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Pesticides in Surface Water, Sediment, and Rainfall of the Northeastern

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Article in Journal of Environmental Quality · September 2002

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 Pesticides in Surface Water, Sediment, and Rainfall of the Northeastern
Pantanal Basin, Brazil
Volker Laabs,* Wulf Amelung, Alicio A. Pinto, Matthias Wantzen, Carolina J. da Silva, and Wolfgang Zech
ABSTRACT
Within the last 25 years an intensive agriculture has developed in
the highland regions of Mato Grosso state (Brazil), which involves
frequent pesticide use in highly mechanized cash-crop cultures. To
provide information on pesticide distribution and dynamics in the
northeastern Pantanal basin (located in southern Mato Grosso), we
monitored 29 pesticides and 3 metabolites in surface water, sediment,
and rainwater of the study area during the main application season.
In environmental samples, 19 pesticides and 3 metabolites were de-
tected in measurable quantities, resulting in at least one pesticide
detection in 68% of surface water samples (n ⫽ 139), 62% of sediment
samples (n ⫽ 26), and 87% of rainwater samples (n ⫽ 91). Surface
water samples were most frequently contaminated by endosulfan com-
pounds (␣-, ␤-, -sulfate), ametryn, metolachlor, and metribuzin, al-
though in low (⬍0.1 ␮g L⫺1) concentrations. Sediment samples exhib-
ited concentrations up to 4.5 ␮g kg⫺1 of p,pⴕ-DDT, p,pⴕ-DDE,
endosulfan-sulfate, ␤-endosulfan, and ametryn. In contrast, rainwater
was polluted with substantial amounts of endosulfan, alachlor, meto-
lachlor, trifluralin, monocrotofos, and profenofos (maximum concen-
trations ⫽ 0.3 to 2.3 ␮g L⫺1) in the highlands. Lowland rainwater
samples taken 75 km from the next application area contained 5- to
10-fold lower mean pesticide concentration than in the highlands.
Cumulative deposition rates of the pesticide sum within the study
period ranged from 423 ␮g m⫺2 in the highlands to 14 ␮g m⫺2 in the
lowlands. The atmospheric input of pesticides to ecosystems seemed
to be of higher relevance in the tropical study area than known from
temperate regions.
P esticide use has increased worldwide to secure the
food supply of the swelling global population. Espe-
cially in tropical regions, agricultural intensification has
led to higher pesticide consumption (Racke et al., 1997).
Although it is undisputed that pesticides are essential
in modern agriculture, there is growing concern about
possible environmental contamination from agrochemi-
cals. In this respect, extensive research has been con-
ducted in temperate regions, assessing the pollution of
rainwater (e.g., Goolsby et al., 1997; Dubus et al., 2000),
surface waters (e.g., Pereira and Hostettler, 1993; Thur-
man et al., 2000), and sediments (e.g., Bester and Hühn-
erfuss, 1996; Daniels et al., 2000) with pesticides. In
contrast, studies on pesticide occurrence in environmen-
tal samples from the tropics are scarce and focus mainly
on organochlorine pesticides (e.g., Caldas et al., 1999;
Botello et al., 2000), which have been banned from use
V. Laabs, W. Amelung, and W. Zech, Institute of Soil Science and Soil
Geography, University of Bayreuth, D-95440 Bayreuth, Germany. A.
Pinto and C.J. da Silva, Projeto Ecologia do Gran Pantanal, Instituto
de Biociências, Universidade Federal de Mato Grosso, 78090-000
Cuiabá, MT, Brazil. M. Wantzen, Max-Planck Institute of Limnology,
Tropical Ecology Working Group, D-24302 Plön, Germany. V. Laabs,
current address: Covance Laboratories GmbH, Kesselfeld 29, 48163
Münster, Germany. Received 9 July 2001. *Corresponding author
(volker.laabs@covance.com).
Published in J. Environ. Qual. 31:1636–1648 (2002).
1636
in most countries during the last two decades. A recent
monitoring of currently used pesticides in Central
American river ecosystems (Castillo et al., 2000; Cas-
tilho et al., 2000) demonstrated that these substances
are also relevant contaminants in the aquatic environ-
ment. As air and soil temperatures are higher in tropical
climates than in temperate regions, an increased pesti-
cide loss to the atmosphere by volatilization has to be
expected. However, rainwater contamination with pesti-
cides in tropical environments has so far not received
due attention. In view of the frequent pesticide detec-
tion in rainfall of pristine environments (Bester and
Hühnerfuss, 2000) or even in surface water of the polar
regions (Chernyak et al., 1996), pesticide atmospheric
deposition needs to be considered as a relevant pesticide
input pathway for ecosystems worldwide.
Brazil is now ranked as the fouth largest national
market for agrochemicals in the world (Racke et al.,
1997). The Brazilian agricultural frontier is located in
the Cerrado Highlands (planalto), where an intensive,
mechanized agriculture has been spreading during the
last 25 yr (Resck, 1998). Many streams of the southern
highlands of Mato Grosso state (central-western Brazil)
drain toward the Pantanal, which is the world’s largest
freshwater wetland and a hotspot of biodiversity. Al-
though pesticide application on the highlands has inten-
sified considerably since the introduction of soybean
[Glycine max (L.) Merr.] and recently cotton (Gossyp-
ium hirsutum L.) to this region, no studies on the envi-
ronmental dispersion of pesticides in this region or the
nearby Pantanal area exist. The objective of our pilot
study was to assess environmental concentrations of
currently used pesticides in the northeastern Pantanal
basin. To this aim, pesticide concentrations were mea-
sured in surface water, sediment, and rainwater samples
of the agricultural highland areas and in the Pantanal
border regions during the main agrochemical applica-
tion season.
