Chemosphere 65 (2006) 1949–1958

www.elsevier.com/locate/chemosphere

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples

in the Northeastern
part of Sa˜o Paulo State, Brazil

Sandra R. Rissato a,*, Ma´rio S. Galhiane a, Valdecir F. Ximenes a, Rita M.B.

de Andrade b, Jandira L.B. Talamoni c, Marcelo Libaˆnio d, Marcos V. de
Almeida e, Benhard M. Apon f, Aline A. Cavalari g

a Department of Chemistry, Paulista State University (UNESP), P.O. Box 473,

17033-360 Bauru, SP, Brazil
b Federal Center of Technologic Education of Ceara´ (CEFET), Fortaleza, CE,
Brazil
c Department of Biology, Paulista State University (UNESP), Bauru, SP, Brazil
d Department of Hydraulic Engineering and Hydric Resource, Federal University of
Minas Gerais (UFMG), Belo Horizonte, MG, Brazil
e Department of Bioengineering, University of Sa˜o Paulo (USP), Sa˜o Carlos, SP,
Brazil
f Chromapon Inc., 9815 Carmenite Road Suite J., 90605 Whittier, CA, United States
g Department of Bioscience, University of Sa˜o Paulo (USP), Sa˜o Paulo, SP,
Brazil

Received 2 November 2005; received in revised form 6 July 2006; accepted 6 July
2006
Available online 17 August 2006

Abstract

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine

pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs),
dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and
congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the
northeastern Sa˜o Paulo, Brazil allowed the evaluation of the contamination status,
distribution and possible pollution sources. The pesticides and PCBs demonstrated
markedly different distributions, reflecting different agricultural, domestic and
industrial usage in each region studied. The ranges of HCH, DDT, and PCBs
concentrations in the soil samples were 0.05–
0.92, 0.12–11.01, 0.02–0.25 ng g 1 dry wt, respectively, and in the surface
water samples were 0.02–0.6, 0.02–0.58 and 0.02–0.5 ng l 1,
respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a
site very close to melting, automotive batteries indus- tries, and agricultural
practice regions. High ratios of metabolites of DDT to DDT isomers revealed the
recent use of DDT in this envi- ronment. The sources of contamination are closely
related to human activities, such as domestic and industrial discharge, street
runoff, agricultural pesticides and soil erosion, due to deforestation as well as
atmospheric transport.
2006 Elsevier Ltd. All rights reserved.

Keywords: Organochlorine pesticides; PCBs; Water; Soil

1. Introduction

Persistent organic pollutants (POPs) are a set of chemi- cals that are toxic,
persist in the environment for long peri- ods of time, and biomagnify as they
move up through the food chain. POPs have been linked to adverse effects on

* Corresponding author. Tel.: +55 14 3103 6135; fax: +55 14 3203 2856.
E-mail address: srissato@fc.unesp.br (S.R. Rissato).
human health and animals, such as cancer, damage to the nervous system,
reproductive disorders, and disruption of the immune system. Because they
circulate globally via the atmosphere, oceans, and other pathways,
POPs released in one part of the world can travel to regions far from their source
of origin (UNEP, 2005).
With mounting evidence, indicating the long-range transport potential of these
substances to regions where they have never been used or produced and the
consequent

0045-6535/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2006.07.011
1950 S.R.
Rissato et al. / Chemosphere 65 (2006) 1949–1958

threats they pose to the environment, the international community has called for
urgent global actions to reduce and eliminate their release into the
environment (Burger et al., 2001).
Organochlorines (OCs), such as polychlorinated biphe- nyls (PCBs) and chlorinated
pesticides, represent an impor- tant group of POPs which have caused worldwide
concern as toxic environmental contaminants (Law et al., 2003; Covacia et
al., 2005; Wurl and Obbard, 2005).
The lipophilic nature, hydrophobicity and low chemical and biological
degradation rates of organochlorine pesti- cides have led to their
accumulation in biological tissues and the subsequent magnification of
concentrations in organisms, progressing through to the food chain (Tanabe,
2002; Helberg et al., 2005). Specifically, one of the key envi-
ronmental concerns, regarding some POPs, is their occur- rence in polar
regions, at surprisingly high levels.
PCBs are very persistent in the environment and are now disseminated
worldwide. They are amongst the indus- trial chemicals banned and included in
the list of priority contaminants to be monitored regularly (USEPA, 1996). They
have been reported to cause a variety of effects including immunologic,
teratogenic, carcinogenic, repro- ductive and neurological problems in
organisms (Nakata et al., 2002).
Chlorinated pesticides such as HCH and DDT are effec- tive pest control
chemicals, used in agriculture and public health activities (malaria
eradication, vectors, etc.) world- wide for the past decades and are still in use
in many devel- oping countries.
In Brazil, as elsewhere, organochlorine pesticides
(OCPs) were used to control pests and thus improved crop yields during the
1970s. Included in the group of OCP- pesticides were DDT, HCH, heptachlor,
aldrin, dieldrin and endrin, among which DDT and HCH were the most
extensively used. Although their use has been discontinued in Brazil since
1985, their persistence has left residual amounts in the soil in many
areas (Rodrigues, 1997; D’amato et al., 2002). At present, the use of DDT is
still allowed in public health programs, to combat etiological vectors
(malarial and leishmaniasis) and emergence agricul- tural use as well.
Historically, South America is regarded as the continent in which DDT, besides
toxaphene and lin- dane, was heavily used. The impact of residues of highly
persistent organochlorine pesticides on environment is par- ticularly interesting.
The pesticides applied to the crops, eventually find their way to the aquatic
environment, thus contaminating it. These are transported to aquatic bodies by
rain runoff, rivers and streams and associated with bio- tic and abiotic
macroparticles (Colombo et al., 1990).
Organochlorine contamination is usually monitored by measuring levels either in
inorganic ecosystem compart- ments (water, air and sediment) or in biota.
The former has the advantage of producing an immediate, geographi- cally
localized measure of contamination, while the latter summarizes a variable
extent of biotransformation and bioaccumulation processes that the
contaminants have
undergone during their passage through biological systems, therefore, providing
a more realistic view of the contami- nant distribution in the environment site.
The present study aims at assessing the occurrence of PCBs, organochlorine
pesticides like HCH isomers (a, b, d and c), and DDT and its metabolites (DDE
and DDD) in soil and surface water from agricultural and industrial sectors
of three regions studied in the northeastern part of Sa˜o Paulo State,
Brazil.
The results provide important information on the cur-
rent contamination status in these regions, and point out to the need of
urgent actions to evaluate the long-term toxi- city of such persistent compounds
and a suitable strategy to improve these areas.

