Pierre Doumenq

Hydrocarbon balance of a site which had been highly and chronically contaminated by petroleum wastes of a refinery (from 1956 to 1992)

Petroleum hydrocarbon pollution in the Gulf of Fos (South France) was studied following the cessation of petroleum waste discharge from an oil refinery in the Lavera area. Sediments were collected in core samples of 30 cm at eight stations along a radial from the refinery to the open sea. Petroleum contamination has been detected up to the beginning of the open sea but decreased gradually (from 40 to 3 g kg−1 sediment dry wt). GC profiles (aliphatics and aromatics) are characteristic of petroleum. They reveal the disappearance of short chain n-alkanes (up to C25) and of one and two aromatic ring compounds, the increase and the modification of the UCM depends on the depth and the situation, resulting from weathering processes. Biomarkers and three to five aromatic ring compounds are unaltered whatever the depth and the location. If some petroleum hydrocarbons are present for the open sea stations (perhaps from other sources), natural and pyrolytic hydrocarbons are also detected. Sediments from the open sea could be considered to be unpolluted (less than 0.1 g kg−1), and unaffected by the refinery wastes two years after the end of overspills.

Distributions and sources of persistent organic pollutants (aliphatic hydrocarbons, PAHs, PCBs and pesticides) in surface sediments of an industrialized urban river (Huveaune), France

Surface sediments from the Huveaune River were analyzed for n-alkanes, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine and organophosphorous pesticides (OCs and OPs) by using gas chromatography-mass spectrometry (GC-MS). Concentrations of total alkanes ranged from 184 to 26,780 μg·kg(-1) sediment dry weight (dw) with a mean concentration of 6,126 ± 8,006 μg·kg(-1)dw, concentrations of total PAHs ranged from 572 to 4,235 μg·kg(-1)dw with a mean concentration of 1966 ± 1,104 μg·kg(-1) dw, concentrations of total PCB ranged from 2.8 to 435 μg·kg(-1)dw with a mean concentration of 148 ± 164 μg·kg(-1)dw and concentrations of total pesticides ranged from 0.07 to 1.25 μg·kg(-1)dw with a mean concentration of 1.23 ± 1.29 μg·kg(-1)dw. The spatial distribution of POPs reveals that pollutant concentration is relatively higher at the mouth of the river. The molecular indices of specific n-alkanes (CPI, NAR and TAR) and molecular indices of PAHs (Ant/(Ant+Phe), Fl/(Fl+Pyr), BaA/(BaA+Chry), IPyr/(Ipyr+BghiP)) were calculated to evaluate the possible sources of hydrocarbons. These molecular indices suggest mainly pyrolytic inputs which are markedly biogenic. All contaminant levels were also compared with Sediments Quality Guidelines (SQG) showing that the contamination levels in all stations were most of the time lower than their respective SQG. While, for PCBs, five stations (H5, H6, H7, H8 and H9) were higher than their effect range median (ERM) values which may indicate high potential toxicity of the sediment with probable adverse effects to the living biota.

Long term evolution of petroleum biomarkers in mangrove soil (Guadeloupe)

Abstract In March 1986, plots of a peaty mangrove were delimited and polluted by Arabian Light crude oil. Superficial sediments were sampled (0–5; 5–10 and 10–20 cm core section) in 1987, 1990, 1994 and petroleum hydrocarbons were analysed by FID-GC, high resolution GC-MS and MRM GC-MS. One year later, no significant evolution of the petroleum chemical composition was noted. Four years later, n -alkanes had strongly decreased and isoprenoids were predominant. Eight years later, isoprenoids were severely degraded and biomarkers were more or less altered as follows in the declining order of importance: steranes > hopanes > bicyclic terpanes > triand tetracyclic terpanes > diasteranes > norhopanes and triaromatic steroids > C-ring monoaromatic steroids. For steranes, the following order of degradation can be proposed C 26 > C 27 > C 28 > C 29 > C 30 with the stereochemical degradation sequence aaa 20R > αββ 20(R + S) > ααα 20S. Regarding pentacyclic terpanes, a decreasing removal is observed in the order C 35 > C 34 > C 33 > C 32 > C 31 with a preferential degradation of the 22R epimers compared to the 22S epimers. The C 30 -17α(H), 21β(H)-hopane appears more sensitive to weathering than its higher homologues. We also observed that there was selective degradation with drimanes/homodrimanes, diasteranes/steranes and norhopanes/hopanes. A light depletion of the C 20 –C 21 triaromatic steroids can be noted whereas no degradation of C-ring monoaromatic steroids is observed. Biomarkers, widely used in geochemistry, can be also used to follow the weathering of petroleum in natural conditions and can be considered as environmental markers.