MATERIALS AND METHODS
Study Area and Sampling Schedule
Sampling was restricted to the northeastern Pantanal basin,
concentrating on the region marked off by the Cuiabá River
in the west, the São Lourenço River in the south and east,
and the interstate highway BR364 in the north (Fig. 1). The
climate in this area is of the savanna type, with mean annual
air temperatures of 23⬚C in the planalto and 25⬚C in the low-
lands, and a mean annual precipitation of 1900 mm in the
planalto and 1500 mm in the lowlands. The monitoring period
(November to March) was selected according to the main
pesticide application season and coincided with the rainy sea-
son in the study region. Sampling locations for surface water
Abbreviations: GC, gas chromatography; MS, mass spectrometry.
 LAABS ET AL.: PESTICIDES IN SURFACE WATER, SEDIMENT, AND RAINFALL
Fig. 1. Study area with sampling locations (S, streams; R, rivers; P, precipitation).
(streams [Sites S1–S6] and rivers [Sites R1–R6]) and sediment
(Sites R1–R6) targeted tributaries of the São Lourenço River
(e.g., the Tenente Amaral), the São Lourenço River itself, the
Cuiabá River, the mouth of the Mutum River at the Sia Mari-
ana lake, and the Sia Mariana lake itself. Rainwater collectors
were installed within the agriculturally used highlands be-
tween São Vincente and Jaciara (P1 and P2), in the Cuiabá
city area (P3 and P4), and in the city area of Barão de Melgaço
(P5), a border town of the Pantanal. The sampling was done
on a regular basis: weekly for stream water, biweekly for river
and lake water, once per month for sediment samples, and
three times per week for rainwater. The sampling period began
on 10 Nov. 1999 and ended on 2 Mar. 2000.
Spectrum of Commercialized and Analyzed Pesticides
The study region shows a dominant division between the
planalto area, which is intensively used for cattle and cash
crop production, and the lowland regions (Fig. 1), which are
used (if at all) as pastures or, in the greater Cuiabá city area,
for small-holder vegetable production. Consequently, the spec-
trum of pesticides in the highlands is dominated by herbicides
and insecticides applied in soybean, cotton, corn (Zea mays
L.), and sugarcane (Saccharum spp.) cultures (e.g., trifluralin,
metolachlor, atrazine, endosulfan, monocrotofos), whereas in
the lowlands mainly insecticides and fungicides used for vege-
table production (e.g., parathion-methyl, chlorpyrifos, tebuco-
nazole) are sold in small quantities (for all pesticide chemical
names, see Table 1). For the monitoring we selected pesticides
that were of the most frequent use in the study region, ac-
cording to a survey among regional pesticide vendors, and that
could be measured with gas chromatography–mass spectrome-
1637
try (GC–MS) (Table 2). The spectrum of analyzed substances
was completed by persistent organochlorine pesticides, which
have been banned from agricultural use for more than a decade
in Brazil. Due to the analytical restrictions, ionic and thermally
unstable pesticides could not be covered by our monitoring
study, although some of them were also frequently used in the
study area (e.g., glyphosate, paraquat dichloride, 2,4-D, acifluor-
fen, chlorimuron-ethyl, diuron, methomyl, teflubenzuron).
Sample Collection
River and stream water samples were taken from 0.3 m
below the water surface with amber 1-L glass bottles that had
been rinsed with ethyl acetate and were heated at 250⬚C (4 h)
before use. For sampling, turbulent midstream positions of
water bodies were chosen to approximate mean concentra-
tions of stream and river water. At Site R6, water was sampled
from the middle of the lake, at 0.3 m below the surface. After
collection, water samples were stored on ice during transport
(⬍6 h) and were kept at 4⬚C in the laboratory (⬍2 d) until
solid-phase extraction. Sediment samples were taken from
river positions where an accumulation of fine-textured sub-
strate (loamy to clayey texture, organic carbon content: 6 to
46 g organic C g⫺1 sediment dry mass) took place, with a Van
Veen sampler. Composite samples were pooled from four or
five subsamples (0–10 cm) of a 10-m2 area, homogenized, and
wrapped in aluminum foil. Samples were immediately stored
on ice (⬍6 h) after collection and stored at ⫺20⬚C in the
laboratory until analysis. Rainwater samples were collected
with stainless steel funnels (110-mm diameter) mounted on
4-L amber glass bottles, which had been wrapped with alumi-
num foil to reduce solar heating. Due to the sampler design,
1638 J. ENVIRON. QUAL., VOL. 31, SEPTEMBER–OCTOBER 2002

Table 1. Chemical names of pesticides discussed in this paper.

