APPLICATION OF ELECTROCHEMICAL OXIDATION IN THE TREATMENT OF LANDFILLOXIDATION IN THE TREATMENT OF LANDFILL LEACHATE AND EVALUATION OF TOXICITY IN

Allium cepaAllium cepa

Cláudia Regina Klauck1

Tatiane Benvenuti2Tatiane BenvenutiLuciano Basso da Silva3

Marco Antonio Siqueira Rodrigues3

1‐ Bacharel em Ciências Biológicas Feevale. PPGQA Universidade Feevale. Bolsista de mestrado CAPES/FAPERGS.1 Bacharel em Ciências Biológicas Feevale. PPGQA Universidade Feevale. Bolsista de mestrado CAPES/FAPERGS. 2‐ Engª de Bioprocessos e Biotecnologia. PPGE3M UFRGS. Bolsista de doutorado CAPES. 

3‐ Professor e pesquisador do PPGQA Universidade Feevale.

Introduction

Solid waste

Environmental problem MORAIS et al., 2005,

Population increase

Consumption

disposal

p MORAIS et al., 2005,ABRELPE, 2011

dumpsite Controlled landfill Sanitary Landfill

25,9%; 24,3% 40,5% Muller 2009

• Leachates are defined as the aqueous effluent generated as a consequence of rainwater percolation through wastes,

Landfill Leachate

25,9%; 24,3% 40,5% Muller, 2009

q g q p g ,biochemical processes in waste's cells and the inherent water content of wastes themselves. Leachates may contain largeamounts of organic matter (biodegradable, but also refractory to biodegradation), where humic‐type constituents consistan important group, as well as ammonia‐nitrogen, heavy metals, chlorinated organic and inorganic salts. The leachate ishighly toxic and genotoxic and should be treated properly before its release in the receiving bodies (Baun et al., 2003).

• The characterization of the landfill leachate varies accordingto their age, due to the different phases of wastedecomposition (Kjeldsen et al 2002)decomposition (Kjeldsen et al., 2002).

• In the initial stage of the decomposition, there is a greaterpresence of biodegradable compounds, susceptible todegradation by biological processdegradation by biological process.

• As the age of the leachate increased, the biodegradablefraction becomes low, and the content of high molecular, gweight substances (such humic substances) are difficult todegradation (recalcitrant), ammonia nitrogen, and toxiccompounds increases.

Average rating of landfill leachate to its composition and age (adapted from RENOU et al., 2008).

• Inhibition of the biological treatment, hindering its treatability by conventionalbiological processes (Rocha et al., 2011).

h d d d ( ) l

Advanced Oxidative ProcessesOxidant agent Potencialeletroquímico (v)

• The Advanced Oxidative Processes (AOP) are alternativestechnologies to the treatment of reaclcitrant compounds asthe compounds presents in landfill leachate (OLLER et al.,2011).

Fluor 3,06

Hydroxyl radical 2,80

Atomic oxygen 2,42

• All AOP’s are based in the generation of hydroxyl radicals(*OH), a higly oxidant agent, that reacts in the presence oforganic matter (Morais et al., 2005).

yg

Ozone 2,08

Hydrogen peroxide 1,78

Hypochlorite 1 49 g ( , )

– Color, organic matter and recalcitrant compoundsreduction and increased biodegradability (OLLER et al.2011)

Hypochlorite 1,49

Chlorine 1,36

Chlorine dioxide 1,27

M l l 1 23 2011).Molecular oxygen 1,23

Main AOPs applied in wastewater treatment

Principal functions of the AOPs in wastewater treatment(Rizzo, 2011).

• Increase quality of the final effluent reducing toxicity

Homogeneous H2O2; O3; Fenton; (withor without UV);

Heterogeneous H O /Sc; H O /Sc/UV;

Increase quality of the final effluent, reducing toxicity.

• Desinfection .

• Increased biodegrability.

l l i i fHeterogeneous H2O2/Sc; H2O2/Sc/UV;

Sc= semiconductor

(Rizzo, 2011).

• Metal removal or conversion to non‐toxic forms .

Electrochemical oxidation• Production of ●OH and oxidation/reduction reactions in DSA electrodes applying an electric

current.

– Direct anode oxidation

– Indirect oxidation: electrochemical generation of mediators oxidants (TURRO et al,2011).

•• AA greatgreat diversitydiversity ofof materialsmaterials are used in the composition of the anode: PbO2/SnO2, Ti/Pt,Ti/PbO2, RuO2 (COMNINELLIS et al., 1994).

Objective

The aim of this study  was evaluated the effectiveness of advanced oxidation process of pelectrochemical oxidation in leachate treatment, and toxicity assessment of the sample beforeand toxicity assessment of the sample before 

and after treatment. 

