthio)benzothiazole, a marker compound for tire leaching.
Asunto(s)
Contaminantes Ambientales , Plaguicidas , Hidrocarburos Policíclicos Aromáticos , Contaminantes Químicos del Agua , Monitoreo del Ambiente , Sedimentos Geológicos , Plaguicidas/análisis , Hidrocarburos Policíclicos Aromáticos/análisis , Aguas Residuales , Contaminantes Químicos del Agua/análisisRESUMEN
Soils in urban and industrial areas, especially in larger metropolitan areas such as the Ruhr area, Germany, are commonly characterized by severe anthropogenic overprinting due to urbanization processes including land development measures. Such urban soils often contain various anthropogenic substrate admixtures, like ash, coal, tailings, building rubble, industrial waste materials, as well as urban dust, soot, fly ash, and others. These admixtures often carry higher contents of pollutants such as polycyclic aromatic hydrocarbons (PAH). Whereas elevated PAH concentrations are commonly attributed to non-point pyrogenic carbon sources like soot and particulate matter, petrogenic PAH sources are still largely neglected in this context. In this study, an extended sample set of 62 samples of PAH source materials and urban soils containing anthropogenic substrate components was investigated by combining extended PAH analysis of 59 PAH, alkylated PAH distributions and benzene polycarboxylic acid (BPCA) analysis with regard to petrogenic and pyrogenic PAH source identification. For more reliability of source apportionment by a more integrative signal, the alkylated PAH distributions of different PAH groups were combined according to their degrees of alkylation. Based on this combination, a new PAH alkylation index (ΣC0/(ΣC0+ΣC2)) was derived, which considers, in contrast to commonly used single PAH ratios, a series of non-alkylated and alkylated PAH. By comparison of this PAH alkylation index with the degree of aromatic condensation a new robust and economic method for identifying petrogenic, pyrogenic and mixed PAH sources within soil samples and sediments was developed. It is shown that coal and coal ash particles are a not negligible PAH source in urban soils of mining-dominated regions and can make up a large proportion of the anthropogenic substrate components encountered. Further analyses of samples with defined levels of petrogenic and pyrogenic PAH are necessary to finally evaluate the usefulness of this proposed new PAH-BPCA approach.
Asunto(s)
Monitoreo del Ambiente , Hidrocarburos Policíclicos Aromáticos/análisis , Contaminantes del Suelo/análisis , Suelo/química , Benceno/análisis , Carbono/análisis , Ácidos Carboxílicos/análisis , Carbón Mineral/análisis , Polvo/análisis , Alemania , Reproducibilidad de los Resultados , Hollín/análisis , UrbanizaciónRESUMEN
Riverbank filtration (RBF) is a reliable water purification technique that has proven to be suitable for the removal of organic micropollutants. Its removal efficiency and dependency on a variety of factors such as redox conditions, temperatures, geology, travel times, level of initial micropollutant concentrations and seasonality were investigated during three seasonal sampling campaigns. Two anoxic (silty sand, Ems river) and two oxic (gravel, Ruhr river) RBF sites in Germany with different travel distances (42-633 m) were studied. Micropollutant concentrations were examined using a large-volume direct injection liquid chromatography method coupled to high-resolution mass spectrometry. Seasonal differences in micropollutant concentrations in the rivers were observed for chlorotolurone, diclofenac, terbuthylazine, mecoprop-P, MCPA (2-methyl-4-chlorophenoxyacetic acid) and propyphenazone. Redox dependencies in RBF were only found for sulfamethoxazole, propyphenazone, terbuthylazine and carbamazepine. Data for oxazepam, tramadol, N-desmethyl-tramadol, tilidin-desmethyl, carbamazepine and carbendazim indicate a required minimum travel distance of e.g. 100-200 m for the complete removal. Notably, travel time did not seem to be a substantial factor for their removal. High conductivity aquifers are also well suited for micropollutant removal. Seasonal initial concentration level variations showed no impact on the resulting abstraction well concentrations. Although the calculated removal efficiencies varied, they proved to be improper for seasonal raw water quality comparison. Knowledge of micropollutant behavior in riverbank filtration was broadened and RBF proved to be well suited for effective micropollutant reduction throughout the year, yet for a complete removal long travel distances or further technical purification steps are required.
