Varying extractability of petrogenic and pyrogenic polycyclic aromatic hydrocarbons (PAH) in urban soils: Evaluation of sample preparation and extraction of 71 PAH and alkylated PAH.

PAH extraction methods have been widely studied over the last decades. However, there is still no consistent method for contaminated soils. Here, for the first time, PAH source characteristics in soils were considered for the investigation of different pretreatment methods, extraction techniques and solvents in nine petrogenic to primarily pyrogenic urban soils.

Polycyclic aromatic compounds including non-target and 71 target polycyclic aromatic hydrocarbons in scrubber discharge water and their environmental impact.

Increasing use of scrubbers on vessels for reduction of SOx emissions has led to environmental concerns due to discharge of partly persistent and toxic substances such as polycyclic aromatic compounds (PAC) into the sea. A comprehensive analysis of the dissolved and particulate phases of the discharge water from open and closed loop operations on four ships was performed. 71 PAC in the discharge waters varied in concentration and were associated with those of the fuels used, as they mainly originate in unburnt fuel.

Impact of different sterilisation techniques on sorption and NER formation of test chemicals in soil.

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.

Unravelling mixed sources of polycyclic aromatic hydrocarbons (PAH) in urban soils by visual characterization of anthropogenic substrates and coal particles, 71 PAH and alkylated PAH patterns.

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.

A look down the drain: Identification of dissolved and particle bound organic pollutants in urban runoff waters and sediments.

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.

Spatiotemporal variations of surface water quality in a medium-sized river catchment (Northwestern Germany) with agricultural and urban land use over a five-year period with extremely dry summers.

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.

Feature-based molecular networking for identification of organic micropollutants including metabolites by non-target analysis applied to riverbank filtration.

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.

Seasonal performance assessment of four riverbank filtration sites by combined non-target and effect-directed analysis.

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.

Impact of seasonality, redox conditions, travel distances and initial concentrations on micropollutant removal during riverbank filtration at four sites.

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.

Novel and specific source identification of PAH in urban soils: Alk-PAH-BPCA index and "V"-shape distribution pattern.

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).

Ultrasensitive detection of polycyclic aromatic hydrocarbons in coastal and harbor water using GC-APLI-MS.

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.

Identification of 7-9 ring polycyclic aromatic hydrocarbons in coals and petrol coke using High performance liquid chromatography - Diode array detection coupled to Atmospheric pressure laser ionization - Mass spectrometry (HPLC-DAD-APLI-MS).

Polycyclic aromatic hydrocarbons containing at least 24 carbon atoms (≥C-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 ≥C-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 ≥C-PAH due to their low vapor pressures.

Ultra-high sensitive analysis of 3-hydroxybenzo[a]pyrene in human urine using GC-APLI-MS.

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.

Analysis of 6- and 7-ring PAH and other non-EPA PAH by atmospheric pressure laser ionization - mass spectrometry (APLI-MS) in environmental certified reference materials NIST 1941b, NIST 1649b, BAM CC013a and IRMM BCR 535.

Proceedings in environmental analytical chemistry of polycyclic aromatic hydrocarbons (PAH) in the past decades cover improvements in laboratory methods as well as new insights in the toxicology of single PAH compounds. A re-evaluation of the established list of 16 priority PAH published by the U. S.

GC-APLI-MS as a powerful tool for the analysis of BaP-tetraol in human urine.

For the first time gas chromatography (GC) coupled to atmospheric pressure laser ionization-mass spectrometry (APLI-MS) has been applied to the analysis of trans-anti-benzo[a]pyrene-tetraol (BaP-tetraol) formed from anti-benzo[a]pyrene diolepoxide (BPDE), the ultimate carcinogen of benzo[a]pyrene. This tetraol is considered to be an ideal urinary biomarker for polycyclic aromatic hydrocarbon (PAH) exposure as it reflects internal body burden and potentially adverse health effects. Optimization of the derivatization and the instrumental set-up led to an instrumental LOD of 0.

Urban soils impacted by tailings from coal mining: PAH source identification by 59 PAHs, BPCA and alkylated PAHs.

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.

Accelerated benzene polycarboxylic acid analysis by liquid chromatography-time-of-flight-mass spectrometry for the determination of petrogenic and pyrogenic carbon.

Pyrogenic carbon species are of particular interest due to their ubiquitous occurrence in the environment and their high sorption capacities for nonpolar organic compounds. It has recently been shown that the analysis of the molecular markers for complex aromatic carbon structures, benzene polycarboxylic acids (BPCA), has a high potential for aid in the identification of different carbon sources. In this study, the first LC method using mass spectrometry (MS) for reliable and accelerated (<24h) quantification of pyrogenic and petrogenic carbon by BPCA analysis has been developed.

Ultra-high sensitive PAH analysis of certified reference materials and environmental samples by GC-APLI-MS.

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.

Toward Streamlined Identification of Dioxin-like Compounds in Environmental Samples through Integration of Suspension Bioassay.

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.

Liquid chromatography-atmospheric pressure laser ionization-mass spectrometry (LC-APLI-MS) analysis of polycyclic aromatic hydrocarbons with 6-8 rings in the environment.

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.

Time to Say Goodbye to the 16 EPA PAHs? Toward an Up-to-Date Use of PACs for Environmental Purposes.

The 16 EPA PAHs have played an exceptionally large role above all in environmental and analytical sciences in the last 40 years, but now there are good reasons to question their utility in many circumstances even though their use is so established and comfortable. Here we review the reasons why the list has been so successful and why sometimes it is seen as less relevant. Three groups of polycyclic aromatic compounds (PAC) are missing: larger and highly relevant PAHs, alkylated PACs, and compounds containing heteroatoms.

Overview of Polycyclic Aromatic Compounds (PAC).

The chemical group of polycyclic aromatic compounds (PAC), including the better-known subgroup of polycyclic aromatic hydrocarbons (PAH) and the heterocyclic aromatic compounds (NSO-PAC, heterocycles), comprise several thousand individual compounds. It is hard to find a comprehensive overview in the literature of these PACs that includes a substantial amount of relevant properties. Here an attempt is made to summarize the most studied but also some less well-known PACs.

Investigations on sediment toxicity of German rivers applying a standardized bioassay battery.

River sediments may contain a huge variety of environmental contaminants and play a key role in the ecological status of aquatic ecosystems. Contaminants adsorbed to sediments and suspended solids may contribute directly or after remobilization to an adverse ecological and chemical status of surface water. In this subproject of the joint research project DanTox, acetonic Soxhlet extracts from three German river sediments from the River Rhine (Altrip and Ehrenbreitstein with moderate contamination) and River Elbe (Veringkanal Hamburg heavily contaminated) were prepared and redissolved in dimethyl sulfoxide (DMSO).

Impact of reference geosorbents on oral bioaccessibility of PAH in a human in vitro digestive tract model.

Former studies on human oral bioaccessibility of polycyclic aromatic hydrocarbons (PAH) from natural soil samples using human in vitro digestive tract models (physiologically based extraction tests, PBET) show highly variable results (0-100% of mobilized PAH). Apart from other factors, the type and amount of present geosorbents are assumed to be significant for the degree of desorption/release of PAH into the digestive juice. Therefore, in this study, the reference geosorbents pure quartz sand, Na-montmorillonite clay, Pahokee peat, and charcoal "Sommerhit" were spiked with selected deuterated PAH and employed as single materials in a PBET.