"PAW" a smart analytical process assessing lipophilicity of solutes in mixtures.

BACKGROUND: The analysis of mixtures of contaminants remains a challenging task in many fields, including water quality and waste management. For example, the degradation of industrial waste such as plastics, leads to complex mixtures with hundreds of organic contaminants and often non-referenced analytes. In such cases, non-targeted or effects-based analyses provide complementary information to classical targeted-analyses, regarding contaminants nature or properties (molecular mass, lability, toxicity). In this study, a novel analytical method is proposed to characterise mixtures of unknown organic contaminants, with a focus on the lipophilicity of solutes. RESULTS: The proposed process, named "PAW" (Partition of Aqueous Waste), aims at the quantification of octanol-water partition coefficients (POW) of mixed organic analytes. The process is based on sequential liquid-liquid partition equilibria. The output result is a lipophilicity histogram of the solutes, screened according to the chosen detection method. The process quantifies the distribution of analytes as a function of their octanol-water partition coefficients, without requiring any identification or prior knowledge. The PAW process is applicable with various detectors (UV-Visible, total carbon, liquid scintillation, etc.) allowing to focus on specific families of contaminants (e.g. organic solutes, colloids, 14C-bearing, etc.). Experimental proofs of concept are proposed, illustrating process implementation and possible fields of application. The first example deals with purity analysis of synthetic radiolabeled compounds. The second example aims the monitoring of cellulose degradation and quantification of the lipophilicity of degradation products. SIGNIFICANCE: The PAW analytical process seems especially useful for characterisation of mixtures containing both hydrophilic and lipophilic compounds, e.g. neutral and ionizable organic contaminants, hardly characterisable simultaneously by chromatographic methods. It could be complementary to more detailed targeted or screening analysis of samples and effluents. For example it may help assessing the composition and environmental fate of mixtures of unknown analytes, thus facilitating waste management or mitigation strategies.

Diffusion of organic anions in clay-rich media: Retardation and effect of anion exclusion.

The transport of emerging organic contaminants through the geosphere is often an environmental issue. The sorption of organic compounds slows their transport in soils and porous rocks and retardation is often assessed by extrapolation of batch experiments. However, transport experiments are preferable to strengthen migration data and modelling. In this context, we evaluated the adsorption of various organic acids by means of through-diffusion experiments in a sedimentary clay-rich rock (Callovo-Oxfordian, East of Paris Basin, France). A low diffusivity of organic anions was quantified with effective diffusion coefficients, De, ranged between 0.5 and 7 10-12 m2 s-1. These values indicated an organic anion exclusion. As for chloride, the porosity accessible to organic anions was lower than that of water: εa(organic anions) < ε(water). The partial exclusion of organic anions from rock porosity was linked to both charge and size effects. A significant retardation was observed for organic anions such as oxalate, citrate or α-isosaccharinate. Yet, retardation measured by diffusion experiments was significantly lower than expected from batch experiments on crushed samples. An empirical correction factor is proposed to account for a possible decrease of retardation with accessible porosity of diffusing solute. This feature has significant implications for the estimation of migration parameters of organic compounds in the environment.

Adsorption of polar organic molecules on sediments: Case-study on Callovian-Oxfordian claystone.

The release and transport of anthropogenic organic matter through the geosphere is often an environmental criterion of safety. Sedimentary rocks are widely studied in this context as geological barriers for waste management. It is the case of Callovian-Oxfordian claystone (COx), for which several studies report adsorption of anthropogenic organic molecules. In this study, we evaluated and reviewed adsorption data of polar organic molecules on COx claystone. Experiments were performed on raw claystone, decarbonated and clay fractions. Adsorption isotherms were measured with adsorbates of various polarities: adipate, benzoate, ortho-phthalate, succinate, gluconate, oxalate, EDTA, citrate. A significant adsorption was observed for multidentate polycarboxylic acids as evidenced with phthalate, succinate, oxalate, gluconate, EDTA and citrate (Rd = 1.53, 3.52, 8.4, 8.8, 12.4, 54.7 L kg-1 respectively). Multiple linear regression were performed as a statistical analysis to determine the predictors from these adsorption data. A linear correlation between adsorption data (Rd) and dipole moment (µ) of adsorbates was evidenced (R2 = 0.91). Molecules with a high dipole moment, µ(D) > 2.5, displayed a significant adsorption, Rd≫1 L kg-1. A qualitative correlation can be easily estimated using the water/octanol partition coefficient, Pow, of adsorbates (R2 = 0.77). In this case, two opposite trends were distinguished for polar and apolar molecules. The use of organic carbon content in sediments is relevant for predicting adsorption of apolar compounds, log (Pow)>+1. The oxides/clays contents may be relevant regarding polar molecules, log (apparentPow)<-1. The proposed scheme offers a general methodology for investigation of geo-barriers towards heterogeneous organic plumes.

Various causes behind the desorption hysteresis of carboxylic acids on mudstones.

Adsorption desorption is a key factor for leaching, migration and (bio)degradation of organic pollutants in soils and sediments. Desorption hysteresis of apolar organic compounds is known to be correlated with adsorption/diffusion into soil organic matter. This work focuses on the desorption hysteresis of polar organic compounds on a natural mudstone sample. Acetic, citric and ortho-phthalic acids displayed adsorption-desorption hysteresis on Callovo-Oxfordian mudstone. The non-reversible behaviours resulted from three different mechanisms. Adsorption and desorption kinetics were evaluated using 14C- and 3H-labelled tracers and an isotopic exchange method. The solid-liquid distribution ratio of acetate decreased using a NaN3 bactericide, indicating a rapid bacterial consumption compared with negligible adsorption. The desorption hysteresis of phthalate was apparent and suppressed by the equilibration of renewal pore water with mudstone. This confirms the significant and reversible adsorption of phthalate. Finally, persistent desorption hysteresis was evidenced for citrate. In this case, a third mechanism should be considered, such as the incorporation of citrate in the solid or a chemical perturbation, leading to strong desorption resilience. The results highlighted the different pathways that polar organic pollutants might encounter in a similar environment. Data on phthalic acid is useful to predict the retarded transport of phthalate esters and amines degradation products in sediments. The behaviour of citric acid is representative of polydentate chelating agents used in ore and remediation industries. The impact of irreversible adsorption on solid/solution partitioning and transport deserves further investigation.