2. Materials and method

2.1. Reagents

All the chemicals and solvents were special grade for pesticide residue
analysis and purchased from Sigma– Aldrich (St. Louis, MI, USA). The
purified water was obtained from a MilliQ water system (Millipore, Bedford, MA,
USA). Pesticide and PCB standards were obtained from Dr. Ehrenstorfer
Laboratories, Augsburg, Germany.
Pesticide and PCB stock solutions (approximately
500 mg/l) of individual standards were prepared by dissolv- ing about 0.050 g of
the pesticide in 100 ml of n-hexane and storing in a freezer 18 C in
glass bottles with PTFE- faced screw caps. The pesticide working solutions were
prepared by an appropriate dilution in n-hexane. Sodium sulfate was
pesticide-grade. Silica Gel, Grade 634, of
100–200 mesh size was used for sample extract clean up.

2.2. Samples

For the present study, sampling was carried out in 2005, during the Fall/Winter,
which is dry and the temperature ranges from 10 to 25 C between the months
of March and June. The sampling points, essentially surrounded by an
agricultural area, possessing no more than 20 acres, were carefully selected
in the Atlantic Forest, mainly in a place about 500 km from the ocean. In this
context, the for- est fragments, according to Viana (1992) may be consid- ered
as the last representative of native biodiversity of the Brazilian forests. The
environments comprising the neigh- borhood of these representatives, are
extremely important for their animal diversity, since the anthropic action may
extinguish a region’s native species through the contamina- tion by organic
pollutants, the difficulty for species to move within fragmented forests and
predation (Blake and Karr,
1987; Metzger and Decamps, 1997).
Soil samples were collected from three regions located in the Northeastern part of
Sa˜o Paulo State, Brazil, namely, Itirapina (region 1 – 22 150 S, 47 510 W),
Bauru (region
2 – 22 210 S, 49 010 W), and Piratininga (region 3 – 22 260
S, 49 030 W) (Fig. 1). The surface water samples were
S.R. Rissato et al. / Chemosphere 65 (2006) 1949–1958
1951

Fig. 1. Map showing the location of soil and water sampling sites in the 3
regions studied.

collected only in regions 2 and 3. These regions present dif- ferent soil types, of
varying aluminum content and fertility. They include structured purple soil,
purple latosol, dark red latosol, red-yellow latosol, lithosol, deep quartz
sands, red-yellow podsol, and hydromorphic soil. The topography varies from flat
to slightly hilly, with accentuated scarps and slopes in some regions.
The vegetation of the regions studied is very heteroge- neous, due, partly,
to climatic conditions and the soil but, mainly, to human interference. Very
fragmented, it consists mainly of cerrados (sparsely arboreal savanna,
short-shrub savanna, and wet meadows), cerrada˜o (arbo- real savanna), semi-
deciduous and riparian forests, and regeneration areas.
Regions 1 and 2, are located within environmental reserves near
melting, automotive batteries industries, and agricultural practice regions,
which are about 160 km from one another. A third area selected (region 3),
at
20 km away from region 2 and 180 km from region 1, is not recognized as an
environmental reserve and presents a mean impact as for anthropic action which
consists of small deforestation areas (Fig. 1).
The surface water samples were collected from rivers in regions 2 and 3. Further
studies will focus on region 1, par- ticularly, because it has a deep and wide
lake which is dif- ficult to be sampled.
2.2.1. Soil
Twenty-nine soil samples were taken at the locations described above, including
forest soils and the top humus layer was included. The samples were collected to
the depth of 1 meter, being the 10-cm upper layer and the whole par- ticle organic
matter discarded. The bulk soil samples were ground and passed through a 2 mm
sieve to remove stones and plant material, after which the samples were homoge-
nized, dry-ice stored and transported in brown glass flasks.

2.2.2. Water
All the water samples were collected in new 2 l polyeth- ylene bottles and
immediately transported to the labo- ratory. Duplicate samples for pesticide
and PCBs measurements were collected from each sampling location. The containers
were carefully filled to overflowing, without passing air bubbles through the sample
or trapping air bub- bles in the sealed containers. Bottles used previously were
washed with detergent, double-rinsed with ultrapure water (Millipore), rinsed
with pesticide grade ethyl alcohol, and dried. After transportation to the
laboratory, the samples were stored at 20 C and the extraction was
normally done within 48 h.
In order to enhance sample integrity, increase the confi- dence of analytical data,
and to prevent reporting ‘‘false’’ positives caused by contamination
incorporated, the study
1952 S.R.
Rissato et al. / Chemosphere 65 (2006) 1949–1958

of a ‘‘field blank’ ’was carried out. The field blank consisted of a sample bottle
that was prepared with the other bottles, packaged and transported to the sample
site and filled with distilled water, stored and transported along with the other
sample bottles, being submitted to analysis. The results showed a ‘‘non-detected’’
(ND) analysis for all pesticides and PCBs, which increased the confidence that the
samples were not contaminated during preparation, field sampling, shipping,
storage or analyses.
Since the samples need to be stored at low temperatures ( 20 C) so as to keep
the integrity of some analytes stud- ied, polyethylene bottles were used and
tests were carried out in order to corroborate the reliability of storage
in polyethylene bottles. For this purpose, the same bottle used in sample
collection was utilized with a Milli-Q water sam- ple, fortified with the analytes
studied at the concentration of 0.10 lg/ml and stored at 20 C. Analyte
recovery was studied for 12, 24, 36, 48, 60 and 72 h, periods which dis- played
recoveries greater than 85% for all analytes.

