Effect of polycyclic aromatic compounds (PAH & Polar-PAC) availability on their ecotoxicity towards terrestrial organisms.

The exposure of terrestrial organisms to soils freshly contaminated by polycyclic aromatic compounds (PACs, including PAHs and polar-PACs) is known to cause significant toxicity effects. However, historically contaminated soils, such as former coking plant soils, usually induce a limited toxic impact, due to the "aging" phenomenon which is the result of several processes causing a reduction of PAC availability over time. For a better understanding of these behaviors, this study aimed to compare the toxic responses of terrestrial organisms exposed to aged contaminated soils and their counterparts submitted to a moderate heating process applied to increase PAC availability.

Handle Matrix Rank Deficiency, Noise, and Interferences in 3D Emission-Excitation Matrices: Effective Truncated Singular-Value Decomposition in Chemometrics Applied to the Analysis of Polycyclic Aromatic Compounds.

The characterization of organic compounds in polluted matrices by eco-friendly three-dimensional (3D) fluorescence spectroscopy coupled with chemometric algorithms constitutes a powerful alternative to the separation techniques conventionally used. However, the systematic presence of Rayleigh and Raman scattering signals in the excitation-emission matrices (EEMs) complicates the spectral decomposition via PARAllel FACtor analysis (PARAFAC) due to the nontrilinear structure of these signals. Likewise, the specific problem of selectivity in spectroscopy for unexpected chemical components in a complex sample may render its chemical interpretation difficult at first glance.

Taxonomic and functional trait-based approaches suggest that aerobic and anaerobic soil microorganisms allow the natural attenuation of oil from natural seeps.

Natural attenuation, involving microbial adaptation, helps mitigating the effect of oil contamination of surface soils. We hypothesized that in soils under fluctuating conditions and receiving oil from seeps, aerobic and anaerobic bacteria as well as fungi could coexist to efficiently degrade hydrocarbons and prevent the spread of pollution. Microbial community diversity was studied in soil longitudinal and depth gradients contaminated with petroleum seeps for at least a century.

Permanganate oxidation of polycyclic aromatic compounds (PAHs and polar PACs): column experiments with DNAPL at residual saturation.

Permanganate is an oxidant usually applied for in situ soil remediation due to its persistence underground. It has already shown great efficiency for dense nonaqueous phase liquid (DNAPL) degradation under batch experiment conditions. In the present study, experimental permanganate oxidation of a DNAPL - coal tar - sampled in the groundwater of a former coking plant was carried out in a glass bead column.

Multistep thermodesorption coupled with molecular analyses as a quick, easy and environmentally friendly way to measure PAH availability in contaminated soils.

Whether it is for risk assessment or for remediation purpose, contaminant availability in polluted soils is a key parameter to determine. Two methods were recently standardized for the estimation of the environmental available fraction of non-polar organics but, in some cases, their application on real historically contaminated soils does not provide satisfactory results. The present study aimed at proposing an alternative method for the estimation of PAH availability in soils, based on analytical thermal desorption and molecular analyses with the hypothesis that the binding strength between PAH and the solid matrix is linked to the desorption temperature.

Fenton-like and potassium permanganate oxidations of PAH-contaminated soils: Impact of oxidant doses on PAH and polar PAC (polycyclic aromatic compound) behavior.

Potassium permanganate and Fenton-like oxidations were applied on two PAH-contaminated soils collected on former coking plant and gas plant sites. The impact of oxidant dose on the polycyclic aromatic compound (PAC) evolution, including 16 US-EPA PAHs, 11 oxygenated- and 4 nitrogen heterocyclic-PACs (O- and N-PACs) was studied for both treatments. The content of extractable organic matter and PACs was determined prior and after oxidation.

Aging as the main factor controlling PAH and polar-PAC (polycyclic aromatic compound) release mechanisms in historically coal-tar-contaminated soils.