From the conventional biological wastewater treatment to hybrid processes, the evaluation of organic micropollutant removal: A review

Because of the recalcitrance of some micropollutants to conventional wastewater treatment systems, the occurrence of organic micropollutants in water has become a worldwide issue, and an increasing environmental concern. Their biodegradation during wastewater treatments could be an interesting and low cost alternative to conventional physical and chemical processes. This paper provides a review of the organic micropollutants removal efficiency from wastewaters. It analyses different biological processes, from conventional ones, to new hybrid ones. Micropollutant removals appear to be compound- and process- dependent, for all investigated processes. The influence of the main physico-chemical parameters is discussed, as well as the removal efficiency of different microorganisms such as bacteria or white rot fungi, and the role of their specific enzymes. Even though some hybrid processes show promising micropollutant removals, further studies are needed to optimize these water treatment processes, in particular in terms of technical and economical competitiveness.

Monitoring of the evolution of an industrial compost and prediction of some compost properties by NIR spectroscopy

Sewage treatment plants produce wastes resulting from the organic matter concentration in the form of sludge. A way of jointly treating and exploiting these increasing wastes jointly is the composting. Composting makes it possible to reduce volumes and the masses of wastes all while developing them in a product usable like organic soil enrichment. In this work, the composting process of an industrial sewage sludge composting plant was monitored to study the evolution of different physico-chemical parameters (temperature, moisture, pH, organic carbon, organic and inorganic nitrogen, organic carbon/organic nitrogen ratio, humic substances) and biochemical parameters (soluble fraction, hemicellulose, cellulose, lignin). Because these analyses are expensive and time consuming, we wanted to develop an alternative method to determine the maturity of compost related to compost properties with raw samples. Acceptable predictions were found for moisture, temperature, pH, organic carbon, organic carbon/organic nitrogen ratio, total-, organic- and ammoniacal nitrogen, fulvic- and humic acids and fulvic acids/humic acids ratio, but the error values were too high for the compost age to consider a quantification model. With regard to the biochemical parameters, this study is rather a preliminary test which shows the interest of the approach, but requires to be continued. Finally, the age of compost can be evaluated with Principal Component Analysis applied to NIR spectra.

Molecular Insights of Oxidation Process of Iron Nanoparticles: Spectroscopic, Magnetic, and Microscopic Evidence

Oxidation behavior of nano-Fe(0) particles in an anoxic environment was determined using different state-of-the-art analytical approaches, including high resolution transmission electron microscopy (HR-TEM) combined with energy filtered transmission electron microscopy (EFTEM), X-ray absorption spectroscopy (XAS), and magnetic measurements. Oxidation in controlled experiments was compared in standard double distilled (DD) water, DD water spiked with trichloroethene (TCE), and TCE contaminated site water. Using HR-TEM and EFTEM, we observed a surface oxide layer (∼3 nm) formed immediately after the particles were exposed to water. XAS analysis followed the dynamic change in total metallic iron concentration and iron oxide concentration for the experimental duration of 35 days. The metallic iron concentration in nano-Fe(0) particles exposed to water, was ∼40% after 35 days; in contrast, the samples containing TCE were reduced to ∼15% and even to nil in the case of TCE contaminated site water, suggesting that the contaminants enhance the oxidation of nano-Fe(0). Frequency dependence measurements confirmed the formation of superparamagnetic particles in the system. Overall, our results suggest that nano-Fe(0) oxidized via the Fe(0) - Fe(OH)2 - Fe3O4 - (γ-Fe2O3) route and the formation of superparamagnetic maghemite nanoparticles due to disruption of the surface oxide layer.

Assessment of potential positive effects of nZVI surface modification and concentration levels on TCE dechlorination in the presence of competing strong oxidants, using an experimental design

Nanoscale zero-valent iron (nZVI) particles are efficient for the remediation of aquifers polluted by trichloroethylene (TCE). But for on-site applications, their reactivity can be affected by the presence of common inorganic co-pollutants, which are equally reduced by nZVI particles. The aim of this study was to assess the potential positive effects of nZVI surface modification and concentration level on TCE removal in the concomitant presence of two strong oxidants, i.e., Cr(VI) and NO3(-). A design of experiments, testing four factors (i.e. nZVI concentration, nZVI surface modification, Cr(VI) concentration and NO3(-) concentration), was used to select the best trials for the identification of the main effects of the factors and of the factors interactions. The effects of these factors were studied by measuring the following responses: TCE removal rates at different times, degradation kinetic rates, and the transformation products formed. As expected, TCE degradation was delayed or inhibited in most of the experiments, due to the presence of inorganics. The negative effects of co-pollutants can be palliated by combining surface modification with a slight increase in nZVI concentration. Encouragingly, complete TCE removal was achieved for some given experimental conditions. Noteworthily, nZVI surface modification was found to promote the efficient degradation of TCE. When degradation occurred, TCE was mainly transformed into innocuous non-chlorinated transformation products, while hazardous chlorinated transformation products accounted for a small percentage of the mass-balance.

