The Fate of Organophosphate in steep-sloped Agriculture Soil under the influence of Runoff Generation
Priana Sudjono Laharko Khatarina Oginawati Kharistia Amaru Dept. of Environmental Engineering, Bandung Institute of Technology Jalan Ganesha, Bandung, Indonesia Email:
[email protected]
Content
The background Goals Methods Results and discussion Conclusion
The Background
The uncontrolled or excessive application of
ORGANOPHOSPHAT leads to SOIL POLLUTION AND DEGRADATION OF GROUNDWATER QUALITY
The Background Almost all water bodies in west java contain organophosphate and one carbamate It was monitored in West Java province that in the nine districts the residue of chlorpyriphos, prophenophos, diazinon, carbofuran, and endosulfan in soil is higher than the threshold values
The Goal The goal: the degradation of organophosphate in steep-sloped of agriculture soil The diminishing of organophosphate because of rainfall events, what it looks like ?
Scope: Transport phenomena of organophosphat in soil
METHOD Location - Cirawa village, desa Cibereum Kertasari,Kab Bandung - Jawa Barat. ± 60 km dari Kota Bandung. Slope 9 - 25 % Luas 62,4 m2
Soil sample - Plot study -
at 4 points, T1, T2, T3, T4 during 3 Periods Period : 24 hour, 48 hour; 72 hour. Depth of sampling: 10, 20, & 30 cm. Disturbed soil sample
Feeding solution -
Dursban 35 EC : Chhlorphirifos = 1652,89 mg/L Curacron : Prophenofos = 166,11 mg/L.
Soil hydraulic conductivity and subsurface flow computation
107o39‘00“
39‘30“
40‘00“
40‘30“
41 00“
07o10‘30”
Study Plot
7o10’57.39” & 107o40’31.44”
07o11‘00”
07o11‘30”
Feeding solution Chlorphirifos
Prophenofos
C1 = 200 gram/L V1 = 125 mL Added water 15.000 mL V2 = 15.125 mL
C1 = 50 gram/L V1 = 50 mL Added water 15.000 mL V2 = 15.050 mL
C1 xV1 C2 V2
C2
C2 = 1652,89 mg/L
C2 = 166,11 mg/L
C1 xV1 V2
DATA COLLECTION Rainfall monitoring at every 5 – 15 minute Overland flow monitoring 1 – 15 minutes Soil sampling
The behavior of pesticide in nature Photo-Degradasi Erosi angin
Volatilization
Runoff
Plant uptake
Adsorption & Stabilization (Biodegradation)
Top soil layer
Lower soil layer
Leaching to Groundwater
4
Hydraulic Conductivity constant head permeameter
Q(sinh 1 ( H / r ) 1) K 2H 2
Runoff Model ISTFM
Rainfall height at every 5 minute
Dimension of the plot
Array (k) Segmen (j) Time (i)
Plot Parameter
Surface slope Septh of soil layer
Water balance in a segment
Vrw Vbi Voi Vri Vv Vbo Vr Vo Vrw
surface Vo
Voi Vri
dd dw
Vr
Vbi
Vbo
l (sources : Sudjono, 1995)
b
THE SIMULATION Input files: Basin File Rainfall File 14
Hujan sangat lemah
24.5
Hujan lemah
12
Hujan normal Hujan deras
8 6 4 2
19.5 Adsorpsi, mg/L (x 10-9)
10
14.5 Adsorpsi ketika Hujan Sangat Lemah
9.5
Adsorpsi ketika Hujan Lemah Adsorpsi ketika Hujan Normal
4.5
Pers. adsorpsi
flow
Adsorpsi ketika Hujan Deras
0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110
Tinggi Curah Hujan (mm)
istfm
Durasi (menit)
-0.5 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Durasi Hujan (menit)
Read
QIST
Langmuir equation for chlorpirifos : x ab Ce 5x1014.Ce CS m 1 bCe 1 0,0005.Ce Langmuir equation for prophenofos :
x ab Ce 1x1012.Ce CS m 1 bCe 1 0,009.Ce
Retardation factor Bulk density = 0,91 Surface area specific, Sa=150 m2/gram Kow chlorpiriphos = 50118,72 (log Kow=4,7) Kow prophenofos = 100 (log Kow= >2) Koc chlorpirifos = 9930 Koc prophenofos = 2016 The equation Kd = foc.Koc,, so it can be calculated
Chlorpiriphos :
Kd = 58, 06 (coef adsorption) R= 89,057
Prophenofos
Kd = 58, 06 R= 89,057
f oc
Sa 200( Kow) 0,84
K d K oc . f oc B R 1 Kd
Hasil dan Pembahasan (1) The Soil Characteristics