Asunto(s)
Monitoreo del Ambiente , Contaminantes Químicos del Agua/análisis , Filtración/métodos , Alemania , Agua Subterránea/química , Oxidación-Reducción , Ríos/química , Purificación del Agua/métodos , Calidad del AguaRESUMEN
Targeting the most relevant organic micropollutants (OMP) in routine analysis appears difficult due to formation of transformation products of unknown concentration or toxicity. Performance assessment of water purification processes is still based upon limited target data. Therefore, we broadened the assessment of the removal efficiencies with combined non-target and effect-directed analysis at four riverbank filtration (RBF) sites in Germany. To assess micropollutant elimination, constancy and formation during different seasons, considering local redox conditions, travel distances and total component number in the river, non-target analysis features were grouped into categories. Furthermore, RBF sites were investigated with four endpoints (baseline toxicity, acetylcholinesterase inhibition, antibiotic effects and estrogenic effects) for thin-layer chromatography - effect-directed analysis for the first time. Results showed elimination or reduction of many features and effects, but also constancy and formation of varying proportions. Fall river samples showed precipitation-caused dilution in both tests. Spring samples showed increased effects only in acetylcholinesterase inhibition and estrogenic effects, probably due to phytoestrogens or algae bloom during vegetation period. Sites were ranked considering the total number of features, group proportions, seasonal variations and intensity and number of effects in abstraction wells. Oxic conditions and low initial component numbers in the river (Ruhr sites) resulted in less effects and fewer formations. Longer travel distances were important for a more efficient reduction of effects and features. Combination of non-target and effect-directed analysis proved to be valuable for a more comprehensive assessment of process performance beyond target analysis as also unknown OMP are observed with both methods.
Asunto(s)
Contaminantes Químicos del Agua/análisis , Filtración/métodos , Alemania , Oxidación-Reducción , Ríos , Estaciones del Año , Purificación del Agua/métodosRESUMEN
Polycyclic aromatic hydrocarbons (PAH) are a group of ubiquitous environmental pollutants among which some compounds show carcinogenic properties. The emission of PAH from anthropogenic and natural sources to the aquatic environment demands monitoring. In this study, ten different surface water samples were collected and analyzed for 48 different PAH compounds by gas chromatography-atmospheric-pressure-laser-ionization coupled to mass spectrometry (GC-APLI-MS) after liquid-liquid extraction. Results varied from 9.22â¯ng/L for fluoranthene in harbor water to 0.01â¯ng/L for 4-methylchrysene in Rhine river water. Overall low PAH concentrations were found in the samples. Toxic equivalent (TEQ) calculations were used to assess the potential environmental impact of the analyzed compounds. The results showed higher concentrations and TEQ for the samples from harbors in comparison to riverine and estuarine sampling locations. Suspected target analysis indicated the occurrence of alkylated PAH in the surface water samples.
