Gilles Varrault

Dissolved organic matter from treated effluent of a major wastewater treatment plant: Characterization and influence on copper toxicity

A combination of reverse osmosis (RO) concentration and DAX-8/XAD-4 resin adsorption techniques is used to isolate the various constituents of urban dissolved organic matter (DOM) from inorganic salts. Three fractions: hydrophobic (HPO), transphilic (TPI) and hydrophilic (HPI) accounting respectively for 35%, 20% and 45% of extracted carbon, are isolated from effluents of a major French wastewater treatment plant. This atypical DOC distribution, in comparison with natural water where the HPO fraction dominates, shows the significance of HPI fraction which often gets neglected because of extraction difficulties. A number of analytical techniques (elemental, spectroscopic: UV, FTIR) allow highlighting the weak aromaticity of wastewater effluent DOM (EfOM) due to fewer degradation and condensation processes and the strong presence of proteinaceous structures indicative of intense microbial activity. Copper toxicity in the presence of DOM is estimated using an acute toxicity test on Daphnia Magna (Strauss). Results reveal the similar protective role of each EfOM fraction compared to reference Suwannee river fulvic acid despite lower EfOM aromaticity (i.e. specific UV absorbance). The environmental implications of these results are discussed with respect to the development of site-specific water quality criteria.

Lead accumulation in the roots of grass pea (Lathyrus sativus L.): a novel plant for phytoremediation systems?

Eleven day-old grass pea plants (Lathyrus sativus L.) were grown hydroponically for 96 h in the presence of 0.5 mM lead nitrate (Pb(NO(3))(2)). The survival rate was 100%. The mean lead content (measured by ICP-OES) in root tissues was 153 mg Pb g(-1) dry matter. Over three quarters of the lead was not labile. Compared with control plants, lead-exposed plants showed a six-fold, two-fold and three and a half-fold reduction in their root calcium, zinc and copper contents, respectively. Together, these results suggested that Lathyrus sativus L. was tolerant to a deficiency in essential nutrients and able to store large amounts of lead in its root tissues. Therefore, it could be used for the development of new rhizofiltration systems.

Accumulation of lead in the roots of grass pea (Lathyrus sativus L.) plants triggers systemic variation in gene expression in the shoots.

The impact of lead nitrate (Pb(NO(3))(2); 0.5mM) on steady-state accumulation of messengers corresponding to stress responsive genes was studied in two local lines of 11-d grass pea (Lathyrus sativus L.) plants exposed for 96 h in a hydroponic system. Real-time reverse transcription polymerase chain reaction technique was used with grass pea-specific primers designed from newly isolated partial cDNA. Increases in accumulation of glutathione reductase, ascorbate peroxidase and glutathione S-transferase transcripts suggested that roots enhanced detoxification mechanisms involving glutathione. In the leaves where no lead was translocated, the pollutant indirectly triggered increases in expression of several genes. This process probably resulted from systemic signals originating from the roots where lead accumulated in large amounts, approximately 150 mg Pbg(-1) dry weight. A preventive and/or adaptive role for the signal is assumed, since it concerned genes implicated in reactive oxygen species scavenging (ascorbate peroxidase), protein protection (heat shock protein 70) and proteolysis (cysteine and aspartic proteases).

Implications of effluent organic matter and its hydrophilic fraction on zinc(II) complexation in rivers under strong urban pressure: Aromaticity as an inaccurate indicator of DOM-metal binding

The zinc binding characteristics of dissolved organic matter (DOM) fractions from the Seine River Basin were studied after being separated and extracted according to their polarity: hydrophobic, transphilic, and hydrophilic. The applied experimental methodology was based on a determination of labile zinc species by means of differential pulse anodic stripping voltammetry (DPASV) at increasing concentrations of total zinc on a logarithmic scale and at fixed levels of: pH, ionic strength, and temperature. Fitting the DOM fractions with two discrete classes of ligands successfully allowed determining the conditional zinc binding constants (Ki) as well as total ligand density (LiT). The binding constants obtained for each DOM fraction were then compared and discussed with respect to the hydrophobic/hydrophilic nature and sample origin. Results highlighted a strong complexation of zinc to the effluent organic matter and especially the most hydrophilic fraction, which also displayed a very low specific UV absorbance. Although the biotic ligand model takes into account the quality of DOM through UV absorbance in the predictions of metal bioavailability and toxicity, this correction is not efficient for urban waters.

Kinetics as a tool to assess the immobilization of soil trace metals by binding phase amendments for in situ remediation purposes

Many soil remediation techniques consist in decreasing the mobility of trace metals by means of adding trace metal binding phases. For this study, whose aim is to assess the efficiency of soil remediation method by binding phase amendment, a kinetic fractionation method that provides the labile and slowly labile trace metal amounts in soil has been introduced. Manganese oxides (vernadite) and insolubilized humic acids (IHA) have been used as binding phases for the remediation of four heavily polluted soils. Vernadite amendments are effective for lead and cadmium remediation, whereas IHA amendments are only effective for copper remediation. In most cases, the labile metal fractions decrease dramatically in amended soils (up to 50%); on the other hand, the amounts of total extracted metal near the point of thermodynamic equilibrium often show no significant difference between the amended soil and the control soil. These results highlight the utility of kinetic fractionation in assessing the efficiency of soil remediation techniques and, more generally, in evaluating trace metal mobility in soils and its potential advantages compared to extraction schemes performed under equilibrium conditions. In the future, this kinetic method could be considerably simplified so as to consume much less time allowing its routine use.

