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Proceedings of the 19th IAHR-APD Congress 2014, Hanoi, Vietnam

ISBN xxx-xxxx-xx-x

ORGANOCHLORINE AND ORGANOPHOSPHORUS PESTICIDE RESIDUES IN SURFACE WATER


NEAR AGRICULTURAL AREAS IN HO CHI MINH CITY
NGUYEN LY SY PHU, TO THI HIEN1
VNUHCM- University of Science, Ho Chi Minh City, Viet Nam
1Email: tohien@hcmus.edu.vn

ABSTRACT
Residual levels of organochlorine and organophosphorus pesticides in surface water in some agricultural areas in Ho Chi
Minh City were investigated in 2013. Five organophosphorus pesticides including Diazinon, Malathion, Parathion, Ethion
and Trithion and eight organochlorine pesticides including Alpha - HCH, beta-HCH, gamma-HCH, Aldrin, Heptachlor
epoxide, Alpha-Endosulfan, 4 4 - DDT and Endosulfan-sulfate were determined in the surface water in four dicstricts :
Binh Chanh, Hoc Mon, Cu Chi and Binh Tan using gas chromatographic method with electron capture detector (GC-
ECD). The results showed that residues of pesticide were found with high concentrations in surface water in agricultural
areas and pesticide residues changed depending on growth stages of crops. The concentration and distribution of
pesticides were different in the water samples at different sites. Residues of pesticides such as Parathion, Ethion and
Trithion were detected in surface water although these chemicals have been banned.
Keywords: organochlorine pesticides, organophosphorus pesticides, surface water, agricultural area

1. INTRODUCTION Tan Nhut, Le Minh Xuan, Vinh Loc A, Vinh Loc B. Cu Chi
district 3 samling sites: Tan Phu Trung, Phuoc Vinh An,
Pesticides used in agriculture activities are causing more
Phuoc Hiep. Binh Tan district 1 sampling sites: Tan Tao A.
serious consequences for humans and ecosystems.
Hoc Mon district 3 sampling sites: Tan Hiep, Ba Diem, Tan
Vietnam is a country with a large agriculture which use
Thoi Nhi.
the large amount of pesticides every year. The benefits of
using pesticide can be seen as higher crop yields than Those are four suburban districts of Ho Chi Minh City
before. However, the problems arise when the pesticides where large agricultural activities take place. At each
were released into the environment. Although this is a location three water samples were taken in different
serious problem, there was a lack of information on places along the irrigation canal or ponds from which the
residues of pesticides released into the environment. water runoff. The sampling locations are well-distributed
over the area so that the sample is representative for the
Pesticides include as many different types such as
quality of surface water in the area. The total 33 samples
organochlorine pesticides, organophosphorus pesticides,
were taken from 2/2013 to 4/2013.
carbamat Organochlorine Pesticides (OCPs) is a group
of persistent organic pollutants (POPs) which are to be 2.2 Sampling method
eliminated or restricted used in many countries. Their
Water samples were collected and stored in 2.5 L glass
persistence in the environment and biological
bottles. All glass bottles were washed with water and
accumulation through the food web cause environmental
detergent, then rinse carefully with distilled water, dried
damage and affect human health. In regards to Organic
at 1050C for 2 hours and then allow to cool before coated
Phosphorus Pesticides (OPPs), they have some restricted
with hexane. Finally, dried the glass bottle. After used,
and prohibited uses and gradually be replaced with
pickled glass bottle with acetone after 12 hours, coated
biologically active substances with environmentally
with hexane and dried. Water samples were extracted at
friendly such as Pyrethorid daisies. However, since OCPs
the sampling location, then preserved in low temperature
and OPPs are more effective than other pesticides and cost
and brought to the laboratory for analysis.
less, people continue using OCPs and OPPs in farming.
Monitoring technique is necessary to create the basic data, 2.3. Extraction and analysis
provide better management to chemica disposal and
minimize their impact on people and the environment. Water samples were filtered prior to extraction to remove
residual, Liquid - liquid extraction methods are applied to
This study was initially conducted to investigate the level extract samples. 250mL water samples extracted with 30
of OCPs and five OPPs in the surface water in some mL methylene chloride (DCM)/hexane or only DCM
agricultural areas in Ho Chi Minh, particularly in the rice- (both DCM, acetone and hexane obtained from Merck &
growing areas. . The study will give information about the Labscan. Inc.) Shake the mixture in 15 minutes, repeat 3
status of vegetables as well as some proposed solutions to times (Method 8141 A,B, 1994; AOAC, 1996) . The extract
minimize the effects of toxic substances to human health was concentrated by rotary evaporation and then were
and the environment. cleaned up on a neutral silica solid phase extraction (SPE)
column (Silica Gel 100/200 mesh) (Method 3630, 1996).
2. MATERIALS AND METHODS
Before use, activate for at least 16 hr at 130 0C in a shallow
2.1 Sampling site glass tray, loosely covered with foil. Store the deactivated
silicagel in a sealed glass jar inside a desiccator Sodium
In this study, 11 samples were taken at 11 locations of four
sulfate (granular, anhydrous), Na2SO4. Purify by
districts including Binh Chanh, Cu Chi, Hoc Mon, Binh
precleaning the sodium sulfate with n hexane. Transfer 3
Tan (see figue 1). Binh Chanh district has 4 sampling sites:

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g portion of deactivated silica gel into a 10 mm ID glass OPPs (g l-1); OCPs (ng l-1)
syringe column and top it with 2 cm of anhydrous sodium
Concentration = mean SD
sulfate. Add 10 mL of hexane to the top of the column to
wet and rinse the sodium sulfate and silica gel. Transfer After analyzing 33 water samples taken from 11 locations
the sample extract onto the column. Rinse the extract vial of four districts, the results have shown that the average
twice with 2 mL of hexane and add each rinse to the concentrations of 8 OCPs is 0.0203 0.0286 g l-1 and OPPs
column. Elute the column with 40 mL of hexane and 30 is 0.95 0.29 g l-1.
mL of methylene chloride for OCPs and 40 mL hexane
and 30 mL acetone for OPPs at a rate of about 5 ml min-1. Among two determined pesticides, the majority of OCPs
Extracts were concentrated by rotary evaporation, blown has been banned for a long time. In regards to 5 OPPs, 3
down with a gentle stream of nitrogen and exchanged into types have been banned (Parathion, and Trithion Ethion)
hexane, nal volume of 1mL inject to GC-ECD. GCECD and 2 types of restrictions have been gradually as
analysis was carried out on an Agilent 7890 with a DB Malathion and Diazinon to progress to replace pesticides
5.625 capillary column (30m length 0.25mm i.d., 0.25 mm derived environmental friendly biological substances.
lm thickness). The oven temperature began at 120 0C for Table 1 shows that, the concentration of 8 OCPs and 5 OPPs in
3 min and increased to 195 0C (5 min hold time) at a rate of 4 districts, the average concentration of OPPs is higher
15 0C min, increased to 205 0C (5 min hold time) at a rate than OCPs. OPPs and OCPs concentration in Binh Tan is
of 10 0C min, increased to 280 0C (8 min hold time) at a is the highest while the lowest was found in Cu Chi. The
rate of 15 0C min. Split injection of 20:1. average concentration of OPPs evenly in 4 districts not
Standard mixture of 8 OCPs compounds include: -HCH, much different among and lower SD. Conversely, the
-HCH, -HCH , Aldrin, Heptachlor epoxide, - average concentration of OCPs is much different in 4
Endosulfan, Endosulfan sulfate, 4,4 DDT, districts with very high SD.
concentrations of 0.001, 0.0025, 0.005, 0.01, 0.03, 0.05 3.1 Characteristic residues of OPPs in surface water
g ml-1 with mixture of standard 5 OPPs Diazinon,
Malathion, parathion, Ethion, Trithion with concentrations
of 0.005, 0.01, 0.02, 0.03, 0.05 and 0.1 g ml-1 was prepared
by diluting the standard of reference for construction. The
recovery of OCPs is 8091 % (SD<5%), with the OPPs is
103109% (SD<5%) The detection limit of OCPs was 0.01
g l-1 and OPPs 0.1 g l-1 . All analytical procedures were
monitored using strict quality assurance and control
measures. Laboratory blanks consisted mili-pore water
were extracted and analyzed in the same way as samples.
OCPs and OPPs were not detected in blanks.

Figure 2. The average concentration of 5 OPPs at 11 sampling


sites.