Asunto(s)
Cromatografía de Gases y Espectrometría de Masas/métodos , Hidrocarburos Policíclicos Aromáticos/análisis , Contaminantes Químicos del Agua/análisis , Alquilación , Carcinógenos/análisis , Estuarios , Alemania , Extracción Líquido-Líquido , Ríos , Sensibilidad y EspecificidadRESUMEN
Polycyclic aromatic hydrocarbons containing at least 24 carbon atoms (≥C24-PAH) are often associated with pyrogenic processes such as combustion of fuel, wood or coal, and occur in the environment in diesel particulate matter, black carbon and coal tar. Some of the ≥C24-PAH, particularly the group of dibenzopyrenes (five isomers, six aromatic rings) are known to show high mutagenic and carcinogenic activita. Gas chromatography - mass spectrometry is a well-established method for the analysis of lower molecular weight PAH but is not optimally suited for the analysis of ≥C24-PAH due to their low vapor pressures. Also, hundreds of ≥C24-PAH isomers are possible but only a few compounds are commercially available as reference standards. Therefore, in this study, a combination of multidimensional liquid chromatography, UV-Vis diode array detection, PAH selective and highly sensitive atmospheric pressure laser ionization - mass spectrometry is used to detect and unequivocally identify PAH. For identification of PAH in two bituminous coals and one petrol coke sample, unique and compound specific UV-Vis spectra were acquired. It was possible to identify ten compounds (naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[e,ghi]perylene, dibenzo[cd,lm]perylene, benzo[a]coronene, phenanthrol[5,4,3,2-abcde]perylene, benzo[ghi]naphtho[8,1,2-bcd]perylene, benzo[pqr]naphtho[8,1,2-bcd]perylene, naphtho[8,1,2-abc]coronene and tribenzo[e,ghi,k]perylene) by comparison of acquired spectra with spectra from literature. Additionally, it was possible to detect similar distribution patterns in different samples and signals related to alkylated naphthopyrenes, naphthofluoranthenes or dibenzopyrenes. Subsequent effect-directed analysis of a bituminous coal sample using the microEROD (ethoxyresorufin-O-deethylase) bioassay showed high suitability and revealed lower EROD induction for the ≥C24-PAH (TEQ range 0.67-10.07â¯ng/g) than for the alloverâ¯<â¯C24-PAH containing fraction (TEQ 84.00â¯ng/g). Nevertheless, the toxicity of ≥C24-PAH has a significant impact compared with Asunto(s)
Carbón Mineral/análisis
, Coque/análisis
, Hidrocarburos Policíclicos Aromáticos/química
, Cromatografía Líquida de Alta Presión
, Cromatografía Liquida
, Espectrometría de Masas/métodos
, Hidrocarburos Policíclicos Aromáticos/análisis
RESUMEN
Urinary 3-hydroxybenzo[a]pyrene (3-OH-BaP) is a known biomarker for human exposure to carcinogenic polycyclic aromatic hydrocarbons (PAH). In this work, a new method for the ultra-sensitive quantification of this biomarker has been developed using the hyphenation of gas chromatography and atmospheric pressure laser ionization-mass spectrometry (GC-APLI-MS). In combination with an advanced sample preparation, a limit of detection (LOD) of 0.6â¯pg/L was achieved which is an improvement by a factor of at least 28 compared with existing methods. The limit of quantification (LOQ) is 1.8â¯pg/L. With this set-up 3-OH-BaP could be analyzed in urine samples of 7 smokers and 7 non-smokers. Concentrations ranged from 37 to 270â¯pg/L for non-smokers and from 374 to 1171â¯pg/L for smokers. For the first time, 3-OH-BaP was quantifiable in all non-smoker samples as no value was below the LOQ. Correlation of the urinary 3-OH-BaP values with the number of daily smoked cigarettes and with urinary cotinine values shows a clear relationship between 3-OH-BaP content and smoking habits. This innovative analytical method enables monitoring of low levels of the biomarker 3-OH-BaP in urine of non-occupationally exposed individuals including smokers, the general population with background PAH exposure and cohorts of low exposition such as newborns and children.
Asunto(s)
Benzopirenos/análisis , Cromatografía de Gases y Espectrometría de Masas/métodos , Exposición por Inhalación/análisis , Fumar/orina , Adulto , Biomarcadores/orina , Alemania , Humanos , Límite de Detección , Modelos Lineales , Reproducibilidad de los Resultados , Contaminación por Humo de Tabaco/análisisRESUMEN
Organic petrographic analysis was applied to provide direct information on carbonaceous geosorbents for PAHs in river floodplain soils. The anthropogenic OM group (primarily coal and coal-derived particles) displayed large volume amounts for all the soil samples. Distinct PAH concentrations with similar PAH distribution patterns were determined in grain size and density fractions for each sample. Two-ring PAHs had stronger correlation to organic carbon (OC) than black carbon (BC) contents, while heavier PAHs showed correlation to BC, rather than OC. In this study, we combined grain size and density separation, PAH determinations, TOC and BC measurements, and organic petrographic identification, and concluded that two-ring PAHs in soils were associated to coal particles. Other heavier PAHs could be more controlled by black carbon (BC), which were mostly coal-derived particles from former coal mining and coal industrial activity.