In situ speciation of trace Fe(II) and Fe(III) in atmospheric waters by the FZ method coupled to GFAAS analysis

A quasi-on-line method of measurement of the oxidation states of iron coupled with a GFAAS analysis is reported for the trace conditions found in atmospheric waters. This technique is based on the formation of a specific complex [Fe(FZ)3]4− between Fe(II) and ferrozine (FZ). tC18 solid-phase extraction cartridges (Sep-Pak) are used to separate the [Fe(FZ)3]4− and Fe(III) so as to limit the risk of redox evolution of the sample. The adaptation to dilute aqueous media, via acidification at pH = 2 of rainwater sample, and atmospheric interferences are discussed, and the Fe(II) recovery in rainwaters is determined. This method coupled with a quasi-on-line sampling protocol has been tested on rains collected in Guadeloupe Island (Caribbean Sea, 16°N, 61°W) during a field campaign in May 2005. Our results show that the proposed method can satisfactorily be applied to the determination of Fe(II) and Fe(III) in atmospheric waters under in situ conditions.

Contribution of domestic effluents to hydrocarbon levels of dry weather flow in combined sewers

The importance of hydrocarbon contamination of the sewer network has been reported by many authors recently. Most of the studies are focused on the introduction of such pollutants into combined sewers by street and roof stormwater, but few evaluate the contribution of domestic inputs to hydrocarbon pollution. As a consequence, this work—carried out on the framework of the OPUR (Observatory of Urban Pollutants) research program—assesses the resolved aliphatic (AH), unresolved complex mixture (UCM) and polycyclic aromatic hydrocarbon (PAH) concentrations of domestic effluents (DE) and evaluates the role played by such effluents on the hydrocarbon levels of dry weather flow (DWF) in combined sewers. Results show hydrocarbon concentrations in the 200 – 300 μg · l−1, 300 – 1 000 μg · l−1 and 0.9 – 1.4 μg · l−1 ranges for AHs, UCM and the 16 PAHs of the US-EPA, respectively. The assessment of hydrocarbon fluxes conveyed by domestic effluents on the scale of the ‘Le Marais’ experimental urban catchment (42 ha, centre of Paris) reveals the predominant contribution of domestic inputs to the DWF pollution and highlights the unsuspected role of households.

Application of a refractory organic matter quantification method to wastewater effluents.

An already established analytical method for the quantification of freshwater refractory organic matter (often called humic substances) has been applied to organic matter from a wastewater treatment plants effluent and a number of downstream locations impacted by the treatment plant. The method is based on measuring the peak currents obtained by adsorptive stripping voltammetry of the complex formed by freshwater refractory organic matter in the presence of trace amounts of Mo(VI). Organic matter is first concentrated by reverse osmosis, then fractionated according to its polarity by the sequential application of DAX-8 and XAD-4 resins. The results obtained show that the voltammetric method measures the refractory organic matter present in the different sewage-derived fractions and that the response obtained follows the trend expected for the fractionation method used (i.e. more hydrophobic fractions largely give the strongest signals). These results have been compared with those obtained from IHSS substances. The results of this study are of particular significance in that it shows that, when applied to surface waters, the voltammetric method measures any refractory organic matter present, irrespective of its origin.

Research of trace metals as markers of entry pathways in combined sewers

Combined sewers receive high toxic trace metal loads emitted by various sources, such as traffic, industry, urban heating and building materials. During heavy rain events, Combined Sewer Overflows (CSO) can occur and, if so, are discharged directly into the aquatic system and therefore could have an acute impact on receiving waters. In this study, the concentrations of 18 metals have been measured in 89 samples drawn from the three pollutant Entry Pathways in Combined Sewers (EPCS): i) roof runoff, ii) street runoff, and iii) industrial and domestic effluents and also drawn from sewer deposits (SD). The aim of this research is to identify metallic markers for each EPCS; the data matrix was submitted to principal component analysis in order to determine metallic markers for the three EPCS and SD. This study highlights the fact that metallic content variability across samples from different EPCS and SD exceeds the spatio-temporal variability of samples from the same EPCS. In the catchment studied here, the most valuable EPCS and SD markers are lead, sodium, boron, antimony and zinc; these markers could be used in future studies to identify the contributions of each EPCS to CSO metallic loads.

Study of the Optical Properties of Dissolved Organic Matter in the Seine River Catchment (France)

In this study, the optical properties of dissolved organic matter (DOM) were investigated using UV/visible photometry and excitation emission matrix (EEM) fluorescence spectroscopy. Differences in quality and quantity of organic carbon were observed and highlighted discrimination of organic matter typologies between the four studied areas in the catchment of the Seine river.