Pesticide Chemical name
Acifluorfen 5-(2-chloro-␣,␣,␣-trifluoro-p-tolyloxy)-2-nitrobenzoic acid
Alachlor 2-chloro-2ⴕ,6ⴕ-diethyl-N-methoxymethylacetanilide
Ametryn N2–ethyl-N4–isopropyl-6-methylthio-1,3,5-triazine-2,4-diamine
Atrazine 2-chloro-N2–ethyl-N4–isopropyl-1,3,5-triazine-2,4-diamine
Carbaryl 1-naphthyl methylcarbamate
Chlorimuron-ethyl ethyl 2-(4-chloro-6-methoxypyrimidin-2-ylcarbamoylsulfamoyl)benzoate
Chlorothalonil tetrachloroisophthalonitrile
Chlorpyrifos O,O-diethyl O-3,5,6-trichloro-2-pyridyl phosphorothioate
Cyanazine 2-(4-chloro-6-ethylamino-1,3,5-triazin-2-ylamino)-2-methylpropiononitrile
␤-Cyfluthrin (RS)-␣-cyano-4-fluoro-3-phenoxybenzyl(1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate
␭-Cyhalothrin ␣-cyano-3-phenoxybenzyl 3-(2-chloro-3,3,3-trifluoropropenyl)-2,2-dimethylcyclopropane-carboxylate
Cypermethrin (RS)-␣-cyano-3-phenoxybenzyl(1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate
2,4-D (2,4-dichlorophenoxy)acetic acid
DDE 1,1-dichloro-2,2-bis(4-chlorophenyl)ethene
DDT 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane
Deltamethrin (S )-␣-cyano-3-phenoxybenzyl (1R,3R )-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropane-1-carboxylate
Desethylatrazine 6-chloro-N4–isopropyl-1,3,5-triazine-2,4-diamine
Dimethoate O,O-dimethyl S-methylcarbamoylmethyl phosphorodithioate
Ditalimfos O,O-diethyl phthalimidophosphonothioate
Diuron 3-(3,4-dichlorophenyl)-1,1-dimethylurea
Endosulfan 6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin 3-oxide
Endosulfan-sulfate 6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin 3,6-dioxide
Fenitrothion O,O-dimethyl O-4-nitro-m-tolyl phosphorothioate
Glyphosate N-(phosphonomethyl)glycine
␣-HCH ␣-1,2,3,4,5,6-hexachlorocyclohexane
Heptachlor 1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methanoindene
Lindane ␥-1,2,3,4,5,6-hexachlorocyclohexane
Malathion diethyl(dimethoxythiophosphorylthio) succinate
Methomyl S-methyl N-(methylcarbamoyloxy)thioacetimidate
Methyl-parathion O,O-dimethyl O-4-nitrophenyl phosphorothioate
Metolachlor 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide
Metribuzin 4-amino-6-tert-butyl-4,5-dihydro-3-methylthio-1,2,4-triazin-5-one
Monocrotofos 3-(dimethoxyphosphinyloxy)-N-methylisocrotonamide
Paraquat dichloride 1,1ⴕ-dimethyl-4,4ⴕ-bipyridinium dichloride
Parathion O,O-diethyl O-4-nitrophenyl phosphorothioate
Permethrin 3-phenoxybenzyl (1RS,3RS;1RS,3SR)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate
Profenofos O-4-bromo-2-chlorophenyl O-ethyl S-propyl phosphorothioate
Quintozene Pentachloronitrobenzene
Simazine 6-chloro-N2,N4–diethyl-1,3,5-triazine-2,4-diamine
Tebuconazole (RS)-1-p-chorophenyl-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl)pentan-3-ol
Teflubenzuron 1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea
Terbuthylazine N2–tert-butyl-6-chloro-N4–ethyl-1,3,5-triazine-2,4-diamine
Triazofos O,O-diethyl O-1-phenyl-1H-1,2,4-triazol-3-yl phosphorothioate
Trifluralin 2,6-dinitro-N,N-dipropyl-4-trifluoromethylaniline

the bulk deposition of pesticides was measured, consisting of
wet and dry deposition. Rain collectors were installed in the
open (1 m above ground), taking care to avoid influence of
adjacent trees or buildings. In the agriculturally used high-
lands, samplers were installed on grassland areas, at least 75 m
from the nearest cropped area to minimize any direct spray
drift contamination. Collector flasks were emptied daily and
water was pooled into samples for every two or three days;
at Site P5 water was pooled into weekly composite samples,
due to shortages of freezer space. After collection, rainwater
samples were immediately stored in a freezer at ⫺20⬚C until
extraction. When less than 50 mL of rainwater were collected
during a sampling interval, the sample was unified with the
one of the following sampling interval.
Sample Extraction
Water samples (ⱕ1 L) were filtered (Schleicher&Schuell
GF6 glass fiber filter; Laborcenter, Nürnberg, Germany), con-
ditioned (acidification with hydrochloric acid to pH 3, addition
of 20 g L⫺1 KCl), and afterwards solid-phase extracted on
8-mL glass C18-cartridges (filled with 1.25 g of C18 Baker-
bond; Baker Chemicals, Gross-Gerau, Germany), which had
been conditioned by elution with 5 mL each of ethylacetate,
methanol, and water. After extraction of the water sample
(approximately 15 mL min⫺1) the cartridges were dried in an
air stream and stored at ⫺20⬚C until elution. Pesticides were
eluted from the cartridges by n-hexane (8 mL) and ethyl ace-
tate (12 mL) and the concentrated eluate was then analyzed
by GC–MS. Further methodological details may be found in
Laabs et al. (2000). Filter residues of samples with positive
pesticide detection in the water phase were shaken for 4 h with
acetone–hexane (1:1, v/v, 25 mL); the concentrated solvent
extract was then analyzed for pesticides.