Treatment conditions 

Electrochemical reator‐ 16 electrodes (70:30 TiO2/RuO2),arranged in parallel

Methodologyarranged in parallel 

Current rectifier:  135A

Volume treated: 150L

Duration: 40 and 60 hours

Collection site: disabled landfill site (Novo Hamburgo)

Duration: 40 and  60 hours

Current density: 14mA.cm²

Above: overview of the pond of treatment ofAbove: overview of the pond of treatment of leachate . Bellow:  entrance of the leachate in the pond, also the collection point of sample. 

The figure above shows the currentrectifier; electrode of TiO/RuO;electrochemical reactor.

ResultsRaw 40h  60h  Local legislation

Parameters leachate treatment treatment CONSEMA 128Chlorides (mg L‐1) 709,10 157,80 157,80 ‐Conductivity(mS cm‐1)  6,60 3,60 3,90 ‐BOD ( L 1) 400 00 15 00 20 00 150BOD5 (mg L‐1) 400,00 15,00 20,00 150COD (mg O2 L‐1) 732,70 345,7 189,40 360Phosphorus(mg L‐1)  3,30 0,60 0,60 4Nit t ( L 1) 18 40 86 0 113 50Nitrate (mg L‐1)  18,40 86,0 113,50 ‐Nitrite (mg L‐1)  0,02 0,03 0,01 ‐Ammonia(mg L‐1)  417,70 n.d. n.d. 20T t l Nit Kj ld hl ( L 1) 537 70 2 20 1 70 20Total Nitrogen Kjeldahl (mg L‐1)  537,70 2,20 1,70 20pH 7,90 8,60 9,30 6‐9Turbidity 47,50 21,30 9,00 ‐Cadmium (mg L‐1) 0 005 0 004 0 003 0 1Cadmium (mg L 1)  0,005 0,004 0,003 0,1Lead (mg L‐1)  0,05 0,05 0,06 0,2Total Chromium(mg L‐1)  0,08 0,10 0,10 0,5Manganese (mg L‐1) 0 40 0 10 0 06 1 0Manganese (mg L 1)  0,40 0,10 0,06 1,0Niquel (mg L‐1)  0,09 0,07 0,05 1,0Zinc (mg L‐1)  0,10 0,30 0,30 2,0

Physical appearance of the sample before and after the treatment

Color removal

Chlorine odor

“Chloride ions present in abundance in theleachate can often act as oxidants in indirectelectrochemical oxidation of organicf gmatter“ (Moraes & Bertazzoli, 2005)

The degradation of complex organic by AOPs can lead the

ConsiderationsThe degradation of complex organic by AOPs can lead theformation of intermediate compounds which may be toxicor even more toxic than the initial compound (Rizzo 2011).

Th f h i f di i l i hTherefore there a necessity for studies involving theassessment of toxicity and its impact on various organisms

(bioindicators)

It causes the integration of the effects of all contaminants,serving as a complement to physical and chemical analysis(Andreozzi et al., 2002; RIZZO et al., 2009).

On this way, the bioassay is proposed as an strategy tosave the characterization of organic pollutants

l d d d h fcomplex, rapid and inexpensive test, used as the firstscreening samples to recognize potentially toxic

Ilustration of the main species used in bioassay.

Toxicity test (root germination) in Allium cepa

The onions are easy to be stored,handled and root cells constitute a

Allium cepa Test

Exposed portion Bulbs with roots of Allium handled and root cells constitute aconvenient system for bothmacroscopic parameters (growth,deformity) and for microscopic

p pcepa

Time 48h

Exposure in Control (H2O) deformity) and for microscopicparameters (chromosomalaberrations). (Fiskesjö 1988)

quintuplicate2

Raw leachateLeachate treated for 40h and 60h

Measurement of root lengthMeasurement of root length

The values found in each treatment were compared with the control group

Results of the toxicity test in Allium cepa

120,00

100,00

80,00

100,00 CONTROLE ‐ C

CHORUME BRUTO

Control

Raw leachate

4044

3840,00

60,00TRATAMENTO 40h

TRATAMENTO 60h

Treated Leachate 40h

Treated Leachate 60h

0,00

20,00

100%

Toxicity Effect – Growth Inibition of 50% root lenght related to the control grouprelated to the control group

Conclusions

• The treatment was effective inremoving the physico‐chemicalparameters required by legislation

• However ecotoxicological test indicatesthat the effluent became as toxic as theinitial sample.

Perspectives

• Optimization of time and current density, pH adjustments.

• Application of integrated treatment systems.

• Ozone, electro, photoelectrooxidation.

• Characterization of the leachate after biological treatment.

T t ith th bi k• Test with other biomarkers.

• Characterization of organic compounds and by products generatedand by‐products generated.

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Acknowledgements

• UFRGS, FAPERGS, CAPES and CNPq‐Brazil for financial support.

Tatiane Benvenuti

benvenuti.tatiane@gmail.com