Figure 2 shows that Malathion and Diazinon residues


predominate and appear frequently in the survey position
than Parathion, Ethion and Trithion. It is due to the fact
that Malathion and Diazinon are still permitted to use.
Comparison between the different sampling site,
Malathion residues discrepancy, average concentration of
Malathion at Binh Chanh (0.29 0.19 g l-1) , Cu Chi (0.41
0.42 g l-1) , Hoc Mon (0.52 0.44 g l-1) , Binh Tan ( 0.51
0.37 g l-1). Also banned compounds such as Parathion,
Trithion and Ethion still be found in some areas, especially
Figure 1. Location of the eleven sampling sites in 4 district
areas found high concentrations Parathion as Vinh Loc B
3. RESULTS AND DISCUSSION (0.82 g l-1). The residues of these chemicals provoked the
query whether banned chemicals are still in use under
Water samples are characterized by the scene with pH in
different names and types.
the range 5.5 - 7.5, relatively low turbidity and low
impurities such as oil and surface active agents. The It can be seen from figure 3 that Diazinon and Malathion
average concentration of OCPs and OPPs are shown in are 2 substances on the list of organic phosphorus
Table 1 pesticide and also permitted for used in Vietnam from
Table 1. Average concentration of OCPs and OPPs in 4 district
2010. The result of the survey showed that in the sampling
areas, a number of plant protection chemical that contain
Binh multiple pesticide Diazinon and Malathion components
Binh Tan Cu Chi Hoc Mon
Chanh are farmers use as: Malate 50EC, 73EC; Malfic 50 EC,
OPPs 0.88 0.35 1.23 0.18 0.76 0.55 0.80 0.55 Danasu, Bashudin ... In 5 OPPs were analyzed, the
average concentrations at all sampling sites of Malathion
OCPs 17.6 25.7 26.1 30.6 5.2 8.9 21.4 42.6

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is highest (0.40 0.15 g l-1) followed by Diazinon (0.26 + In Asia, DDT is a ubiquitous contaminant through various
0.16 g l-1). environmental matrices. In particular, the dominance of
DDT compounds among POP chemicals is common in
developing Asian countries including Vietnam, China,
Thailand, and India (Hong et al, 2008). DDT has been
banned in Viet Nam since 1997, the presence of 4,4 - DDT
in this study may be due to desorption of residual DDT
from contaminated soil by previous fumigation activities.
During the ooding seasons, rainwater could wash the
soil and release residual DDT to the canal. DDT is a
persistent pesticide that can remain in the soil for up to 30
years (Golnopoulos et al., 2003). DDT metabolizes to
DDD and DDE, and DDE are slowly degradable. It
suggested that HCHs and DDTs mainly came from the
early usage.
Lindane (-HCH) level in this study (4.5 ng l-1) is lower
than the level detected to the level detected in the surface
waters of Northern Greece (81.0 ng l-1) (Golnopoulos et
Figure 3. The average concentration of 5 OPPs. al., 2003) and Selangor River, Malaysia (90.3 ng l-1) (Leong
et al., 2007).
The Malathion level in this study (0.15 0.72 g l-1), Ethion
(not detected 0.09 g l-1) is comparable to the level
detected in the surface waters of Kanpur, Uttar Pradesh,
India (0.12 2.61 g l-1) while Ethion is not detected
(Sankararamakrishnan et al., 2005). Malathion level in this
study was lower than that in Indian estuary (1.37313.013
g l-1) (Sujatha et al., 1999), but higher than that in
Humber Estuary (19 ng l-1) (Zhou et al., 1996). Diazinon
level in this study (0.14 0.70 g l-1) near the level detected
in surface waters of Selangor River Malaysia (0.12 - 0.51 g
l-1) (Leong et al., 2007).
Pesticides after use will be entering to the water
environment due to runoff. In addition, uncollected
chemicals containers waste also causes a large spread of
pesticides into the environment.
Figure 5. Average concentrations of HCH isomers and
endosulfan-sulfate at the sampling sites.