Sediment samples (approximately 25 g dry weight) were
extracted with a mixture of acetone, ethylacetate, and water
(Laabs et al., 1999). After extraction the shaking flasks were
centrifuged and the sample extract was then decanted and
filtrated (Schleicher&Schuell 5961/2). Following the removal
of the organic solvents with a rotary evaporator, the remaining
water phase was liquid–liquid extracted with dichloromethane
(3 ⫻ 25 mL). The organic phase was then dried with sodium
sulfate and concentrated again with a rotary evaporator. After-
wards the extract was purified by flash chromatography with
an 8-mL glass column packed with 1.0 g of aluminum oxide
(deactivated with 0.06 g water g⫺1 sorbent) on top of 1.0 g
Florisil (deactivated with 0.1 g water g⫺1 sorbent) (Promo-
chem, Wesel, Germany). After the sample extract had been
transferred to the column in approximately 0.5 mL of toluene,
the pesticides were consecutively eluted from the column with
10 mL of n-hexane and 10 mL of n-hexane–diethyl ether 1:1
(v/v). The eluate was concentrated with a rotary evaporator
and then analyzed by GC–MS. All organic solvents used for
analysis were of “picograde” purity (Promochem, Wesel, Ger-
many). Glassware used during sample processing was rinsed
with ethylacetate and baked at 250⬚C (⬎4 h) before every use.
 LAABS ET AL.: PESTICIDES IN SURFACE WATER, SEDIMENT, AND RAINFALL 1639

Table 2. Studied pesticides and metabolites, monitored ions, recovery (standard error), and routine limit of quantification (RLQ) in
water and sediment samples.
Water samples Sediment samples
Substance Type† Use in study area SIM ions‡ Recovery RLQ Recovery RLQ
m z⫺ 1 % of spike§ ␮g L⫺1¶ % of spike# ␮g kg⫺1††
Alachlor H corn, soybean, cotton 160, 188, 146 108 (1) 0.002 99 (1) 0.8
Ametryn H sugarcane 227, 212, 170 107 (2) 0.002 87 (2) 0.4
Atrazine H corn 200, 215, 173 103 (1) 0.002 97 (1) 0.4
Chlorothalonil F vegetables, fruit cultures 266, 264, 268 124 (4) 0.002 – –
Chlorpyrifos I corn, cotton, vegetables 197, 199, 314 65 (4) 0.005 87 (4) 0.8
Cyanazine H corn, cotton 125, 240, 198 119 (1) 0.025 70 (9) 4
␤-Cyfluthrin I soybean, cotton 163, 165, 206 81 (4) 0.005 84 (4) 4
␭-Cyhalothrin I soybean, cotton 181, 197, 141 80 (3) 0.002 88 (3) 0.8
Cypermethrin I soybean, cotton 163, 165, 181 89 (4) 0.010 99 (5) 4
p,pⴕ-DDE metabolite of DDT 246, 248, 318 76 (4) 0.002 99 (3) 0.4
p,pⴕ-DDT I no current use 235, 237, 165 97 (2) 0.002 122 (5) 0.4
Desethylatrazine metabolite of atrazine 172, 174, 187 114 (1) 0.002 97 (13) 0.4
Deltamethrin I soybean, cotton 181, 253, 251 92 (3) 0.010 94 (6) 4
Dimethoate I vegetables, cotton 87, 93, 125 77 (6) 0.010 – –
␣-Endosulfan I cotton, soybean 195, 237, 241 100 (1) 0.002 98 (0) 0.4
␤-Endosulfan I cotton, soybean 195, 237, 159 105 (1) 0.002 94 (1) 0.4
Endosulfan-sulfate endosulfan metabolites (␣-, ␤-) 272, 274, 237 130 (1) 0.002 97 (1) 0.4
Heptachlor I no current use 272, 267, 274 74 (4) 0.002 127 (13) 0.4
Lindane I no current use 181, 183, 219 97 (4) 0.002 115 (4) 0.4
Malathion I vegetables 173, 125, 158 74 (6) 0.005 80 (7) 2
Methyl-parathion I vegetables 263, 109, 125 102 (5) 0.025 82 (4) 4
Metolachlor H corn, soybean, cotton 162, 238, 240 108 (2) 0.002 99 (1) 0.8
Metribuzin H soybean 198, 199, 144 116 (4) 0.002 74 (4) 0.8
Monocrotofos I soybean, cotton 127, 109, 192 119 (6) 0.025 – –
Parathion I vegetables 291, 139, 155 79 (5) 0.025 82 (3) 4
Permethrin I soybean, cotton 183, 163, 165 82 (3) 0.002 101 (2) 0.8
Profenofos I soybean, cotton 139, 206, 339 128 (4) 0.005 – –
Quintozene I no current use 237, 249, 295 63 (5) 0.002 86 (2) 0.8
Simazine H corn, sugarcane 201, 186, 173 108 (2) 0.002 95 (1) 0.4
Tebuconazole F vegetables, fruit cultures 250, 252, 127 84 (4) 0.010 – –
Triazofos I soybean, cotton 161, 162, 257 98 (6) 0.005 85 (9) 2
Trifluralin H soybean, cotton 306, 264, 290 77 (2) 0.002 86 (5) 0.4
† F, fungicide; H, herbicide; I, insecticide.
‡ Ions used for substance quantification (first ion) and identification (second and third ions) during the selected ion monitoring (SIM).
§ Spike of 0.1 ␮g L⫺1 (n ⫽ 4), samples of 1 L.
¶ Samples of 1 L.
# Spike of 0.1 mg kg⫺1 sediment (n ⫽ 3), samples of 25 g sediment dry mass.
†† Samples of 25 g sediment dry mass.