2.3. Extraction procedure

2.3.1. Soil
Five grams of dried and homogenized soil samples were extracted for 3 h in a
Soxhlet apparatus with 130 ml pes- ticide grade n-hexane: acetone 1:1 v/v.
After extraction, the sample was concentrated up to a volume of about
5 ml with a rotary vacuum evaporator at 45 C. A clean-
up column containing 6 g of silica gel topped with 2 cm of anhydrous sodium
sulfate was washed with 2 · 15 ml hexane. The sample extract was transferred
to the column and eluted with 130 ml of hexane and 15 ml of dichloro- methane
(USEPA Method 3630C, 1996). The fractions were collected as a single
fraction and concentrated up to 5 ml by a rotary vacuum evaporator at 45 C,
and fur- ther to 1 ml under a gentle gas stream of purified nitrogen. The extracts
were kept in sealed bottles at 20 C, prior to analysis. The recovery efficiency
was evaluated by extracting spiked soil samples (at 0.1 lg g 1 for each com-
pounds; Table 1).

2.3.2. Water
Liquid–liquid extraction, followed by gas chromato- graphic analysis (USEPA,
1980), was used for the determi- nation of pesticide residues. In general, the EPA
protocols, with certain modifications, were used for the analysis. Around 1
liter of the water sample was filtered using a
0.45-lm Whatman glass fiber paper filter, treated with
10 g of sodium sulfate and extracted thrice with 75 ml of methylene chloride.
The combined extracts were filtered and concentrated in a vacuum rotary
evaporator. The solu- tion obtained was filtered with a pinch of sodium sulfate
and completed with hexane, up to 5 ml, and one microliter of this solution was
injected and analyzed. The recovery was evaluated by extracting spiked
water samples at a
0.1 lg ml 1 concentration.

Table 1
The detection limit (LOD), mean recovery, relative standard deviation (RSD) and
calibration curve (r2) for OCPs and PCBs in water and soil samples
OCPs Water
Soil
LOD (lg l 1)
LOQ (lg l 1)
Precision
(RSD)
Recovery
(%)
LOQ
(ng g 1)
Precision
(RSD)
Recovery
(%)
Calibration curve r2
1. a-HCH 0.002 0.007 8.5
95 0.03 8.8 105
0.9986
2. c-HCH 0.001 0.005
6.7 82 0.05 6.4
99 0.9997
3. b-HCH 0.002 0.006
10.3 95 0.05 5.9
85 0.9982
4. Heptachlor 0.003 0.008 4.8
92 0.05 6.1 77
0.9995
5. d-HCH 0.001 0.005
7.2 81 0.05 7.2
75 0.9979
6. Aldrin 0.001 0.005
9.1 88 0.04 3.9
91 0.9993
7. Heptachlor-epoxide 0.005 0.012 6.3
91 0.03 5.2 125
0.9981
8. Endosulfan I 0.001 0.005 5.3
83 0.05 9.1 109
0.9980
9. p,p0-DDE 0.002 0.005
4.9 82 0.01 6.0
93 0.9993
10. Dieldrin 0.001 0.005
6.6 94 0.05 5.8
88 0.9978
11. Endrin 0.002 0.005
7.1 90 0.05 7.3
97 0.9996
12. o,p0-DDT 0.002 0.005
8.3 93 0.01 6.4
81 0.9988
13. p,p0-DDD 0.002 0.005 5.8
86 0.01 10.3 102
0.9991
14. Endosulfan II 0.001 0.005 3.9
83 0.05 5.9 97
0.9985
15. p,p0-DDT 0.002 0.005
8.2 89 0.01 3.7
79 0.9982
16. Endosulfan sulfate 0.001 0.005 6.3
95 0.01 10.5 84
0.9991
17. Metoxichlor 0.003 0.01
4.7 91 0.10 9.3
102 0.9993
18. Mirex 0.003 0.01
5.5 89 0.10 8.4
97 0.9975

PCB28 0.002 0.005

12.5 77 0.02 5.8
77 0.9978
PCB52 0.002 0.005
6.9 119 0.02 6.3
109 0.9982
PCB101 0.003 0.005
10.2 104 0.02 7.2
97 0.9973
PCB118 0.002 0.005
8.7 112 0.02 9.1
110 0.9981
PCB138 0.003 0.005
5.9 92 0.02 4.5
86 0.9964
PCB153 0.002 0.005
7.7 87 0.02 8.0
91 0.9983
PCB180 0.002 0.005
8.0 79 0.02 7.2
96 0.9976
S.R. Rissato et al. / Chemosphere 65 (2006) 1949–1958
1953

2.4. Analytical procedure

Sample analyses were conducted using a Hewlett Pack- ard Model 5890 Series II
gas chromatograph with a HP
5972 mass selective ion detector (quadrupole) and a fused-silica
capillary column DB-5 – 5% phenyl 95% di- methylpolysiloxane (30 m · 0.32 mm
I.D, film thickness
0.25 lm). Purified helium was used as the carrier gas with a flow rate of 1.5 ml/
min. Four microliters of sample were injected into the GC–MS in splitless mode
with an injection time of 1 min and the injection temperature was set to
280 C. The oven temperature for analysis of OCPs and
PCBs was programmed from 70 to 140 C, at a rate of
25 C/min, 140 to 179 C, at a rate of 2 C/min, 179 to
210 C, at a rate of 1 C/min, 210 to 300 C, at 5 C/min, and held for 10
min. The analysis was conducted in the selective ion monitoring mode (SIM) and
the mass spectro- metric parameters are: impact ionization voltage 70 eV; ion
source temperature 230 C; transfer line 300 C; electron multiplier voltage
1200 V; solvent delay 2.9 min; electron scan rate 1.5 scan/s; scanned-mass
range 40–600 m/z.