In industrial sites, historically contaminated by coal tar (abandoned coking and manufactured gas plants), other families of organic pollutants than the 16 PAHs (polycyclic aromatic hydrocarbons) classified by the US-EPA can occur and induce potential risk for groundwater resources. Polar PACs (polycyclic aromatic compounds), especially oxygenated and nitrogenated PACs (O-PACs and N-PACs), are present in the initial pollution and can also be generated over time (i.e.

Fast method to quantify PAHs in contaminated soils by direct thermodesorption using analytical pyrolysis.

A method for polycyclic aromatic hydrocarbon (PAH) quantification, based on pyrolysis at 450°C combined with gas chromatography coupled with mass spectrometry and flame ionization detection (Py-GC-MS/FID), was developed and compared to a conventional PAH quantification method using accelerated solvent extraction and GC-MS analyses. The PAH contents of three coking plant soils, one gas plant soil, two wood-treating facility soils and one certified reference material (CRM - BCR 524) were determined using both methods. The results obtained with both methods showed a good match, especially in the case of the CRM.

Bioremediation of PAH-contamined soils: Consequences on formation and degradation of polar-polycyclic aromatic compounds and microbial community abundance.

A bioslurry batch experiment was carried out over five months on three polycyclic aromatic compound (PAC) contaminated soils to study the PAC (PAH and polar-PAC) behavior during soil incubation and to evaluate the impact of PAC contamination on the abundance of microbial communities and functional PAH-degrading populations. Organic matter characteristics and reactivity, assessed through solvent extractable organic matter and PAC contents, and soil organic matter mineralization were monitored during 5 months. Total bacteria and fungi, and PAH-ring hydroxylating dioxygenase genes were quantified.

Effect of thermal pre-treatment on the availability of PAHs for successive chemical oxidation in contaminated soils.

This is the premier study designed to evaluate the impact of thermal pre-treatment on the availability of polycyclic aromatic hydrocarbons (PAHs) for successive removal by chemical oxidation. Experiments were conducted in two soils having different PAH distribution originating from former coking plant sites (Homécourt, H, and Neuves Maisons, NM) located in northeast of France. Soil samples were pre-heated at 60, 100, and 150 °C for 1 week under inert atmosphere (N2).

Behavior of PAH/mineral associations during thermodesorption: impact for the determination of mineral retention properties towards PAHs.

Polycyclic aromatic hydrocarbons (PAHs) associated with two minerals (silica sand and bentonite) presenting opposite retention properties were analyzed with a thermodesorption (Td)-GC-MS coupling in order to validate this technique as a new and rapid way to evaluate the solid sorption properties. Two analysis modes were used, evolved gas analysis (EGA) and Td with cryo-trap. EGA allowed a real-time monitoring of the compounds desorbed during a temperature program and gave a first screening of the samples while Td gave more precise indications on compound abundances for selected temperature ranges.

Effect of pre-heating on the chemical oxidation efficiency: implications for the PAH availability measurement in contaminated soils.

Three chemical oxidation treatments (KMnO4, H2O2 and Fenton-like) were applied on three PAH-contaminated soils presenting different properties to determine the potential use of these treatments to evaluate the available PAH fraction. In order to increase the available fraction, a pre-heating (100 °C under N2 for one week) was also applied on the samples prior oxidant addition. PAH and extractable organic matter contents were determined before and after treatment applications.

Role of goethite during air-oxidation of PAH-contaminated soils.

The impact of goethite on air-oxidation of PAH-contaminated soils was studied through two sets of experiments. (i) Soil extractable organic matter (EOM) and (ii) whole coking plant soils were oxidized at 60 and 100 °C for 160 d, with/without goethite. Organic matter (OM) mineralization was monitored via CO2 production and polycyclic aromatic compounds (PACs) oxidation was investigated by GC–MS analyses.

Two-dimensionally stacked heterometallic layers hosting a discrete chair dodecameric ring of water clusters: synthesis and structural study.