In 8 OCPs surveyed in this study, HCH isomers and


Endosulfan-sulfate dominated compared with other
OCPs. Endosulfan-sulfate was detected at multiple
positions at high levels compared with other OCPs. The
concentration between positions are different, the average
concentration in Tan Nhut is greater than the other
sampling sites (0.013 g l-1). From Fig 4 shows that
Endosulfan sulfate (metabolite of endosulfans) was
relatively higher than - Endosulfan, which suggested the
residue of early usage (Zulin et al, 2002). On the other
hand, the presence of Endosulfan indicated there
might be recent are still some input sources.
Figure 4. The average concentration of 8 OCPs. In all survey locations, the average concentration of
Endosulfan-sulfate at Tan Nhut (0.013 g l-1), Vinh Loc A
The figure 4 clearly shows that, the average concentration
(0.007 g l-1) and Tan Thoi Nhi (0.007 g l-1) are higher
of -HCH (0.00445 g l-1) and Endosulfan sulfate (0.00450
than other sampling sites. The cause may be due to the
g l-1) are higher than other OCPs. It can be seen from fig 5
position of a large area of crops. Endosulfan compounds
that the HCH isomers appeared in most of sampling sites.
are more commonly in arable crops and vegetables. (Jun et
-HCH isomers dominate with relatively high levels
al, 2007)
compared with other isomers. All survey locations at
Pacific region appear -HCH isomers. The ratio of - Our study has revealed a signicant number of pesticides
HCH/-HCH value varied from 0.04 to 5.35, which residues in 11 sampling sites. Frequency of detection, -
indicated that the early usage pattern of HCH is the HCH, -HCH, -HCH , Aldrin, Heptachlor epoxide, -
mixture of industrial HCH and Lindane (Iwata et al., Endosulfan, Endosulfan sulfate, 4,4 DDT (Fig. 6). The
1995). In the industrial HCHs, the constituent distribution detected pesticide levels in dierent parts of the 11
of 4 congener is a (6570%) > (1214%) > (6%) > (5 sampling sites are different and in the same location, the
6%) , while is above 99% in Lindane (Kamrin, 2000). The samples taken in the various canals also difference. This
value of -HCH/-HCH is 4.645.83 for industrial HCHs, could be due to the evaporation of these volatile pesticides
and 0 for Lindane respectively (Zulin et al, 2002). in tropical temperatures, dilution or adsorption of the

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pesticide residues into river sediments. The presence of pesticides detected were Diazinon, Malathion, Ethion,
OCPS can be inferred that the environment may be Trithion, -HCH, -HCH, -HCH , Aldrin, Heptachlor
considerably degraded by pesticides providing additional epoxide, -Endosulfan, Endosulfan sulfate, 4,4 DDT.
impact to the biota and bringing a potential risk to human The ratio of -HCH/-HCH suggested that the HCHs
health (M.G Govedatti, 2001). application had been the mixture of industrial HCHs and
Lindane used in the pass. This study has shown the
presence of organochlorine pesticides despite the fact that
they have been banned for a considerable amount of time
in Viet Nam. This is a consequence of the use of pesticides
of unknown origin, imported from many places, especially
China. The concentrations varied between sampling sites.
Point sources of pollution are obvious and easy to identify
and measure. On the other hand, the non-point sources of
pollutions are difficult to identify and control. This
monitoring study is providing more information on the
OCPs and OPPs contaminations in Ho Chi Minh. For the
risk assessment, it was found that Malathion was
produced the most risk molecule among our studied
compounds. Other organic pesticides (Endosulfan,
Parathion) also threaten the water quality and lead to
Figure 6. Percentage detection frequency of OCPs environmental degradation. Future work will investigate
multi-phase distribution of pesticides in Ho Chi Minh city,
The estimated risk of some compounds of OPPs and OCPs
especially for OPPs, as well as identifying the transfer,
was given as the following. We did the quality estimation
transport models and fate of organic pollutants in the
of pesticides in surface water near agricultural areas in Ho
estuary in order to provide the best management for
Chi Minh city, following Eq (Zulin et al, 2002).
pesticides.
ACKNOWLEDGMENTS

In Eq., which C is the concentration of pollutant; S, the This study was funded by JICA Project. The authors
criteria of water quality; and I, the water quality index of thanks to colleagues at the Faculty of Environmental
the pollutant. If I > 1, means that the pollutant in water Science University of Sciences - Ho Chi Minh City has
have exceed the criteria; while I < 1, it means that there is helped me performed this study. The authors want to
meet to the water quality criteria (QCVN 08: thanks to Ms. Do Thi Thuy Quyen who have spent time
2008/BTNMT). So we calculated the I value which is listed for the review of the English text.
in Table 2. REFERENCES
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