2.5. Quality assurance

The residue levels of OCPs and PCBs were quantita- tively determined by the
external standard method using peak area. Linear calibration curves for all
pesticides and PCBs over five calibration levels, from 0.01 to 0.5 lg l 1, and
all standard curves were within the acceptable limits of the linearity criterion,
which are shown in Table 1.
The potential contamination of solvents used was checked by measuring
POPs in the first and last 100 ml of the solvent used from every 4-liter
stock bottle. The blank methods were carried out for every six samples col-
lected. The control standards were carried out for every four samples
analyzed so as to check the performance of the analytical system, during
analysis.
The detection limits (LOD) of OCPs and PCBs were determined as the concentration of
analyses in a sample that gives rise to a peak with a signal-to-noise ratio (S/N)
of 3.
The limit of quantification (LOQ) for PCBs and OCPs was based on GC/MS
performance and on laboratory background levels, which were determined by
analyzing procedural blanks. Procedural blank levels were consistent (RSD < 30%)
and therefore the median blank value was used for subtraction. LOQs were
established at three times the standard deviation of the procedural blank level,
result- ing in a certainty of more than 95% for results given to the samples.
The method was optimized and validated using control water and soil samples
spiked in 0.1 lg ml 1 and 0.1 ll g 1, respectively. Spiked water and soil
samples (n = 5) were determined with good recoveries and precision (Table
1). The same procedure was applied for both spiked and real samples.
In all 4 sites, triplicate samples were collected during each survey, to
evaluate the reproducibility of the overall
method. The relative standard deviations (RSD) for tripli- cate samples were
less than 11% for OCPs and 13% for PCB congeners (Table 1).
The data confirmed the practicability of the analytical protocols herein in the
determination of OCPs and PCBs residues in the water and soil samples.

3. Results and discussion

3.1. Soil

This paper reports on the results obtained from a com- prehensive study in the
Northeastern part of Sa˜o Paulo, Brazil, for levels of organic contaminants, and
represents an attempt to improve our understanding of pollution from non-point
sources. As a result, the following interpretation and discussion focused on
organochlorine pesticides and PCBs, in surface water and soil.
The distribution of various organochlorine pesticides in the soils, from 3 sampling
areas, revealed a wide range of fluctuations, as shown in Table 2. The
concentration of four important HCHs isomers revealed a heterogenic dis-
tribution nature (Fig. 2a). The composition of HCH iso- mers a-, b- and c-HCH
(lindane) was detected in some samples, whereas d was below the detection levels
in most cases. This may be related to the isomerization of HCHs during the
transformation process in the soil, owing to bac- teria or humic substances action
(Waliszewski et al., 2004; Kumar et al., 2005). The a-isomer was the
predominant one, followed by the c-isomer, reflecting the use of a tech- nical
mixture of HCHs (Kannan et al., 1995). Alpha-HCH has higher values of the Henry’s
law constant and vapor pressure than b-HCH and c-HCH, indicating greater effi-
ciency by atmospheric transport of a-isomer than other iso- mers (Iwata et al.,
1994).
A slightly higher trend of HCH concentrations in region
2 was observed, most likely, due to the a higher level of agricultural and
industrial activity near this site.
The concentrations of DDT and its metabolites, DDD
and DDE, were higher in the sample locations around regions 1 and 2. As
reported, DDE was the main contrib- utor to the sum of DDTs, indicating
that the transfor- mation of DDT into DDE, is favoured by
aerobic conditions (Manirakiza et al., 2001). Owing to its extremely low
solubility in water, DDT is retained in a greater degree, by soils (WHO, 1989). The
presence of DDT and its meta- bolites can be attributed to the use of this
insecticide in agriculture, as well as antimalaria sanitary activities,
carried out throughout the country (D’amato et al., 2002) (Fig. 2b).
This study revealed that the concentrations of HCHs were lower than those of
DDTs. This may be due to their differences in physicochemical and biosolubility
properties, with HCHs having higher water solubility than DDTs, vapor
pressure and biodegradability and lower lipophilicity and particle affinity as
compared to DDTs (Loganathan and Kannan, 1994).
1954 S.R.
Rissato et al. / Chemosphere 65 (2006) 1949–1958

Table 2
Residue results of organochlorine pesticides and PCBs (ng g 1) obtained in soil
analysis of the samples in regions studied 1, 2 and 3
OC pesticides Residuea (ng g 1)
Region 1 Region 2
Region 3
1. a-HCH 0.06 (<0.03–0.22)
0.26 (0.09–0.51) <0.03 (<0.03–0.08)
2. c-HCH <0.05 (<0.05–0.09)
0.15 (<0.05–0.4) ND
3. b-HCH <0.05 (<0.05–0.05)
0.15 (<0.05–0.34) <0.05 (<0.05–0.06)
4. Heptachlor <0.05 (<0.05–0.05)
ND <0.05 (0.05–0.08)
5. d-HCH ND
0.07 (<0.05–0.21) ND
6. Aldrin <0.04 (<0.04–0.09)
0.08 (<0.04–0.23) ND
7. Heptachlor-epoxide ND
0.05 (0.08–0.2) ND
8. Endosulfan I 0.71 (<0.05–2.09)
<0.05 (<0.05–0.06) <0.05 (<0.05–0.05)
9. p,p0-DDE 5.16 (2.05–8.8)
5.26 (2.39–10.23) 0.21 (0.05–0.44)
10. Dieldrin <0.05 (<0.05–0.05)
0.21 (0.05–0.96) ND
11. Endrin 0.08 (<0.05–0.25)
0.11 (<0.05–0.13) ND
12. o,p0-DDT 0.47 (0.05–1.69)
1.15 (0.08–2.58) 0.07 (<0.01–0.16)
13. p,p0-DDD 0.48 (<0.01–1.23)
0.1 (<0.01–1.39) 0.07 (<0.01–0.09)
14. Endosulfan II 1.77 (<0.05–3.69)
0.12 (0.06–0.29) <0.05 (<0.05–0.05)
15. p,p0-DDT 0.5 (0.03–1.12)
0.64 (0.09–1.39) 0.07 (<0.01–0.13)
16. Endosulfan sulfate 1.77 (<0.05–3.69)
0.15 (0.06–0.41) <0.05 (<0.05–0.05)
17. Metoxichlor ND
<0.1 (<0.1–0.1) ND
18. Mirex 1.41 (<0.1–2.78)
0.26 (<0.1–0.47) ND

PCBs
PCB28 <0.02 (0.03–0.1)
0.07 (0.03–0.25) ND PCB52
0.07 (0.03–0.22) 0.07 (0.03–0.25)
ND PCB101 0.05 (0.03–0.12)
0.12 (0.03–0.23) ND PCB118
0.04 (<0.02–0.11) 0.13 (0.06–0.28)
ND PCB138 <0.02 (<0.02–0.03)
0.09 (<0.02–0.19) ND PCB153
0.05 (<0.02–0.23) 0.06 (0.05–0.16)
ND PCB180 <0.02 (<0.02–0.08)
0.07 (<0.02–0.15) ND
a Each value represents the mean of N = 9 samples. Range of values is in
parentheses.
2.5
50
a-HCH
g-HCH
b-HCH
d-HCH 40

p.p' DDE o.p' DDT p.p' DDD p.p' DDT

2.0
30
1.5
20
1.0

10
0.5

0.0

Region 1 Region 2 Region 3

0
Region 1 Region 2 Region 3

1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
PCB28
PCB52
PCB101
PCB118
PCB138
PCB153
PCB180

Region 1 Region 2

Fig. 2. Concentrations of DDTs (a), HCHs (b) and PCBs (c) in soil samples from
the 3 regions studied.