Analysis of Pesticides and Quality Control
Pesticides were quantified with GC–MS (Hewlett-Packard
6890 series gas chromatograph coupled with a Hewlett-Pack-
ard 5972A mass selective detector–electron impact ionization;
Hewlett Packard GmbH, Waldbronn, Germany), which was
operated in the selected ion-monitoring mode at the following
conditions: injector block temperature ⫽ 250⬚C; carrier gas ⫽
helium; oven temperature program ⫽ initial temperature of
92⬚C held for 2.5 min, heating up to 175⬚C at 15⬚C min⫺1,
175⬚C held for 14.5 min, heating up to 280⬚C at 15⬚C min⫺1,
280⬚C held for 9 min; and transfer-line temperature ⫽ 290⬚C.
Quantification and identification of substances were achieved
by measuring one target and two additional qualifier ions,
respectively, per substance (Table 2). The calibration was per-
formed with three-point linear functions, with external and
internal standards. Internal standards (␣-HCH, terbuthylaz-
ine, ditalimfos) were added (1 ␮g each) to samples before
extraction to compensate for processing losses and to control
the analytical quality. Internal standard recovery was calcu-
lated by relating their concentration to fluorene-d10, which
was added (1 ␮g) to concentrated sample extracts prior to
GC injection. Samples were injected in toluene (1 ␮L). The
routine limits of quantification (RLQ) are listed for all com-
pounds in Table 2.
The three internal standards were chosen to represent pesti-
cides of different chemical and polarity classes during extrac-
tion and analysis. These pesticides were of no current use
in the studied area, as terbuthylazine and ditalimfos are not
commercialized in Brazil and lindane (and its potential by-
product ␣-HCH) was banned from agricultural use more than
10 yr ago. Eventual traces of the persistent ␣-HCH in the low
nanogram range in samples would not interfere with pesticide
quantification by this internal standard, as to every sample
fixed quantities of internal standard were added in high amounts
(1 ␮g per sample).
Individual sample processing quality was checked by calcu-
lating the recovery of internal standards (usually ⬎75% of
the spiked amount). Pesticide peaks in sample extracts were
identified by retention time, presence of target and qualifier
ions, and respective ratios of target and qualifier ions. When-
ever possible (at concentrations greater than 0.5 ␮g mL⫺1
sample extract), full-scan spectra of substances were recorded
to fingerprint pesticides and identify unknown compounds by
comparison with reference spectra of spectral libraries.
During the extraction of water samples, blanks were pro-
cessed regularly, in which of all pesticides only alachlor and
metolachlor were infrequently detected in low concentrations
(⬍0.005 ␮g L⫺1) in 1-L samples of distilled laboratory tap
water. Malathion occurred in higher concentrations in blanks
(⬍0.050 ␮g L⫺1) during the antimosquito spray campaign in
the Cuiabá city area (January to February 2000). Blank con-
centrations were subtracted from calculated sample concentra-
tions for the respective pesticides and processing lots, as they
were thought to derive from condensation of pesticides on
surfaces of glass vessels within the laboratory.
1640 J. ENVIRON. QUAL., VOL. 31, SEPTEMBER–OCTOBER 2002

Pesticide Recovery or swampy grassland, which usually accompanied the

The quality of the analytical methods was assessed by pesti-
cide recovery experiments with water and sediment matrices
(Table 2). The efficiency of the water extraction procedure
was tested by spiking 1-L samples of distilled tap water with
0.1 ␮g each of pesticide standards dissolved in acetone. After-
wards the samples were extracted and analyzed according
to the procedure outlined above. Similarly, uncontaminated
sediment from Site R4 (texture: clay; organic C: 9.1 g kg⫺1;
pH 5 [in H2O]) was spiked with known quantities of pesticides
before extraction (2.5 ␮g per substance in 25 g of sediment
dry mass) and processed and analyzed as described above.
Pesticide concentrations measured in environmental samples
were corrected for their respective recovery values (Table 2)
determined during these experiments.
RESULTS AND DISCUSSION
Surface Water
Stream water samples of Sites S1 to S6 generally did
not contain significant amounts of suspended sediments,
although turbidity in these streams is known to increase
strongly during rain events (Wantzen, 1998). We attrib-
uted this finding to the fact that most of the stream
banks in the study area were covered by gallery forest
streams on both sides in a 5- to 50-m-wide strip. Thus
a continuous input of soil particles to the water body
by surface runoff was inhibited, except during heavy
storm events. In contrast, river water samples were
mostly clouded by suspended sediments (Sites R1–R4)
or were rich in dissolved organic carbon (Sites R5 and
R6), as indicated by their brown color after filtration.
Suspended sediment of water samples, however, never
contained pesticides in detectable amounts. We attrib-
uted this on the one hand to the small mass of sediment
suspended in river water (⬍5 g L⫺1), which led to pesti-
cide concentrations below the analytical detection limit,
and on the other hand to a possible desorption of the
more polar pesticides from sediment particles during
their riverine transport (Squillace and Thurman, 1992).
The concentrations of individual pesticides measured
in surface water of the study area (Table 3) never ex-
ceeded 0.1 ␮g L⫺1 (established limit by laws of the Euro-
pean Community), with the exception of malathion in
the Cuiabá River, and lay below the respective maxi-
mum contaminant levels of pesticides (e.g., 2 to 4 ␮g
L⫺1 for alachlor, atrazine, and simazine) established for
drinking water by the USEPA (2000). The current Bra-

Table 3. Detection frequency and pesticide and metabolite concentrations in surface water samples.
