Assessing Transformations of Algal Organic Matter in the Long-Term: Impacts of Humification-Like Processes.

Algae and cyanobacteria are important contributors to the natural organic matter (NOM) of eutrophic water resources. The objective of this work is to increase knowledge on the modifications of algal organic matter (AOM) properties in the long term to anticipate blooms footprint in such aquatic environments. The production of AOM from an alga (Euglena gracilis) and a cyanobacteria (Microcystis aeruginosa) was followed up and characterized during the stationary phase and after one year and four months of cultivation, in batch experiments. Specific UV absorbance (SUVA) index, organic matter fractionation according to hydrophobicity and apparent molecular weight were combined to assess the evolution of AOM. A comparison between humic substances (HS) mainly derived from allochthonous origins and AOM characteristics was performed to hypothesize impacts of AOM transformation processes on the water quality of eutrophic water resources. Each AOM fraction underwent a specific evolution pattern, depending on its composition. Impacts of humification-like processes were predominant over release of biopolymers due to cells decay and led to an increase in the hydrophobic compounds part and molecular weights over time. However, the hydrophilic fraction remained the major fraction whatever the growth stage. Organic compounds generated by maturation of these precursors corresponded to large and aliphatic structures.

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) coupled to XAD fractionation: Method to algal organic matter characterization.

This work is focused on the development of an analytical procedure for the improvement of the Organic Matter structure characterization, particularly the algal matter. Two fractions of algal organic matter from laboratory cultures of algae (Euglena gracilis) and cyanobacteria (Microcystis aeruginosa) were extracted with XAD resins. The fractions were studied using laser desorption ionization (LDI) and Matrix-Assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF). A comparison with the natural organic matter characteristics from commercial humic acids and fulvic acids extracted from Suwannee River was performed. Results show that algal and natural organic matters have unique quasi-polymeric structures. Significant repeating patterns were identified. Different fractions extracted from organic matter with common origin had common structures. Thus, 44, 114 and 169Da peaks separation for fractions from E. gracilis organic matter and 28, 58 and 100Da for M. aeruginosa ones were clearly observed. Using the developed protocol, a structural scheme and organic matter composition were obtained. The range 600-2000Da contained more architectural composition differences than the range 100-600Da, suggesting that organic matter is composed of an assembly of common small molecules. Associated to specific monomers, particular patterns were common to all samples but assembly and resulting structure were unique for each organic matter. Thus, XAD fractionation coupled to mass spectroscopy allowed determining a specific fingerprint for each organic matter.

Organic matter produced by algae and cyanobacteria: quantitative and qualitative characterization.

This work aims at characterizing organic matter produced by an alga Euglena gracilis and a cyanobacteria Microcystis aeruginosa and assessing the evolution of its characteristics during growth. A culture medium was optimized. The species growth phases were monitored using both visible spectrophotometry and flow cytometry cell counting. Organic matter fractionation according to hydrophobicity and specific UV absorbance (SUVA) index were used to specifically characterize the produced algal organic matter (AOM). The AOM characteristics were both growth phase and species dependent. However, a similar evolution was observed. The hydrophilic fraction (HPI) was the major fraction whatever the growth phases and was almost the only one produced during lag and exponential phases. It represented around 75% of AOM during exponential phase and then decreased when the stationary phase appeared. It represented 46% and 60% of the AOM during late decline phase for the cyanobacteria and the alga respectively. The hydrophobic (HPO) and transphilic (TPH) fractions started to appear from the beginning of the stationary phase with more hydrophobic compounds coming from intracellular organic material of dying cells. HPO and TPH percentages still increased during the decline phase probably because of two additional processes: photo-dissolution and leaching of particulate organic matter from cells fragments. A comparison of AOM during late decline phase and natural organic matter (NOM) from Glane River (France) underlined that AOM was more hydrophilic and presented a lower SUVA for each fractions than NOM. However, the difference between NOM and AOM hydrophobicity narrowed during decline phase.

Formation of iodinated organic compounds by oxidation of iodide-containing waters with manganese dioxide.

This study shows that iodinated organic compounds can be produced when iodide-containing waters are in contact with manganese oxide birnessite (delta-MnO2) in the pH range of 5-7. In the absence of natural organic matter (NOM), iodide is oxidized to iodate that is also adsorbed onto delta-MnO2. In the presence of iodide and NOM, adsordable organic iodine compounds (AOI) are formed at pH < 7 because of the oxidation of iodide to iodine by delta-MnO2 and the reactions of iodine with NOM. In addition, iodoacetic acid and iodoform have been identified as specific iodinated byproducts. Formation of iodoform is not observed for high NOM/delta-MnO2 ratios due to inhibition of the catalytic effect of delta-MnO2 by NOM poisoning. Experiments with model compounds such as resorcinol and 3,5-heptanedione confirmed that the delta-MnO2/l(-) system is very effective for the formation of iodinated organic compounds. These results suggest that birnessite acts as a catalyst through the oxidation of iodide to iodine and the polarization of the iodine molecule, which then reacts with NOM moieties. Furthermore, our results indicate that during water treatment in the presence of manganese oxide, iodinated organic compounds may be formed, which may lead to taste and odor or toxicological problems.

Oxidation of iodide and iodine on birnessite (delta-MnO2) in the pH range 4-8.

The oxidation of iodide by synthetic birnessite (delta-MnO(2)) was studied in perchlorate media in the pH range 4-8. Iodine (I(2)) was detected as an oxidation product that was subsequently further oxidized to iodate (IO(3)(-)). The third order rate constants, second order on iodide and first order on manganese oxide, determined by extraction of iodine in benzene decreased with increasing pH (6.3-7.5) from 1790 to 3.1M(-2) s(-1). Both iodine and iodate were found to adsorb significantly on birnessite with an adsorption capacity of 12.7 microM/g for iodate at pH 5.7. The rate of iodine oxidation by birnessite decreased with increasing ionic strength, which resulted in a lower rate of iodate formation. The production of iodine in iodide-containing waters in contact with manganese oxides may result in the formation of undesired iodinated organic compounds (taste and odor, toxicity) in natural and technical systems. The probability of the formation of such compounds is highest in the pH range 5-7.5. For pH <5 iodine is quickly oxidized to iodate, a non-toxic and stable sink for iodine. At pH >7.5, iodide is not oxidized to a significant extent.

Study of interactions of concentrated marine dissolved organic matter with copper and zinc by pseudopolarography.

The interaction of dissolved organic matter (DOM) with copper and zinc in a concentrated seawater sample was characterised by pseudopolarography. Measurements performed at increased concentrations of copper(II) ions showed successive saturation of active DOM sites which indicate possible partition of copper between (i) free or labile complexes, (ii) reduced and released within the potential window of the method, and (iii) electroinactive copper complexes. Pseudopolarograms measured at pH 4 indicate a release of copper which was bound to the active sites of DOM that formed non-labile complexes. Variation of the peak position and half-peak width along the scanned deposition potentials and with the increasing concentration of copper bear the information about the complex electrochemical processes at the electrode surface and in the bulk of the solution. Pseudopolarograms of zinc showed a strong dependence of the peak current and the peak position along the scanned deposition potentials on pH values, indicating preferentially complexation of zinc with carboxylic-like active sites of DOM in the measured sample. Pseudopolarography is a valuable method in the trace metal complexation and speciation studies, serving as a fingerprint of the analysed sample.