The stacked two-dimensional supramolecular compound catena-{Co(amp)3Cr(ox)3·6H2O} (amp = 2-picolylamine, ox = oxalate) has been synthesized from the bimolecular approach using hydrogen bonds. It is built from layers in which both Co(amp)(3+) (D) and Cr(ox)(3-) (A) ions are bonded in a repeating DADADA… pattern along the a and c axes by multiple hydrogen bonds. These layers host a well resolved R12 dodecameric discrete ring of water clusters built by six independent molecules located around the 2c centrosymmetric Wyckoff positions of the P21/n space group in which the compound crystallizes.

Evolution of dissolved organic matter during abiotic oxidation of coal tar--comparison with contaminated soils under natural attenuation.

In former coal transformation plants (coking and gas ones), the major organic contamination of soils is coal tar, mainly composed of polycyclic aromatic compounds (PACs). Air oxidation of a fresh coal tar was chosen to simulate the abiotic natural attenuation impact on PAC-contaminated soils. Water-leaching experiments were subsequently performed on fresh and oxidized coal tars to study the influence of oxidation on dissolved organic matter (DOM) quality and quantity.

Impact of clay mineral on air oxidation of PAH-contaminated soils.

This work investigated the impact of a clay mineral (bentonite) on the air oxidation of the solvent extractable organic matters (EOMs) and the PAHs from contaminated soils. EOMs were isolated from two coking plant soils and mixed with silica sand or bentonite. These samples, as well as raw soils and bentonite/soil mixtures, were oxidized in air at 60 and 100 °C for 160 days.

A Technosol as archives of organic matter related to past industrial activities.

To better understand formation, functioning and evolution of a Technosol developing on a former settling pond of iron industry under forest cover, organic matter (OM) of layers along the soil profile was investigated. Spectroscopic and molecular analyses of extractable OM gave information on OM origin and state of preservation. In the surface layer, OM fingerprints indicated fresh input from vegetation while they revealed well preserved anthropogenic compounds related to industrial processes in deeper layers.

Impact of oxidation and biodegradation on the most commonly used polycyclic aromatic hydrocarbon (PAH) diagnostic ratios: Implications for the source identifications.

Based on the isomer stability during their formation, PAH diagnostic ratios have been extensively used to determine PAH contamination origin. Nevertheless, it is known that these isomers do not present the same physicochemical properties and that reactions occurring during the transport from an atmospheric source induce changes in the diagnostic ratios. Yet, little is known about reactions occurring in soils contaminated by other sources such as coal tar and coal.

The use of sterol distributions combined with compound specific isotope analyses as a tool to identify the origin of fecal contamination in rivers.

The sterol distributions of 9 sediment samples from the Illinois River Basin (OK and AR, USA) were examined in order to identify the source of fecal contamination. The samples were extracted with organic solvent using sonication and the fractions containing the sterols were isolated and analyzed by gas chromatography-mass spectrometry. The sterol distributions of the Illinois River samples were dominated by phytosterols.

In situ assessment of phytotechnologies for multicontaminated soil management.

Due to human activities, large volumes of soils are contaminated with organic pollutants such as polycyclic aromatic hydrocarbons, and very often by metallic pollutants as well. Multipolluted soils are therefore a key concern for remediation. This work presents a long-term evaluation of the fate and environmental impact of the organic and metallic contaminants of an industrially polluted soil under natural and plant-assisted conditions.

Low temperature oxidation of a coking plant soil organic matter and its major constituents: an experimental approach to simulate a long term evolution.

In contaminated soils, several natural processes (biodegradation, oxidation, etc.) can induce degradation of organic pollutants. The aim of this work was to evaluate the impact of an abiotic low-temperature oxidation on a coking plant soil and its main organic constituents (coal, coke, coal tar and road asphalts) in order to understand its long term evolution.