Résumés
Résumé
Des essais en erlenmeyers de 0,5 L ont été faits afin d'évaluer les possibilités d'application d'un procédé de solubilisation biologique aux sédiments. Ce procédé utilise la capacité des thiobacilles de lixivier les métaux en milieu acide. Au cours des essais, l'influence, sur la solubilisation des métaux, de la quantité de substrat (FeSO4 × 7H2O), du pourcentage d'inoculum et de la teneur en solides totaux a été suivie. La concentration de substrat n'a pas d'effet sur l'enlèvement du Cd, du Zn, du Mn et du Cu. Les taux d'enlèvement moyens pour le Cd, Zn et Mn, sont, après 46 heures, de 70 à 90 %, 90 à 100 % et 64 à 72 % pour des concentrations de substrat variant de 0 à 30 % FeSO4 × 7H2O (poids sec/poids sec). A 29 et 46 heures, des coefficients de détermination (r2) de 0,46 et 0,59 entre le pH et la concentration de FeSO4 × 7H2O, et de 0,92 et 0,55 entre le POR et la concentration de FeSO4 × 7H2O ont été trouvés. A plus forte teneur en FeSO4 × 7H2O, le POR est moins élevé, surtout au début des essais. La présence des ions ferreux en plus grande quantité expliquerait les plus faibles valeurs du potentiel-rédox.
A 20 % d'inoculum, la solubilisation des métaux est optimale avec une solubili- sation de 86 % pour le Cd et 73 % pour le Cu et le Mn. La forte corrélation entre le POR, le pH et le pourcentage d'inoculum (r2 à 29, 46 et 70 heures de 0,94, 0,94 et 0,63 pour le POR et le pourcentage d'inoculum et de 0,80, 0,69 et 0,60 pour le pH et le pourcentage d'inoculum), a permis d'établir une corrélation entre le POR, le pH et la solubilisation du Cu. Les seuils trouvés permettant une solubilisation du Cu supérieure à 10 % sont un pH de 3,75 et un POR de 260 mV.
L'augmentation des solides totaux (ST) semble limiter le développement des thiobacilles et diminue les rendements de solubilisation du Cd (à 21 heures) et du Zn (à 45 heures). Ainsi, pour le Cd, les pourcentages de solubilisation passent de 71 % à 24 % pour 3 et 15 % ST, alors que dans le cas du Zn, ils diminuent de 94 % à 81 % pour 3 et 15 % ST. La solubilisation du Mn serait, pour sa part, plutôt de type chimique.
Mots-clés:
- Olubilisation biologique,
- Thiobacillus ferrooxidans,
- métaux,
- sédiment,
- Cu,
- Zn,
- Cd,
- Mn
Abstract
In the province of Québec, the St-Lawrence Seaway as well as the harbour areas undergo frequent dredging. Each year, more than 106 cubic metres of sediments must be dredged from the st-Lawrence river. The dredged sedirnents are generally dispersed in the water column. However, heavy metal contamination of these sediments may preclude open-water disposal and necessitate their confinement.
The research work presented in this article applies to dredged sediments that are too contaminated for open-water disposal. In order to permit their safe disposal, it is necessary to have a method which effectively removes metals from these sediments. One of the effective methods of metal removal from contaminated sediments could be a microbial solubilization process, which was developed at INRS-Eau for sewage sludge decontamination and which has been tested on a pilot scale during the past year. In order to appty such a process to decontaminate sediments, it was necessary to study the influence of various factors affecting the microbial leaching process. This research verified the possibility of using a modified microbial leaching process to decontaminate sediments and also studied the influence of the enerry substrate, the microbial inoculum and the sediment total solids concentration on such a modified process.
The experimental methodology consisted of mixing the contaminated sediment in a 500 ml Erlenmeyer flask for a period of 96 hours in the presence of thiobacillus inoculum and ferrous sulfate (FeSO4 • 7H2O) as the enerry substrate. Before each experiment sediments were adjusted to the desired total solids concentration with deionized water and were acidified with sulfuric acid to obtain the starting pH conditions.