Soil profile belong to Horison O (surface layer) dan horison A (Second layer) Colour: black-brown Day temperature: 18 – 25 oC. Texture: Clay loam gravel= 1 % sand= 32 % Silt = 62 % clay= 5 %
Hydraulic conductivity : 0,02 – 2 m/day
Metoda klasifikasi tanah : US. Department of Agriculture
Retardation factor
:
Ce / Cs (mg/L)
1.00E+09 9.00E+08 8.00E+08 7.00E+08 6.00E+08 5.00E+08 4.00E+08 3.00E+08 2.00E+08 1.00E+08 0.00E+00 1652.8
y = 1E+10x - 2E+13 R² = 0.9634
1652.8
1652.8
1652.8
1652.8
Ce (mg/L)
Cs the adsorbed contaminant by the soil Ce the concentration remain in the solution
1652.9
Degradation
:
7.00E+08
Ce / Cs (mg/L)
6.00E+08 5.00E+08 4.00E+08 3.00E+08
y = 9E+09x - 1E+12 R2 = 0.6642
2.00E+08 1.00E+08 0.00E+00 166.06
166.07
166.08
166.09
Ce (mg/L)
166.10
Retardation factor
:
0.20
Chlorphyriphos, mg/l
0.18 0.16 0.14 0.12
0.10 0.08
10 cm depth 20 cm depth 30 cm depth
0.06 0.04 0.02 0.00 0
12
24
36
Time, hour
48
60
72
Degradation
0.08
Prophenophos, mg/l
:
0.07 0.06 0.05 10 cm depth
0.04
20 cm depth
0.03
30 cm depth
0.02 0.01 0.00 0
12
24
36
Time, hour
48
60
72
:
the soil samples were taken from 4 points located along a line to the downstream direction to the river. There will be possibility of some residue from upstream sampling point moves to the down site.
Retardation factor
:
The estimated degradation coefficient (k) for chlorpyriphos is 0,13 – 0,272/ day with half-life (t½)of about 2,55 – 5,244 days, and k for Prophenophos is 0,3661 – 0,56/day and the half-life (t½) is 1,23 – 1,89 days.
14
Hujan sangat lemah Hujan lemah
12
Hujan normal Hujan deras
8 6 4 2
19.5 Adsorpsi, mg/L (x 10-9)
10
14.5 Adsorpsi ketika Hujan Sangat Lemah
9.5
Adsorpsi ketika Hujan Lemah Adsorpsi ketika Hujan Normal
4.5
Adsorpsi ketika Hujan Deras
Durasi (menit)
95 10 0 10 5 11 0
90
85
80
75
70
65
60
55
50
45
40
35
30
25
20
15
5 10
0 0
Tinggi Curah Hujan (mm)
24.5
-0.5 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Durasi Hujan (menit)
Simulation using various rainfall intensity found that adsorpsion is not significantly under the influence of rainfall intensity. However, adsorption increase signifanctly during very high rainfall after a few minutes (at the 10th step)
6 5 2.5
4 3 Adsorpsi pada slope 15 % Adsorpsi pada slope 25 %
2
Adsorpsi pada slope 45 % Adsorpsi pada slope 65 %
1
Adsorpsi, mg/L (x 10-9)
Adsorpsi, mg/L (x 10-9)
3
2
Adsorpsi pada kedalaman 30 cm Adsorpsi pada kedalam 80 cm
1.5
Adsorpsi pada kedalaman 100 cm 1 0.5
0 11 0 .0 11 5 .0 11 5 .05 9.4 5 9.4 5 11 .5 11 11 .5 .25 9.4 9.4 9.4 8.2 5 8.2 5 8.2 5 7.7 7.7 7.7 6.2 6.2 6.2 1.1 1.1
0 0
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 105 110 Waktu (menit)
Tinggi Curah Hujan (mm)
In flat land, the adsorption is high while in steep-sloped land the adsorpsion is low. Because subsurface flow velocity is steep-sloped land is high. Simulation on adsorption using several depth of soil layers found that there is no significant discrepancy for the adsorption to the depth of soil layer.
Conclusion Chlorpiriphos
Kd = 0,13-0,27 per day Decay rate 2,55 – 5,24 day
Prophenophos
Kd = 0,36 – 0,56 per day Decay rate 1,23 – 1,89 day
Simulation using several variables found that: Adsorption is high in flat lands rather than that in steep sloped lands. Besides, the adsorption was high during very heavy rainfall. But depths of soil layers do not produce significant variation on adsorption. It is postulated that the concentration of organophosphate in soil water decreases as rundown water through soil particles dilutes the organophosphate in the soil.