Asunto(s)
Carbono/química , Hidrocarburos Policíclicos Aromáticos/química , Ríos , Contaminantes del Suelo/análisis , Monitoreo del Ambiente , Sedimentos Geológicos/análisis , Suelo/análisisRESUMEN
Urban soils in mining and industrial regions like the Ruhr Area are characterized by admixtures of anthropogenic substrates, e. g. tailings, coals, ashes, debris or scoria. These soils often show elevated concentrations of polycyclic aromatic hydrocarbons (PAHs) which are commonly attributed to non-point pyrogenic carbon sources like soot and particulate matter. An emission source of PAHs into urban soils in these regions, that surprisingly is still largely neglected, are the millions of tons of tailings from underground coal mining that have been used as material for road construction, terrain leveling, river channeling and support of embankments. Here we classify the PAH sources of 13 urban soils as either petrogenic or pyrogenic. The soils contained (1) tailings, (2) ashes and (3) different anthropogenic substrates. The classification is based on a comprehensive analysis of 59 PAHs and alkylated PAH distributions by GC-MS and BPCA analyses by LC-TOF-MS. PAH concentrations (∑59 PAHs) of all soils ranged from 60 to 140â¯mg/kg, except one soil showing 559â¯mg/kg. The PAH source in the urban soils containing tailings was identified as petrogenic carbon due to (1) the dominance of low molecular weight PAHs, (2) bell shape distribution patterns of the alkylated PAHs, and (3) comparable BPCA distribution patterns to bituminous coals. In contrast, the PAH source of the ash-containing soil was identified as pyrogenic carbon by high molecular weight PAH percentages >80%, slope shape distribution patterns of the alkylated PAHs and a higher degree of aromatic condensation (B6CA/BPCA) than bituminous coals, coal ashes or charcoal. The urban soils containing different anthropogenic substrates revealed the occurrence of both a petrogenic and a pyrogenic PAH source. Surprisingly, the separate analyses of isolated coal ash particles revealed typical petrogenic indicators showing that by visual approach coal ashes cannot generally be classified as being of a pyrogenic PAH source.
Asunto(s)
Minas de Carbón , Monitoreo del Ambiente , Hidrocarburos Policíclicos Aromáticos/análisis , Contaminantes del Suelo/análisis , Suelo/química , Alquilantes , Carbono/análisis , Cromatografía Liquida , Carbón Mineral/análisis , Ríos/químicaRESUMEN
In this study 59 PAH were analyzed in samples of petrogenic and pyrogenic sources as well as mixed environmental matrices. Among the analytes, PAH of molecular weights from 128 Da to 302 Da in alkylated and in native form were included. Results show that non-EPA PAH make up 69.395.1% of the overall toxic equivalents (TEQ) as based on the toxic equivalent factors (TEF) of 24 PAH. Particularly 7H-benzo[c]fluorene, dibenzopyrene isomers and alkylated PAH (in particular 5-methylchrysene and 1-methylpyrene) turned out to have a huge impact on the toxicity and must not be neglected in future risk assessment. In detail, dibenzopyrenes have a high impact on toxicity predominantly in pyrogenic materials (21% to 84%; mean: 59%) whereas 7H-benzo[c]fluorene dominates toxicity of petrogenic materials (up to 80%; mean: 26%). However, in the studied mixed environmental samples the toxic impact of both groups together is as high as about 80%. Many non-EPA PAH are not considered in risk assessment and amongst them there are some very toxic ones. This needs to be carefully evaluated in future studies.