Biolixiviation des métaux lourds et stabilisation des boues municipales: effet de la forme du souffre élémentaire utilisé comme substrat Heavy metal bioleaching and stabilization of municipal sludges : effect of the form of elemental sulfur used as substrate

Résumé

La présence de concentrations élevées en métaux lourds retrouvés dans les boues de stations d'épuration est un facteur important limitant ainsi leurs différents modes de dispositions (rejet en mer, enfouissement, incinération, ou même recyclage comme fertilisant agricole ou forestier) par crainte de dégâts considérables qui pourraient être causés à l'environnement. L'objectif de ce travail consistait à mettre au point un procédé qui permettrait conjointement la stabilisation des boues municipales et l'enlèvement des métaux lourds qui y sont associés. L'approche poursuivie dans cette étude était de vérifier si ce procédé microbien, conçu pour enlever les métaux lourds associés aux boues municipales, pourrait éventuellement remplacer les procédés conventionnels de stabilisation des boues municipales, ce qui réduirait considérablement les temps et coûts de traitement. Ce procédé microbien consiste à utiliser des souches de thiobacilles qui oxydent le soufre élémentaire, produisant ainsi de l'acide sulfurique, et par la même occasion une forte baisse de pH (1.5). Les résultats obtenus en cultures discontinues, en bioréacteurs, avec des boues primaires provenant de la station d'épuration de la Communauté Urbaine de Québec (C.U.Q.- Est) montrent que cette chute de pH entraîne une solubilisation importante des métaux (Cr: 56 %, Cu: 97 %, Fe: 30 à 40 %, Pb: 69 %, Zn: 98 % ), du phosphore (52 %), ainsi qu'une réduction appréciable des matières volatiles en suspension (40 à 50 % ), et ce, après seulement 7 jours de traitement. Le soufre nécessaire à la biolixiviation- stabilisation est introduit, dans le cas de notre étude, sous forme de granules ou de blocs. Ce choix de la forme de soufre influe beaucoup sur la qualité de la boue produite, ainsi que sur son pouvoir acidophile après neutralisation. Le soufre en blocs s'avère plus efficace et aussi préférable au soufre en granules quant au pouvoir acidophile, après neutralisation, de la boue produite.

Mots-clés:

• Métaux lourds,
• boues d'épuration,
• soufre élémentaire,
• biolixiviation,
• stabilisation des boues

Abstract

Given the potential geochemical mobility and recognizd toxicity of heavy metals, their presence at high concentrations in sewage sludges imposes serious limitations on various sludge disposal practices (ocean disposal, landfill, incineration, or use as a fertilizer in agriculture or forestry), The objectve of this work was to develop a process that would permit the simultaneous stabilization of sewage sludges and the removal of heavy metals associated with them. The approach followed was to verify if this microbial leaching procedure could eventually replace conventional sludge stabilization processes and hence considerably reduce the time and cost of treatment. The microbial process consists of using thiobacillus strains which, in the presence of air, oxidize elemental sulfur to sulfuric acid, thus reducing the pH to very acidic levels (pH 1.5). This biological oxidation of elemental sulfur is brought about by two groups of sulfur-oxidizing bacteria, the less-acidophilic and the acidophilic thiobacilli. The initial acid production and pH reduction is due to the less-acidophilic bactena (Thiobacillus thioparus) which lower the pH to about 4.0. This is followed by the growth of acidophilic bacteria (Thiobacillus thiooxidans) and fruther pH reduction.

Batch culture experiments were carried out in 30 L and 8 L reactors with primary sludges obtained from the Quebec urban community's wastewater treatment centre. Elemental sulfur and inoculum were added at the beginning of each experiment The inoculum was prepared by adding 1 % tyndalized sulfur powder to fresh secondary sludge and incubating for 8 days (final pH 1.5 to 2.0). A small portion (5 %) of this acidified sludge was then used as an inoculum for another batch of fresh sludge and this process was repeated several times until an acclimatized inoculum was obtained which could oxidize elemental sulfur rapidly, without an appreciable lag phase. The elemental sulfur necessary as substrate for the simultaneous bioleaching and sludge stabilization was introduced in the form of granules (2.4 to 4 mm diameter) or blocks (25 mm diameter).

Sludge pH and ORP were measured at 24 hour intervals and all other measurements were carried out at 48 hour intervals. The results demonstrate that the addition of elemental sulfur and inoculum resulted in a considerable lowering of the sludge pH during the incubation period. Such pH lowering was not observed in cultures to which sulfur and inoculum were not added. This lowering of pH (2.1) was related to the quantity of substrate (sulfur) and inoculum present in the medium. An increase in the medium ORP (from -50 to about 500 mV) was also observed. Acidification of the medium along with the elevated ORP levels resulted in the solubilization of metals initially present in the sludge. This pH reduction, after only 7 days of treatment, effected an important metal solubilization (Cr: 56 %, Cu: 97 %, Be: 30-40 %, Pb: 69 %, Zn: 98 %), as well as an appreciable reduction in phosphorus (52 %) and in the volatile suspended solids concentration (40-50 %). In addition, the sludge which initially had a highly repulsive odour was rendered odourless.

In a previous study we had showm that for an optimum rate of acidification of the sludge a minimum concentration of elemental sulfur (2 g/L) was necessary, even though only 40 % of this sulfur was oxidized. In the present experiment the physical form of the sulfur was shown to influence both the quality of sludge produced and its acid-generating capacity after neutralization. Sulfur in the form of blocks was more efficient than granules in that the elemental sulfur could be readily separated from the sludge at the end of the treatment, yielding a sludge after neutralization that had a low acid-generating capacity. In the case of granules, the unused sulfur was broken down into a fine powder during the course of the bioleaching experiment and could not be separated from the leached sludge - even after neutralization, the leached sludge exhibited a high acid-generating capacity, which would limit its use as a fertilizer on agricultural land.

Keywords:

• Heavy metals,
• sewage,
• elemental sulfur,
• bioleaching,
• sludge stabilization