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2. ENVIRONMENTAL ChEMISTRy & TEChNOLOGy 2.1. Lectures

2. ENVIRONMENTAL ChEMISTRy & TEChNOLOGy 2.1. Lectures

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Chem. Listy, 102, s265–s1311 (2008) Environmental Chemistry & Technology<br />

P02 REMOVAL OF 2-MERCAPTObENZOThIAZOLE<br />

FROM SyNThETIC<br />

wASTEwATER<br />

BEáTA ALMáSIOVá, Ján DERCO, AnGELIKA<br />

KASSAI and eVA HáSOVá<br />

Slovak University of Technology, Faculty of Chemical and<br />

Food Technology, Institute of Chemical and Environmental<br />

Engineering, Radlinského 9, 812 37 Bratislava 1, Slovak<br />

Republic,<br />

beata.almasiova@stuba.sk<br />

Introduction<br />

2-Mercaptobenzothiazole (MBT) is the most important<br />

member of the benzothiazole group of heterocyclic aromatic<br />

compounds. It is a pale yellow, crystalline substance with an<br />

unpleasant odor and a bitter taste . This xenobiotic compound<br />

is used mainly in the manufacture of rubber additive chemicals<br />

but also has other uses, notably as a corrosion inhibitor,<br />

antifreeze for automobiles. It is known as a toxic and poorly<br />

biodegradable pollutant. It is able to pass conventional treatment<br />

systems, widespread with surface and underground<br />

waters and enters into organisms 1 . Data concerning biodegradation<br />

of MBT are inconclusive. Some authors 2 have suggested<br />

it is recalcitrant to biodegradation.<br />

Genotoxicity investigations in bacterial and mammalian<br />

test systems provide some evidence indicating that MBT has<br />

the potential to induce mutations and chromosomal aberrations.<br />

Toxicity studies in rats and mice chronically exposed<br />

to MBT identified increases in various tumors 3 . Epidemiological<br />

investigations indicate that workers occupationally<br />

exposed to MBT have an increased risk of death from bladder<br />

cancer. MBT interfered with the nitrification processes and<br />

exhibited biocidal effects. MBT inhibits the degradation of<br />

easily degradable organics 4 .<br />

This work was aimed at study biodegradation of MBT<br />

and effect of this compound on activated sludge. Degradation<br />

of MBT by ozone was also studied.<br />

Experimental<br />

B i o d e g r a d a b i l i t y o f M B T<br />

Adaptation of activated sludge to MBT was carried out<br />

in semicontinuos bioreactor. We were adapted MBT with<br />

maximal concentration 25 and 50 mg dm –3 on the activated<br />

sludge. Time of adaptation was 3 weeks. During the adaptation<br />

Table I<br />

Specific sorptive capacity of activated sludge<br />

c MBT MTB decrease MTB decrease<br />

at solution by adsorption by adsorption<br />

[mg dm –3 ] [mg dm –3 ] [mg g –1 ]<br />

10 4.2 42<br />

20 5.9 59<br />

60 6.8 68<br />

s336<br />

we measured inhibition effect of MBT on the activated sludge<br />

by respirometric measurements.<br />

Adsorption tests were performed both with adapted and<br />

nonadapted activated sludge to MBT. Adsorption of MBT on<br />

activated sludge was studied at various concentration values<br />

of MBT. We were measured the specific sorptive capacity of<br />

sludge at low (10, 20 and 60 mg dm –3 ) and high concentration<br />

of MBT (100, 200 and 500 mg dm –3 ).<br />

O z o n a t i o n o f M B T<br />

The feasibility of utilisation of ozone for degradation<br />

of MBT was investigated in laboratory scale equipment. The<br />

experiments were performed in bubble ozonation column.<br />

The ozonation equipment consists of two glass columns,<br />

0.04 m diameter and 1.70 m height. The first column was<br />

filled with synthetic water with MBT, and the other one was<br />

filled with solution of potassium iodide to destroy residual<br />

ozone in the outlet of the first ozonation column. The system<br />

was operated in batch mode. Synthetic wastewater containing<br />

MBT was added into ozonation reactor at the beginning of<br />

trials. Continuous flow of oxygen 30 dm 3 h –1 was applied for<br />

generation of ozone. The Lifetech ozone generator with the<br />

maximum ozone production 5 g h -1 and Lifetech ozone UV<br />

detector were used. Ozonation trials were carried out at 70 %<br />

of the power maximum of ozone generator. Initial concentration<br />

of MBT in synthetic water was 50 mg dm –3 .<br />

Results<br />

MBT is not consumed by non adapted activated sludge.<br />

Decrease of respiration rate of non adapted activated sludge<br />

was observed with the increase of 2-MBTconcentration.<br />

Rapid decrease of respiration activity was observed for activated<br />

sludge after adaptation. The endogenous respirometric<br />

rate decreased by 6 % at concentration 25 mg dm –3 MBT in<br />

comparison with reference model. The endogenous respirometric<br />

rate decreased by 39 % at concentration 50 mg.dm –3<br />

MBT in comparison with reference model.<br />

The decrease of dissolved MBT concentration was<br />

observed at the low concentration levels. The value of COD<br />

and TOC increased after 10 days, which is caused by increase<br />

of concentration of MBT in solution.<br />

Table I shows the results of adsorption test carried out at<br />

lower concentration values of MBT. negligible adsorption of<br />

MBT on activated sludge was observed at MBT concentration<br />

higher than 100 mg dm –3 .<br />

According to results shown in the Fig. 1. the highest COD<br />

removal was observed during the first 20 minutes of ozonation.<br />

The initial COD value conversion achieved about 98 %<br />

after 50 minutes. The efficiency of TOC removal was 54 %<br />

after 50 minutes of ozonation. Almost total removal (96 %)<br />

of 2-MBT from the sample was achieved after 5 minutes of<br />

ozonation. Simultaneously the presence of benzothiazole was<br />

identified as ozonation intermediate. The presence of benzothiazole<br />

(BT) was identified in the sample after 50 minutes<br />

of ozonation. Fien et al. 5 show, that MBT and its breakdown<br />

products had a high affinity towards ozone as indicated by the

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