GC/FT-IR Analysis of Fatty Acid Methyl Esters:

An analytical method, based on coupled gas capillary chromatography and Fourier transform infrared spectrometry (GC/FT-IR), has been developed to determine the structure of fatty acid mixtures often found in the marine environment. In the case of saturated fatty acids, the method provides useful information concerning chain lengths and the presence of (1) branched methyl groups (iso or anteiso), (2) cyclopropanic structures, and (3) hydroxyl groups (two or three positions). Furthermore, the presence or absence of double bonds, as well as their stereochemistry and their number, in the case of cis polyunsaturated derivatives, can be determined. The method has required the development of a specific GC/FT-IR library of 46 fatty acid methyl esters generally found in the marine environment.

Parameters optimization using experimental design for headspace solid phase micro-extraction analysis of short-chain chlorinated paraffins in waters under the European water framework directive

The water framework directives (WFD 2000/60/EC and 2013/39/EU) force European countries to monitor the quality of their aquatic environment. Among the priority hazardous substances targeted by the WFD, short chain chlorinated paraffins C10-C13 (SCCPs), still represent an analytical challenge, because few laboratories are nowadays able to analyze them. Moreover, an annual average quality standards as low as 0.4μgL(-1) was set for SCCPs in surface water. Therefore, to test for compliance, the implementation of sensitive and reliable analysis method of SCCPs in water are required. The aim of this work was to address this issue by evaluating automated solid phase micro-extraction (SPME) combined on line with gas chromatography-electron capture negative ionization mass spectrometry (GC/ECNI-MS). Fiber polymer, extraction mode, ionic strength, extraction temperature and time were the most significant thermodynamic and kinetic parameters studied. To determine the suitable factors working ranges, the study of the extraction conditions was first carried out by using a classical one factor-at-a-time approach. Then a mixed level factorial 3×2(3) design was performed, in order to give rise to the most influent parameters and to estimate potential interactions effects between them. The most influent factors, i.e. extraction temperature and duration, were optimized by using a second experimental design, in order to maximize the chromatographic response. At the close of the study, a method involving headspace SPME (HS-SPME) coupled to GC/ECNI-MS is proposed. The optimum extraction conditions were sample temperature 90°C, extraction time 80min, with the PDMS 100μm fiber and desorption at 250°C during 2min. Linear response from 0.2ngmL(-1) to 10ngmL(-1) with r(2)=0.99 and limits of detection and quantification, respectively of 4pgmL(-1) and 120pgmL(-1) in MilliQ water, were achieved. The method proved to be applicable in different types of waters and show key advantages, such as simplicity, automation and sensitivity, required for the monitoring programs linked to the WFD.

Conservation of Moroccan manuscript papers aged 150, 200 and 800 years. Analysis by infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), and scanning electron microscopy energy dispersive spectrometry (SEM-EDS).

The preservation of manuscripts and archive materials is a serious problem for librarians and restorers. Paper manuscript is subjected to numerous degradation factors affecting their conservation state. This research represents an attempt to evaluate the conservation restoration process applied in Moroccan libraries, especially the alkaline treatment for strengthening weakened paper. In this study, we focused on six samples of degraded and restored paper taken from three different Moroccan manuscripts aged 150, 200 and 800 years. In addition, the Japanese paper used in restoration has been characterized. A modern paper was also analyzed as reference. A three-step analytical methodology based on infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD) and scanning electron microscopy coupled to energy dispersive spectrometry (SEM-EDS) analysis was developed before and after restoration in order to determine the effect of the consolidation treatment on the paper structure. The results obtained by XRD and ATR-FTIR disclosed the presence of barium sulfate (BaSO4) in all restored paper manuscripts. The presence of calcium carbonate (CaCO3) in all considered samples was confirmed by FTIR spectroscopy. The application of de-acidification treatment causes significant changes connected with the increase of intensity mostly in the region 1426 cm(-1), assigned to the asymmetric and symmetric CO stretching mode of calcite, indicating the effectiveness of de-acidification procedure proved by the rise of the alkaline reserve content allowing the long term preservation of paper. Observations performed by SEM magnify the typical paper morphology and the structure of fibbers, highlighting the effect of the restoration process, manifested by the reduction of impurities.