Concentrations
Substance Positive detections Minimum Maximum Mean of detections
% of samples ␮g L⫺1
Stream water samples, Sites S1 to S6 (n ⫽ 94)
Alachlor 6.4 0.004 0.009 0.006
Ametryn 12.8 0.002 0.009 0.004
Atrazine 5.3 0.002 0.018 0.008
Chlorothalonil 1.1 – – 0.002
Desethylatrazine 1.1 – – 0.002
␣-Endosulfan 13.8 0.003 0.032 0.012
␤-Endosulfan 13.8 0.002 0.030 0.009
Endosulfan-sulfate 31.9 0.002 0.038 0.012
Metolachlor 25.5 0.002 0.007 0.003
Metribuzin 20.2 0.003 0.007 0.005
Monocrotofos 2.1 0.025 0.035 0.030
Profenofos 1.1 – – 0.006
Simazine 5.3 0.009 0.013 0.011
Tebuconazole 1.1 – – 0.014
Trifluralin 5.3 0.003 0.016 0.006
River water samples, Sites R1 to R3 (n ⫽ 26)
Alachlor 15.4 0.003 0.016 0.011
Ametryn 50.0 0.003 0.082 0.020
Atrazine 15.4 0.008 0.010 0.009
␣-Endosulfan 7.7 0.006 0.016 0.011
␤-Endosulfan 3.8 – – 0.007
Endosulfan-sulfate 50.0 0.002 0.018 0.008
Malathion 26.9 0.010 0.174 0.042
Metolachlor 30.8 0.002 0.013 0.005
Simazine 19.2 0.007 0.013 0.009
Trifluralin 15.4 0.003 0.019 0.007
Surface water samples of the Pantanal area, Sites R4 to R6 (n ⫽ 19)
Alachlor 21.1 0.007 0.019 0.013
Ametryn 5.3 – – 0.013
Chlorothalonil 5.3 – – 0.002
Chlorpyrifos 5.3 – – 0.011
Endosulfan-sulfate 10.5 0.003 0.004 0.003
Malathion 26.3 0.012 0.057 0.042
Metolachlor 26.3 0.004 0.014 0.009
Metribuzin 5.3 – – 0.008
Simazine 10.5 0.009 0.011 0.010
Tebuconazole 5.3 – – 0.044
Trifluralin 15.8 0.017 0.019 0.019
 LAABS ET AL.: PESTICIDES IN SURFACE WATER, SEDIMENT, AND RAINFALL
zilian legislature (Ministério da Saúde, 1990) does not
define maximum contaminant levels of the studied pesti-
cides in water resources, except for some formerly used
organochlorine pesticides (e.g., DDT, heptachlor, lin-
dane), which were not detected in water samples in
our study.
The sampled streams drained catchments of intensive
agricultural use, where 40 to 60% of the land surface
was used for soybean, corn, sugarcane, and cotton pro-
duction. In 68% of stream water samples, one to eight
pesticides were detected per sample. Individual detec-
tion frequencies and concentration spans of pesticides
are presented in Table 3. The highest maximum concen-
trations were found for endosulfan and its metabolite
endosulfan-sulfate, as well as for monocrotofos, which
was only detected twice during the sampling period.
Besides endosulfan, the greatest percentages of positive
detections were recorded for the herbicides metolachlor,
metribuzin, and ametryn (⬎12%). The other substances
were detected in less than 6% of the analyzed samples.
The concentrations of the most frequently detected
pesticides at Site S2 are shown in Fig. 2.
Endosulfan was applied in the study area onto cotton
fields by plane, which presumably accounts for the fre-
quent detection of this nonpolar insecticide (water solu-
bility of 0.32 mg L⫺1) in water samples. Probably, spray
drift and wash-off from stream bank vegetation caused a
major part of the observed contamination. The frequent
detection of more polar substances like metribuzin and
metolachlor (Fig. 2, Table 3) at low concentrations
throughout the study period points to a continuous input
of pesticides by subsurface flow from fields to the sur-
face water. These assumptions were supported by the
finding that these pesticides were detected in water sam-
ples free of suspended sediment, indicating that surface
runoff from fields did not contribute to the measured
contamination of streams with pesticides in this case.
Fig. 2. Concentrations of selected pesticides and metabolites in stream water at Site S2.
1641
In contrast, readily degradable substances, such as mo-
nocrotofos and alachlor, or apolar substances, such as
tebuconazole and trifluralin, were only detected at a
few sampling dates. In general, the measured pesticide
concentrations in streams were low (⬍0.04 ␮g L⫺1). We
attributed this finding in part to the stream discharge-
independent sampling strategy, which was not able to
seize short-term peak concentrations related to runoff
events. It is known that pesticide concentrations during
discharge events in streams may increase 20-fold as com-
pared with their concentrations at base flow (Spalding
and Snow, 1989).
In comparison with monitoring data from the mid-
western USA (Spalding and Snow, 1989; Schottler et
al., 1994), concentrations of typical pollutants such as
alachlor, atrazine, and metolachlor were at least 5- to
10-fold lower in base flow of streams in our study. This
might be explained by the higher intensity and unifor-
mity of land use in the North American region, where
regionally up to 80% of the land surface are used to
grow corn and soybean (Spalding and Snow, 1989), re-
sulting in a more intensive use of the respective herbi-
cides in these areas. In addition, effective anti-erosion
measures in Brazilian agriculture and the fast dissipation
of pesticides in tropical soils after application (Laabs et
al., 2000) might have contributed to the low contamina-
tion level of streams with pesticides in our study area.