HCHs and DDTs concentrations were generally low in comparison with those of
other countries (as shown in
Table 3), indicating that the Northeastern part of Sa˜o Paulo
State was not grossly polluted by organic contaminants.
S.R. Rissato et al. / Chemosphere 65 (2006) 1949–1958
1955

Table 3
Comparison of organochlorine (ng g

1) in soil samples from other

pesticides and PCB concentrations suggests that most sites
(1–9) in region 2, were extensively exposed to the same mix-
locations of the world
Locations DDTs HCHs References
Shangai (China) 18–142 <0.03–2.4 Nakata et al. (2005)
ture of pollutants. This hypothesis is based on the assump- tion that the observed
concentrations are rather due to the input of contaminants than to the specific
accumulation
Guanting Reservoir
(China)
Tasman, Waikato, Auckland
(New Zeland)
ND–94.07 ND–8.96 Zhang et al. (2005)

30–34500 – Gaw et al. (2006)

and storage properties of the studied soils. An example are samples 7, 8
and 9 (region 2), which exhibit relatively high PCB concentrations, significantly
differing from the remaining samples. Region 2 is located in a protected forest
Beijing (China) 0.77–2178 1.36–56.61 Zhu et al. (2005)
Tanzania <0.1–97 <0.1–59 Kishimba et al.
(2004)
area, but close to a batteries industry. However, there is no
information available which confirms a specific source.
South California
(USA)
0.11–44.8 <0.1–0.54 Kannan et al. (2003)
Nevertheless, the total levels for PCBs in region 1 (0.03–
0.35 ng g 1) were lower than those detected in region 2
Georgia (USA) 0.34–33.6 <0.1–0.54 Kannan et al. (2003)
Northeastern part of Sa˜o Paulo
0.12–11.01 0.05–0.92 Present study
(0.03–0.89 ng g 1), but higher than those detected in region
3 (below detection limit) (Table 2). The levels of PCB found
State (Brazil)

Total DDT (0.12–11.01 ng g 1 dry wt.) concentrations found in this area of

Sa˜o Paulo State are comparable with those of Georgia (Kannan et al., 2003) and
lower than the residues found in other countries.
HCHs residues in this area were lower than those of almost all locations,
except for South California and Geor- gia (USA) (<0.1–0.54 ng g 1) (Kannan
et al., 2003). According to (Cavanagh et al., 1999), organochlorine con-
centrations in soils from tropical regions were observed to be low due to rapid
evaporation. He also claimed that vol- atilization of persistent organic
compounds such as orga- nochlorine occurs in climate of tropical regions. Hence,
it is possible that the major loss of many organochlorine pes- ticides used in
Brazil occurs through volatilization.
The currently used pesticides were identified as dieldrin, endrin, endosulfan I,
endosulfan II, endosulfan sulfate and mirex . Their contamination was
widespread in the soil with different quantities, which confirms the persistent
character of these molecules and their adsorption to soil. In contrast, levels
of heptachlor-epoxide, heptachlor and methoxychlor, even used as wood
preservative, for exam- ple, were below the detection limit (either <0.05 or
<0.10).
Endosulfan was detected in nearly all soil samples in regions 1 and 2, at
medium concentrations, mainly repre- sented by isomer II, which differs from the
technical formu- lation and can be related to the faster degradation of
isomer I, in soils. Indeed, the measured half-lives for I- and II-
endosulfan were 60 and 200 days, respectively (ATSDR, 1993). The concentration of
endosulfan sulfate was always higher than the sum of both endosulfan iso-
mers, as it is the major degradation product by soil bacte- ria, which raises
concerns about its toxicity, since it is known to be as toxic as the
parent compound (Awasthi et al., 2000). However, the endosulfan residues in
regions
3 were lower than the quantification limit or not detected
(Table 2).
Table 2 summarizes the PCB levels (sum of seven PCBs) in the soil samples. The
major PCB and OC pesticide levels were found in region 2. The pronounced
correlation of OC
in region 1, can be related to the sites located close to the automotive industry
(Fig. 2c).
The comparison of contaminant levels and the use of the soils revealed a relatively
higher amount of PCB in the soils around the forests and lower levels in the
center of regions
1 and 2 (sites 7, 8, 9). PCB congeners in forest soils indicate a gradient towards
lower relative shares of the lower chlo- rinated congeners. These characteristics
of forest soils have been described in the literature (Wania and McLachlan,
2001). The canopy of forests act as an efficient trap, ampli- fying the transfer
of semi-volatile organic compounds (SOCs) to the soil. The gaseous
fraction of the contami- nants is absorbed by diffusion into the cuticular
surface of the leaves, increasing the transfer of pollutants to the soil, by
litter fall. Horstmann and McLachlan (1998) pro- posed three categories of
chemicals differing in their parti- tioning characteristics: More volatile SOCs, as
represented by PCB 28–118, can achieve a partitioning equilibrium between the
gaseous phase and the leaf, leading to a rela- tive decrease in the congener
pattern. In contrast, the uptake capacity of the leaves for SOCs of
intermediate vol- atility is not limited by reaching the partitioning
equilib- rium which favours the enrichment of the respective compounds and causes
high relative concentrations in the congener and homolog patterns (PCB 138–
180). For the third category, including the relatively non-volatile SOCs, the
gaseous deposition, is insignificant, in comparison with particle-bound deposition.
Hence, the high levels in these forest soils are presumably rather due to higher
deposition rates than to higher gaseous or particle-bound air concen- trations in
the respective locations. Horstmann and McLachlan (1998) have shown that, an
extreme case depo- sition of airborne SOCs in a forest, can be enhanced by a
factor of up to 10, as compared to a nearby non-forest area, exposed to
the same aerial gaseous or particle-bound PCB concentrations.
A comparison between the PCB levels found in the sam- pling carried out in sites
surrounding the forest, in relation to interior sites, reveals a decrease,
suggesting that part of the results may be attributed to the volatility of these
congeners, which are more exposed to environmental conditions.
1956 S.R.
Rissato et al. / Chemosphere 65 (2006) 1949–1958