Daftar Pustaka
1. 2. 3. 4. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17.
Cheng,H.H, 1990, Pesticides in The Soil Environment : Processes, Impacts, and Modeling, Soil Science Society of America, Inc, Winconsin, USA. Murty, A.S, 1986, Toxicity of Pesticides to Fish, CRC Press Inc. Florida.pp 5 – 28. McEwen, F.L and Stephenson, G.R, 1979, The Use and Significance of Pesticides in The Environment, Jhon Willey and Sons, New York. pp 229 – 260. Departemen Kesehatan, Daftar Penggunaan Pestisida di Indonesia, Jakarta, 1998. Notodarmojo,Suprihanto, 2004, ‘Pencemaran Tanah dan Air Tanah’, Penerbit ITB, Bandung. Clark,M.M.,(1996), Transport Modelling for Environmental Engineering and Scientist, New York, John Willey & Sons,Inc, 1 – 19, 109 – 214, 387 – 431. Eweis,J.B., Ergas,S.J., Chang,D.P.Y., Schroeder,E.D. (1998), Bioremediation Principles, Singapore, McGraw-Hill Companies, 23 – 59. Gorelick,S.M., Freeze,R.A., Donohue,D., Keely,J.F., (1993), Groundwater ContaminationOptimal Capture and Contaiment, Florida USA, Lewis Publishers, Alafiah.T.,2001, Ekokinetika Dan Traspor Pestisida Endosulfan Pada Tanah Andosol, Tesis Magister Teknik Lingkungan, Institut Teknologi Bandung. Foth, H. D., 1995, Dasar-dasar Ilmu Tanah. Gadjah Mada University Press. Yogyakarta, Indonesia Kecamatan Kertasari, 2006, Monografi Kecamatan Kertasari Kabupaten Bandung. Kirby, M.J., editor, 1978, Hillslope Hydrology, School of Geography, University of Leeds, A Wiley – Interscience publication, Great Britain. Nuraini.A.,(2000), Transpor dan Perilaku Pestisida Klorpirifos Pada Tanah Andosol, Tesis Magister Teknik Lingkungan, Institut Teknologi Bandung. Thandung, H.,2006, Degradasi Klorpirifos Pada Tanah Jenis Liat, Air dan Sedimen di DAS Citarum Hulu, Tesis Magister Teknik Lingkungan, Institut Teknologi Bandung. Wardhani.N.K., 2003, Degradasi Pestisida Klorpirifos Dalam Tanah Pada Proses Bioremediasi Dengan Penambahan Nutrien, Tesis Magister Teknik Lingkungan, Institut Teknologi Bandung.
Acetilkolin Mekanism
KARAKTERISTIK ORGANOFOSFAT PROFENOFOS
Nama IUPAC : O-(4-bromo-2-chlorophenyl)-O-ethyl-S-propyl phosphorothioate Nama Dagang : Curacron, Policron, Selecron Rumus Molekul : C11H15O3PSBrCl
Titik Didih : >110oC Densitas : 1,46 g/ cm2 pada suhu 21oC Kelarutan pada air : 20 ppm pada suhu 25oC Berat Molekul = 373,65 g/mol Waktu Paruh : 9 hari Koefisien Partisi Oktanol-Air Log Kow = > 2 pada suhu 25oC Koefisien Adsorpsi Tanah : Koc = 2016 Stabilitas : Stabil pada kondisi netral dan sedikit asam, tidak stabil pada kondisi basa.
KLORPRIFOS
Nama IUPAC : O,O-diethyl-O-(3,5,6-trichloro-2pyridinyl) phosphorothioate Nama Dagang : Dursban, Lorsban, Dowcow Rumus Molekul : C9H11C13NO3PS
Titik Didih : >300oC Titik Leleh : 42-43,2oC Densitas : 1,51 g/ cm2 pada suhu 21oC Kelarutan pada air : 1,54 ppm pada suhu 25oC Berat Molekul = 350,6 g/mol Waktu Paruh : 22 hari Koefisien Partisi Oktanol-Air Log Kow = 4,7 pada suhu 20oC Log Kow = 4,76 pada suhu 25oC Koefisien Adsorpsi Tanah : Koc = 9930 Stabilitas : Laju Hidrolisis meningkat dengan bertambahnya pH dan kehadiran logam Cu