Our results compare well with stream water concentra-
tions of endosulfan (␣-, ␤-) and ametryn reported in
monitoring studies from tropical environments in Cen-
tral America (Castillo et al., 2000; Castilho et al., 2000).
River water was sampled only biweekly, as the dy-
namics of pesticides in larger water bodies are expected
to be less rapid than in smaller streams (Baker and
Richards, 2000). Of all samples taken, 81% were contami-
nated by pesticides, with up to five compounds present
in one sample. The most frequently detected insecticides
1642 J. ENVIRON. QUAL., VOL. 31, SEPTEMBER–OCTOBER 2002
and metabolites were endosulfan-sulfate and malathion,
while the most frequently detected herbicides in samples
were ametryn, metolachlor, and simazine (Table 3). It
is noteworthy that also the herbicides alachlor, atrazine,
and the nonpolar trifluralin were detected in more than
15% of the analyzed samples. The frequent detection
of malathion at high concentrations in river water (re-
stricted to Sites R3 and R4 of the Cuiabá River) was
attributed to its use during antimosquito campaigns in
the city area of Cuiabá (January to February 2000). In
Fig. 3, the concentrations of the most frequently de-
tected pesticides are shown for Site R1. The high detec-
tion frequency and high concentrations of ametryn in
river water samples at Sites R1 and R2 was attributed
to the regionally intense cultivation of sugarcane in the
upper basin of the São Lourenço River. There, ametryn
was exclusively used in large-sized sugarcane planta-
tions, where it was also applied in direct vicinity to the
river banks. Otherwise, the pesticide spectrum at Site
R1 was characterized by the frequent detection of endo-
sulfan compounds and sporadic occurrences of triazines
(simazine, atrazine).
A smaller number of pesticides was detected in river
water (10 different compounds) than in stream water
(15 different compounds). We attributed this finding to
an elimination of easily degradable substances such as
monocrotofos and profenofos (Hornsby et al., 1996)
during the riverine transport, or to dilution effects (e.g.,
chlorothalonil, tebuconazole). Some herbicides (e.g.,
ametryn, atrazine, metolachlor, simazine) were detected
more often and at similar or higher concentrations in
river water samples (Sites R1–R4) than in stream water
samples (Sites S1–S6). These results corroborated the
finding of Baker and Richards (2000) that generally
higher intermediate concentrations of pesticides are
found in rivers than in smaller streams of a watershed
(“peak broadening”). Yet, also a more intensive use of
Fig. 3. Concentrations of selected pesticides and metabolites in river water at Site R1.
these herbicides in other subcatchments of the greater
river watershed than in the sampled ones can explain
our results. The lower ratios of endosulfan (␣- ⫹ ␤-) to
endosulfan-sulfate concentrations in water samples of
rivers (mean ratio of 0.18) in comparison with stream
water (mean ratio of 0.50) pointed to an increasing deg-
radation of endosulfan during its transport toward the
lowlands in surface water. Endosulfan-sulfate was
shown to be the main metabolite of endosulfan degrada-
tion in aquatic systems (Navarro et al., 2000).
In comparison with river monitoring studies from
temperate regions (Pereira and Hostettler, 1993; Grif-
fini et al., 1997), measured mean concentrations in tropi-
cal river water were 5- to 10-fold lower for many com-
pounds (alachlor, atrazine, metolachlor, simazine). This
may be attributed to a generally higher land-use inten-
sity in such agricultural centers of temperate regions,
like the upper Mississippi River basin (USA) or the
Arno River basin (Italy), in comparison with the still-
developing tropical study region. The relatively frequent
detection of some apolar pesticides (e.g., endosulfan,
trifluralin), in comparison with the one of triazines and
acetanilides, in tropical rivers points to an increased
dispersion of these more volatile compounds in the stud-
ied tropical environment. Yet, their relative intensity of
use, as well as their application mode (aerial application
of cotton insecticides in the study region), may also play
an important role in this respect.
In the Pantanal area only 47% of water samples con-
tained detectable pesticide residues, mostly in low con-
centration (Table 3). Malathion, metolachlor, alachlor,
and trifluralin were detected most frequently (⬎15%
of sampling events) in water of the Pantanal border
zone. Endosulfan-sulfate was detected at low concentra-
tions (3–4 ng L⫺1); its parent compounds could not be
detected any more above their limit of quantification.
However, in comparison with data from sampling sites
 LAABS ET AL.: PESTICIDES IN SURFACE WATER, SEDIMENT, AND RAINFALL
in the planalto, some pesticides occurred at similar or
slightly higher concentrations in the Pantanal border
zone (e.g., alachlor, metolachlor, trifluralin). Possibly,
the main riverine flux of these pesticides, which are
applied at the very beginning of the rainy season (Octo-
ber to November), already had passed on to the Panta-
nal area. Ametryn and endosulfan compounds were
detected most frequently in the São Lourenço River
throughout the study period with maximum concentra-
tions of 18 and 82 ng L⫺1 (Sites R1 and R2). It seems
therefore probable that also these substances would
reach the Pantanal border zone to the south of our study
area, warranting further investigations in this region.