Table 4
Residue results of organochlorine pesticides and PCBs (lg l 1) obtained in
surface water analyses of the samples in regions 2 and 3
3.2. Water
The results of water sample analyses from 2 studied
a 1
OC pesticides Residue (lg l )
Region 2 Region 3
1. a-HCH 0.09 (0.05–0.19) 0.013 (0.01–0.022)
2. c-HCH 0.137 (0.009–0.39) 0.01 (0.005–0.03)
3. b-HCH 0.04 (0.06–0.1) 0.037 (0.07–
0.08)
4. Heptachlor ND ND
5. d-HCH <0.005 (<0.005–0.005) <0.005 (<0.005–0.005)
6. Aldrin <0.005 (<0.005–0.006) ND
7. Heptachlor-epoxide ND ND
8. Endosulfan I 0.048 (<0.005–0.1) 0.021 (<0.005–0.08)
9. p,p0-DDE 0.13 (0.01–0.38) 0.036 (<0.005–
0.07)
10. Dieldrin <0.005 (<0.005–0.005) ND
11. Endrin ND <0.005
(<0.005–0.005)
12. o,p0-DDT 0.006 (<0.005–0.01) 0.013 (0.01–0.02)
13. p,p0-DDD 0.045 (0.01–0.11) 0.041 (<0.05–0.09)
14. Endosulfan II 0.038 (<0.005–0.08) <0.005 (<0.005–0.005)
15. p,p0-DDT 0.022 (<0.005–0.08) 0.04 (0.01–0.13)
16. Endosulfan sulfate 0.006 (<0.005–0.01) 0.006 (<0.005–0.018)
17. Metoxichlor <0.01 (<0.01–0.01) <0.01 (<0.01–0.01)
18. Mirex <0.01 (0.05–0.12) 0.03 (0.03–0.08)

PCBs
PCB28 0.127 (0.03–0.33) 0.047 (0.02–
0.09) PCB52 0.041 (<0.005–0.11) 0.025
(0.02–0.05) PCB101 0.042 (0.03–0.14) 0.013
(<0.005–0.04) PCB118 <0.005 (<0.005–0.005) 0.017
(<0.005–0.07) PCB138 ND
<0.005 (<0.005–0.005) PCB153 <0.005 (<0.005–0.015)
<0.005 (<0.005–0.005) PCB180 ND
ND
a Each value represents the mean of N = 4 samples. Range of values is in
parentheses.
regions are shown in Table 4. The dominant isomers from both regions were b- and c-
HCH and are consistent with b- HCHs environmental degradation difficulty and the
large use of c-HCH (lindane). Moreover, losses by volatilization are higher for
the a isomer.
The a-HCH/c-HCH ratio can be used to identify the source of HCHs in water
(Maldonado and Bayona, 2002; Zhang et al., 2003). An a-HCH/c-HCH ratio in
areas where lindane has been used, typically ranges from 0.2 to
1, due to the photochemical transformation of c-HCH into a-HCH, compared to a
range of 4–15 for technical mix- tures of HCH (McConnell et al., 1993). In
this study, the a-HCH/c-HCH ratio in surface water ranged between
0.28 and 5.55 in region 2, and 0.67 and 4.4 in region 3. The results showed
that in 25% of all samples, the a- HCH/c-HCH ratio was below 1, indicating
lindane as the HCH source. Higher ratios may be explained by the use of
technical HCH mixtures in the past, and/or due to pho- tochemical transformation
of c-HCH into a-HCH in the atmosphere, with subsequent deposition in the
surface water (Table 4). The key environmental sources of the sur- face water may
be the regional use of HCH isomer pesti- cides in adjacent horticultural areas,
in both regions, or as wood preservative (Fig. 3a).
The ratios of DDE/PDDTs and DDD/PDDTs can be
used to assess how recent DDT contaminations occurred in
0.55
0.50
0.45
0.40
0.35
0.30
0.25
0.20
0.15
0.10
0.05
0.00

Region 2

a-HCH
g-HCH
b-HCH
d-HCH

Region 3

0.5

0.4

0.3

0.2

0.1

0.0
Region 2

p.p'DDE o.p'DDT p.p'DDD p.p'DDT

Region 3

0.5

0.4
PCB28
PCB52
PCB110
PCB181
PCB135

0.3

0.2

0.1

0.0

Region 2

Region 3

Fig. 3. Concentrations of DDTs (a), HCHs (b) and PCBs (c) in water samples from
the 3 regions studied.
S.R. Rissato et al. / Chemosphere 65 (2006) 1949–1958
1957

the environment (Maldonado and Bayona, 2002). In this study, in region 2, the
DDE/PDDTs and DDD/PDDTs
ratios in surface water ranged between 0.75–38 and 0.12–
11, respectively, and in region 3, between 0.25–2.34 and

