ECP - O08

Degradation of a pesticide mix by Heterogeneous

Photocatalysis and Photo electro-Fenton
Elizarragaz-De La Rosa D.,1 Guzmán-Mar J.L.,1 Hernández-Ramírez
A.,1 Hinojosa-Reyes L., Octavio Gaspar-Ramírez2, Ruiz-Ruiz E.1.
(1)
Universidad Autónoma de Nuevo León, Facultad de Ciencias
Químicas, , N.L., México. (2) Centro de Investigación y Asistencia en
Tecnología y Diseño del Estado de Jalisco A.C., Sede Noreste,
Apodaca, Nuevo León, México .*e-Mail: edgar.ruizrz@uanl.edu.mx

INTRODUCTION
Over the past decades the use of pesticides in agriculture has increased around the world. These pollutants
can move through different environmental matrices, resulted in widespread environmental contamination
being aquatic resources the most affected in agricultural areas. In a previous work of our research group, a
total of 15 pesticides were detected (at ng L-1 to µ L-1 concentration level) in groundwater near to agricultural
areas in the state of Nuevo León, Mexico. Since the occurrence of these substances in water represents a
potential risk to humans and aquatic ecosystems we proposed here the application of advanced oxidation Graphical Abstract
processes as photo electro-Fenton (PEF) and heterogeneous photocatalysis (HP) that have been
demonstrated to be effective in the destruction of different pollutants in water. So, the aim of this work is the
degradation of the pesticides recently detected in groundwater in northeast México, applying the AOP to a
pesticide mix (15 substances) at a concentration level similar to that found in groundwater samples (µ L —1).

METHODOLOGY RESULTS AND DISCUSSION

Determination of Pesticides
Darkness
It was carried out by solid phase micro extraction followed
by gas chromatography–mass spectrometry (7890A GC and a) b)
5975C MS) detection in the following conditions:
Injection: splitless at 250°C.
Column: DB-5 MS capillary Ionizatipn mode: electron
column (15m × 0.250mm × impact (at 70 eV)
0.25 µm) Transfer line and ion source
Carrier gas: Helium at temperatures: 250 and
constant flow of 1.0 mL min-1 220°C, respectively.

Volume: 500 mL. Pesticides mix FIGURE 3- Pesticide degradation by a) HP 0.2 g L-1 of TiO2 and b) PEF at 150 mA cm-2. Both under UV radiation.
Plaguicide concentration: 5 µg L-1 of each one. 5 µg L-1 of each one
TABLE 1- Pesticide degradation by HP and PEF at different conditions.
Radiation: UV-Vis Lamp (intensity 13 W/m2, 310-400 nm) Pesticide % Absorption on % deg. % deg. % deg. % Deg.
TiO2 at 60 min HP-TiO2 HP-TiO2 PEF PEF
200 mg L-1 400 mg L-1 75 mA cm-2 150 mA cm-2

Photocatalytic degradation Hexaclorociclohexano

(HCH)
18 8 32 63 78

TiO2 Degussa P25 at natural pH (6.8). Hexaclorobenceno

(HCB)
95 100 100 95 96

Amount of catalyst added: 0.2 and 0.4 g L-1. Pentachloroanisole

Aldrin
82
90
96
100
98
100
100
100
100
100
2,4-D 90 100 100 80 100
Oxyfluorfen 67 100 100 43 100
Photo-Fenton degradation Perthane 94 100 100 47 94
DDTp, p’- 94 100 100 64 88
Na2SO4 0.05 M solution at pH 3 and 0.3 mmol L-1 of Fe2+ Quinoxyfen 51 91 97 82 100
Bifenthrin 99 100 100 40 100
Current densities: 75 or 150 mAcm-2. Fenoxycarb 11 98 100 94 100
Tetradifon 64 74 74 97 100
Anode: Carbon cloth air diffusion electrode (1.33 cm2) Pyridaben 87 100 100 62 92
Fenazaquin 80 100 100 91 99
Cathode: BDD (6.25 cm2 ). Fenvalerate I 77 100 100 100 100

RESULTS AND DISCUSSION CONCLUSIONS

30
When HP is applied to the pesticide mixture, the concentration of each of them was
25 below to 0.1 µg L-1 after three hours of reaction. The exception was for HCH,
20 pentachloroanisole, quinoxyfen and tetradifon that remaining in the solution at higher
H2O2 (mmol L )
-1

15 concentration values at the end of the reaction. However, the removal of these
10
pollutants is largely due to the adsorption process and not to degradation.
The PEF process eliminated the same pesticide mixture at concentration level below to
5
0.1 µg L-1 after 3 h of reaction. The exception was for HCH, HCB, Perthane, DDT,
0
0 60 120 180 240 300 Tetradifon and Pyridaben. The removal of contaminants by the PEF process is directly
Tiempo (min)
Time (min)
attributed to degradation by ●OH produced in the anode and from the Fenton´s
Time (min) Time (min)
Time (min) reaction.
FIGURE 1- H2O2 electrogeneration at (■) 75 mAcm-2 FIGURE 2- Pesticide degradation by photolysis
and (●) 150 mAcm-2, Na2SO4=0.05M, pH 3 under UV radiation UV (13 W m­2) .

ACKNOWLEDGMENTS
The authors thank the financial support from the Consejo Nacional de Ciencia y
Tecnología (CONACyT), México, PDCPN-2015, No. 505 and the PAICYT program and
Facultad de Ciencias Químicas of the Universidad Autónoma de Nuevo León. D.
Elizarragaz acknowledges the granted scholarship (scholarship number 443152)
awarded by CONACyT.
REFERENCES
[1] D.J. Ecobichon, Environmental Health Perspectives 160 (2001) 27–33.
[2] E.D. Ongley, Lucha Contra la Contaminación Agrícola de los Recursos Hídricos, Food
& Agriculture Organization of the United Nations (Fao), Canada, 1997.
[3] A.R. Ribeiro, et al. Environment International, 75 (2015) 33–51.
[4] I. Sirés, et al. Environmental Science and Pollution Research, 21 (2014) 8336–8367.