The solubilization of Cd, Cu, Zn and Mn was monitored at regular intervals in order to evaluate the influence of the various factors studied. Subsamples were removed, the sediments were digested and the metals were analyzed by inductively coupled plasma atomic emission spectrophotometry (ICP-AES). The elements analyzed were Al, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb,Zn as well as S, P and C. All the digestions and analyses performed made according to the APHA guidelines. The total solids, both volatile and inert, were also determined according to APHA method no.209F (APHA, 1985).
Regarding the influence of the ferrous sulfate concentration on the application of the microbial leaching process, the removal rates of Cd, Zn and Mn did not vary more than 12 %. For all experiments, the final pH value approached 2,5. The oxidation-reduction potential (ORP) varied for all experiments from 462 to 560 mV. An energy source could therefore be present in the sediments, which would support the growth of thiobacillus bacteria.
During the experiments conducted to study the influence of inoculum concentration on the microbial leaching process, it was found that the pH decreased from 3.5 to 2.4 and the ORP increased from 284 to 593 mV when the inoculum addition increased from 0 to 30 % (v/v). This tendency was also observed during the removal of Cd and above all, Cu. Between 0 and 20 % (v/v) inoculum concentration, Cd removal increased from 64 to 86 % whereas Cu removal increased from 20 to73 %. However, these two metals did not show any appreciable increase in solubilization when the inoculum was increased from 20 to 30 % (v/v). In the case of Mn, it was not possible to determine the solubilization pattern since the inoculum concentration did not influence the solubilization of this element, Between 0 and 30 % inoculum, the Mn removal varied from 56 to 73 %. Hence the microbial influence on Mn solubilization may be negligible.
The study on the influence of total solids content on the microbial leaching process showed that the total solids concentration had an influence on pH and ORP. The final pH increased from 2.43 to 3.32 and ORP decreasedfrom 492 to 321 mV when the total solids content was varied from 3 to 15 % . The percent solubilization of Cd after 21 h was 7l %, 69 %, 43 %, 44 % and, 24 % at 3, 5, 7, 10 and 15 % total solids respectively, On the other hand, Zn solubilization after 45 h was 94 %, 90 %, 84 %, 97 % and 8l % for the same concentrations of total solids. An increase in total solids content decreased the solubilization efficiency of Cd (at t=2l h) and, to a lesser extent, Zn (att=48h). However,in the case of Mn, the maximum solubilization was achieved right at the beginning and varied little with time. Its solubilization varied between 61 and 70 % for 3 % total solids, between 67 and, 79 % for 5 % total dolids, between 52 and,62 % for 7 % totaf solids, between 57 and, 75 % for l0 % total solids and tretween 40 and 63 % for 15 % total solids. In general, for the sediments studied here, total solids content has little influence on Mn solubilization.
In conclusion, use of a microbial leaching process to remove metals from contaminated sediments seems to be less complex than for sewage sludges, since the maximum removal of metals is achieved in less than 48 h in a bench-scale experiment. The average metal solubilization was above 80 % for Cd, 73 % for Cu, 90 % for Zn and 65 % for Mn. The development of thiobacillus does not seem to be dependent upon the presence of an added energy substrate. Only a minimal quantity of substrate, say 5 % ferrous sulfate (dry wt./dry wt.), is required in order to assure optimal conditions for thiobacillus growth. It is probable that with time, without ferrous sulfate, the microbial conditions would deteriorate due to exhaustion ofthe enerry substrate. A 20 % microbial inoculum seems to be enough to assure an efficient metal solubilization process. Except for Mn, the increase in total solids concentration had a negative influence on the metal solubilization. It is hence preferable to work with a total solids concentration of less than 5 %. Nevertheless, it should be noted that this percentage is more than that used for sewage sludge decontaminaton (around 2 % total solids).
Keywords:
- Microbial solubilization,
- thiobacillus ferrooxidans,
- bioleaching,
- heavy metals,
- sediment,
- Cu,
- Zn,
- Cd,
- Mn
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