0.6–2. In region 2, only 30% of the water samples presented the DDE/PDDTs and
DDD/PDDTs ratios below unity,
while in region 3, the studied samples resulted in values above these. It
appears that DDT contaminations are still going on in region 3, or may be
derived from atmospheric transport from other parts of Sa˜o Paulo State (Fig.
3b).
The results revealed that the HCHs concentrations were
lower than DDTs’. This may be due to their differences in physicochemical and
biological properties, having HCHs a higher water solubility, vapor pressure,
biodegradability, lower lipophilicity and particle affinity as compared to
DDTs properties (Loganathan and Kannan, 1994).
Endosulfan I, endosulfan II, endosulfan sulfate, meth- oxychlor and mirex were
detected in some sample locations at low concentrations. The presence of
residues of such compounds, in the samples analyzed, can be attributed to
arbitrary applications in adjacent horticultural properties where vegetables and
grain crops are grown.
The behaviour of PCBs, in water, is entirely different
from that of soil in the same location (Fig. 3c). In water, the results of low
chlorinated biphenyls (di-, tri- and tetra-) were 72.7% and 78.6% in regions 2,
and 3, respectively, while the results for high chlorinated biphenyls
(penta-, hexa- and hepta-) were 27.3% and 21.4% (Table 4). Low chlorinated
biphenyls are more water-soluble than high chlorinated biphenyls, which might
account for the elevated levels of di- to tetrachloro biphenyls, in relation to
penta- to heptachloro biphenyls, in water. As suggested by Zhang et al.
(2003), high chlorinated PCBs with high Kow, are probably more adsorbed to
suspended particulate material than the low chlorinated PCBs. These materials,
then, prob- ably settle onto the bottom sediment, near to the source. The
total PCBs, in the water from region 2, varied from
0.03 to 0.58 lg l 1, which is 3 times higher than those in
region 3 (ranging from 0.02 to 0.18 lg l 1). The higher concentration of
these pollutants in region 2 may be associ- ated with the melting and battery
industries, besides eucalyptus-wood treating companies in the area (Fig. 1).

4. Conclusions

This study has provided the first data on the levels of persistent chlorinated
pesticides and PCBs in soil and sur- face water of the northeastern region of
Sa˜o Paulo State, Brazil.
The results indicated that DDT was the major contam- inant in most samples
analyzed in this study. Although the use of DDT has been officially banned in
Brazil for over 20 years, the concentrations found in soil and surface water
samples suggested the recent use of this insecticide in agri- culture, as well as
in antimalaria sanitary activities.
The presence of the a-isomer HCH, followed by the c- isomer, was detected in
both soil and surface water sam-
ples, in all studied regions, indicating lindane as the main
HCH source.
The low chlorinated biphenyls (di-, tri- and tetra-) were present at relatively
high concentrations in the surface water samples as compared to soil
samples, in which the high chlorinated biphenyls predominated. The probable reason
is that the low chlorinated biphenyls are more water-soluble while the
high chlorinated biphenyls with a high Kow, are probably more adsorbed to
suspended partic- ulate material.
The regions studied presented differences in pesticides and PCBs levels, which
are related to the diversity of poten- tial inputs from sources such as industry,
wastewater, street runoff, agricultural pesticides as well as soil erosion, due to
deforestation.
The baseline data can be used for regular ecological monitoring, considering the
industrial and agricultural growth around these important ecosystem regions
studied.

Acknowledgement

The authors would like to thank the financial support granted by FAPESP
and Professor Jose´ H. Toffanello Cardoso.

References

ATSDR (Agency for Toxic Substances and Disease Registry), US

Department of Health and Human Services, 1993. Toxicological profile for
endosulfan. TP-91/16, ATSDR, Atlanta, GA, 181.
Awasthi, N., Ahuja, R., Kumar, A., 2000. Factors influencing the
degradation of soil applied endosulfan isomers. Soil. Biol. Biochem.
32, 1697–1705.
Blake, J.G., Karr, J.R., 1987. Breeding birds in isolated woodlots: area and
habitat relationships. Ecology 68, 1724–1734.
Burger, J.K., Giesy, J.P., Grue, C.E., Gochfeld, M., 2001. Effects of environmental
pollutants on avian behaviour. In: Dell’Omo, G. (Ed.), Behavioural Ecotoxicology.
John Wiley & Sons, West Sussex, UK, pp. 337–376.
Cavanagh, J.E., Burns, K.A., Brunskill, G.J., Coventry, R.J., 1999.
Organochlorine pesticide residues in soils and sediments of the Herbert and
Burdekin River regions, North Queensland-implications for contamination of
the Great Barrier Reef. Mar. Pollut. Bull. 39, 367–
375.
Colombo, J.G., Khali, M.F., Horth, A.C., Catoggio, J.A., 1990. Distri-
bution of chlorinated pesticides and individual polychlorinated biphe- nyls in
biotic and abiotic compartments of the Rio de La Plate. Environ. Sci.
Technol. 24, 498–505.
Covacia, A., Gheorgheb, A., Voorspoelsa, S., Maervoeta, J., Redekerc, E.S.,
Blustc, R., Schepensa, P., 2005. Polybrominated diphenyl ethers, polychlorinated
biphenyls and organochlorine pesticides in sediment cores from the Western
Scheldt river (Belgium): analytical aspects and depth profiles. Environ. Int. 31,
367–375.
D’amato, C., Torres, J.P.M., Malm, O., 2002. DDT (Dicloro Difenil Tricloroetano):
Toxicidade e Contaminac¸a˜o Ambiental – Uma Revisa˜o. Qu´ım. Nova 25,
995–1002 (in Portuguese).
Gaw, S.K., Wilkins, A.L., Kim, N.D., Palmer, G.T., Robinson, P., 2006.
Trace element and PDDT concentrations in horticultural soils from
the Tasman, Waikato and Auckland regions of New Zealand. Sci. Total
Environ. 355, 31–47.
Helberg, M., Bustnes, J.O., Erikstad, K.E., Kristiansen, K.O., Skaare, J.U.,
2005. Relationships between reproductive performance and
1958 S.R.
Rissato et al. / Chemosphere 65 (2006) 1949–1958

organochlorine contaminants in great black-backed gulls (Larus marinus).

Environ. Pollut. 134, 475–483.
Horstmann, M., McLachlan, M.S., 1998. Atmospheric deposition of semivolatile
organic compounds to two forest canopies. Atmos. Environ. 32, 1799–
1809.
Iwata, H., Tanabe, S., Aramoto, M., Sakai, N., Tatsukawa, R., 1994.
Persistent organochlorine residues in sediments from the Chukechi
Sea, Bering Sea and Gulf of Alaska. Mar. Pollut. Bull. 28,
746–753.
Kannan, K., Battula, S., Loganathan, B.G., Hong, C.-S., Lam, W.H.,
Villeneuve, D.L., Sajwan, K., Giesy, J.P., Aldous, K.M., 1995. Geographical
distribution and accumulation features of organochlo- rine residues in fish in
tropical Asia and Oceania. Environ. Sci. Technol. 29, 2673–2683.
Kannan, K., Battula, S., Loganathan, B.G., Hong, C.-S., Lam, W.H.,
Villeneuve, D.L., Sajwan, K., Giesy, J.P., Aldous, K.M., 2003. Trace organic
contaminants, including toxaphene and trifluralin, in cotton field soils from
Georgia and South Carolina, USA. Arch. Environ. Contam. Toxicol. 45, 30–36.
Kishimba, M.A., Henry, L., Mwevura, H., Mmochi, A.J., Mihale, M., Hellar,
H., 2004. The status of pesticide pollution in Tanzania. Talanta
64, 48–53.
Kumar, M., Chaudhary, P., Dwivedi, M., Kumar, R., Paul, D., Jain, R.K.,
Garg, S.K., Kumar, A., 2005. Enhanced biodegradation of beta- and delta-
hexachlorocyclohexane in the presence of alpha- and gamma-isomers in
contaminated soils. Environ. Sci. Technol. 39,
4005–4011.
Law, R.J., Alaee, M., Allchin, C.R., Boon, J.P., Lebeuf, M., Lepom, P.,
2003. Levels and trends of polybrominated diphenylethers and other brominated
flame retardants in wildlife. Environ. Int. 29, 757–770.
Loganathan, B.G., Kannan, K., 1994. Global organochlorine contami-
nation trends: an overview. Ambio 23, 187–191.
Maldonado, C., Bayona, J.M., 2002. Organochlorine compounds in the Northwestern
Black Sea water: distribution and water column process. Estuar. Coast. Shelf Sci.
54, 527–540.
Manirakiza, P., Covaci, A., Andries, S., Schepens, P., 2001. Automated Soxhlet
extraction and single step clean-up for the determination of organochlorine
pesticides in soil by GC–MS or GC–ECD. Int. J. Environ. Anal. Chem. 8, 25–
39.
McConnell, L.L., Cotham, W.E., Bidleman, T.F., 1993. Gas exchange of
hexachlorocyclohexane in the Great Lakes. Environ. Sci. Technol. 27,
1304–1311.
Metzger, J.P., Decamps, H., 1997. The structural connectivity threshold: a
hypothesis in conservation biology at the landscape scale. Acta Oecol.
– Int. J. Ecol. 18, 1–12.
Nakata, H., Kawazoe, M., Arizono, K., Abe, S., Kitano, T., Shimada, H.,
2002. Organochlorine pesticides and polychlorinated biphenyl residues in foodstuffs
and human tissues from China: status of contamination, historical trend, and
human dietary exposure. Arch. Environ. Contam. Toxicol. 43, 473–480.
Nakata, H., Hirakawa, Y., Kawazoe, M., Nakabo, T., Arizono, K., Abe, S.I.,
Kitano, T., Shimada, H., Watanabe, I., Li, W., Ding, X., 2005. Concentrations
and compositions of organochlorine contaminants in sediments, soils, crustaceans,
fishes and birds collected from Lake Tai, Hangzhou Bay and Shanghai city region,
China. Environ. Pollut. 133,
415–429.
Rodrigues, G.S., 1997. In: Libro Verde – Elementos para una politica
agroambiental en el Cono Sur. Programa cooperativo para el
desarrollo Tecnologico Agropecuario del Cono Sur – PROCISUR – Subprograma
Recursos Naturales y Sostenibilidad Agr´ıcola. Instituto Interamericano de
Cooperacio´n para la Agricultura, Montevideo, Uruguay (in Spanish).
Tanabe, S., 2002. Contaminations and toxic effects of persistent endocrine
disrupter in marine mammals and birds. Mar. Pollut. Bull. 45, 69–77. UNEP, 2005.
<http://www.chem.unep.ch/pops/default.html> (accessed in
October 2005).
US Environmental Protection Agency, 1996. PCBs: a cancer dose– response
assessment and applications to environmental mixtures. EPA/600/P-96/001F.
USEPA, US Environmental Protection Agency, 1996. Method 3630, Revision C.
Washington, DC, USA.
USEPA (United States Environmental Protection Agency), 1980. In: Watts,
R.R. (Ed.), Analysis of Pesticide Residues in Human and Environmental Samples –
Compilation of Methods Selected for Use in Pesticide Monitoring Programs. EPA-
600/80-038.
Viana, V.M., 1992. Restaurac¸a˜o e manejo de fragmentos florestais. In:
Congresso Nacional sobre Esseˆncias Nativas, Sa˜o Paulo: Instituto Florestal 2,
pp. 400–406 (in Portuguese).
Waliszewski, S.M., Carvajal, O., Infanzon, R.M., Trujillo, P., Aguirre,
A.A., Maxwell, M., 2004. Levels of organochlorine pesticides in soils and rye plant
tissues in a field study. J. Agric. Food Chem. 52, 7045–
7050.
Wania, F., McLachlan, M.S., 2001. Estimating the influence of forests on the
overall fate of semivolatile organic compounds using a multimedia fate model.
Environ. Sci. Technol. 35, 582–590.
World Health Organization (WHO), 1989. Environmental health Criteria
83, DDT and its Derivatives Environmental Effects. World Health
Organization, Geneva.
Wurl, O., Obbard, J.P., 2005. Organochlorine pesticides, polychlorinated biphenyls
and polybrominated diphenyl ethers in Singapore’s coastal marine sediments.
Chemosphere 58, 925–933.
Zhang, Z.L., Hong, H.S., Zhou, J.L., Yu, G., 2003. Fate and assessment
of persistent organic pollutants in water and sediments from Minjiang
River Estuary, Southeast China. Chemosphere 52, 1423–1430.
Zhang, H., Lu, Y., Dawson, R.W., Shi, Y., Wang, T., 2005. Classification and
ordination of DDT and HCH in soil samples from the Guanting Reservoir, China.
Chemosphere 60, 762–769.
Zhu, Y., Liu, H., Xi, Z., Cheng, H., Xu, X., 2005. Organochlorine
pesticides (DDTs and HCHs) in soils from the outskirts of Beijing, China.
Chesmosphere 60, 770–778.