Sediments
Sediment samples were only collected at Sites R1 to
R6, because stream bank and bottom sediments at Sites
S1 to S6 consisted of coarse sands, which do not adsorb
pesticides in significant amounts (e.g., Moreau and
Mouvet, 1997). It has to be noted that river sediments
at Sites R1 to R3 were taken from lateral still-water
zones, which were more turbulent during major storm
flow events. Therefore, sediments at these locations
could only accumulate during periods of low water level
in the rivers. At the other sampling sites, bottom sedi-
ments of rivers and lakes were taken where a continuous
sedimentation took place.
In comparison with water samples, only a small num-
ber of pesticides was encountered in sediments (Table
4). Concentrations were generally below 5 ␮g kg⫺1 sedi-
ment (dry weight), except for one detection of triazofos.
This finding was in agreement with the lack of pesticide
detections in suspended sediment of water samples. At
Sites R1 to R3, organochlorine insecticides (p,p⬘-DDT,
p,p⬘-DDE, endosulfan compounds) were detected most
frequently, followed by the herbicide ametryn. In sedi-
ment samples of the Pantanal, only p,p⬘-DDT and p,p⬘-
DDE were detected, again at low concentrations. Al-
though the agricultural use of DDT was banned in Mato
Grosso (Brazil) in 1985, this insecticide was still the
most frequently detected pesticide in sediments of all
compounds investigated. This demonstrated again the
well-known persistence of this substance even in tropical
Table 4. Detection frequency and pesticide and metabolite con-
centrations in sediment samples.
Concentrations
Positive
Substance detections Minimum Maximum Mean of detections
% of samples ␮g kg⫺1†
River sediments, Sites R1 to R3 (n ⫽ 14)
Ametryn 29 0.5 1.1
p,pⴕ-DDE 36 0.4 1.4
p,pⴕ-DDT 79 0.4 1.5
Desethylatrazine 7 – – 0.4
␤-Endosulfan 29 1.0 2.7
Endosulfan-sulfate 57 0.5 3.7
Simazine 7 – – 0.5
Triazofos 7 – – 10.1
Sediments of the Pantanal area, Sites R4 to R6 (n ⫽ 12)
p,pⴕ-DDE 25 0.5 1.7
p,pⴕ-DDT 25 0.8 4.5
† Concentrations in ␮g kg⫺1 dry weight of sediment.
1643
environments (e.g., Castilho et al., 2000; Kidd et al.,
2001) and justifies its prohibition from agricultural use
in Brazil. Our results are corroborated by Matsushita
et al. (1996) who measured similar background concen-
trations of p,p⬘-DDT and p,p⬘-DDE (0.2 to 0.6 ␮g kg⫺1)
in sediments of rivers in Paraná state, Brazil.
Endosulfan-sulfate and ␤-endosulfan were also fre-
quently detected in sediments of the São Lourenço
River (Sites R1 and R2), indicating that this insecticide
and/or its metabolite might accumulate in the sediment
compartment of the studied river. Castilho et al. (2000)
reported similar concentrations of endosulfan (1 to 9
␮g kg⫺1) in bottom sediments of a Nicaraguan river
system, where cotton production was intense. The ab-
sence of ␣-endosulfan in the analyzed samples, despite
its dominance in the applied pesticide formulations (66–
70% of the active ingredient mass in the formulation
are comprised of ␣-endosulfan), pointed to a decreased
persistence of this isomer in aquatic systems in compari-
son with ␤-endosulfan. This finding corroborated results
of Navarro et al. (2000) and Leonard et al. (2001) who
measured a faster dissipation of the ␣ than the ␤ isomer
in aquatic systems.
Rainwater
Collectors for rainwater were passive pan samplers,
which were shown to possess good reproducibility for
the collection of pesticide bulk deposition (Cessna et
al., 2000). As it is commonly assumed that the dry depo-
sition of pesticides is of minor importance for the total
pesticide deposition (e.g., Dubus et al., 2000), we re-
garded the measured pesticide deposition in first approxi-
mation as wet deposition. A deposition of pesticides with
dust or eroded soil was thought to be negligible in our
study, because no visible accumulation of particles oc-
curred on the C18-cartridges during the solid-phase ex-
traction of water samples. A description of sampling
sites is given in Table 5. Besides the distinctive differ-
ences in land use between lowland and planalto, the
higher cumulative precipitation at the highland sites
(P1 and P2) also has to be mentioned. Pesticides were
identified in 87% of all collected rainwater samples (n ⫽
91), with up to nine pesticides detected in one sample.
In planalto samples, endosulfan compounds were de-
tected most frequently (Table 6), followed by the herbi-
cides alachlor, metolachlor, and trifluralin (⬎30% of
samples). The organophosphorus pesticides monocro-
tofos and profenofos were detected less frequently (26
and 29% of samples), but at the highest mean and maxi-
mum concentrations of all pesticides investigated (0.3
0.8 to 0.7 and 2.2 to 2.3 ␮g L⫺1, respectively). Within the
0.7
0.8
study period (113 d), the highest deposition rates were
measured for endosulfan (␣- ⫹ ␤-) and profenofos
1.5 (⬎140 ␮g m⫺2), followed by monocrotofos (94 ␮g m⫺2)
1.6
and the herbicides metolachlor and alachlor (⬎40 ␮g
m⫺2). In Fig. 4 and 5, the measured concentrations of
selected pesticides at Sites P1 and P2 are presented.
0.9 Pesticide deposition was initially dominated at both sites
2.2 by selective corn and preemergence herbicides (alachlor,
metolachlor, trifluralin), which are usually applied by
1644 J. ENVIRON. QUAL., VOL. 31, SEPTEMBER–OCTOBER 2002

Table 5. Characterization of rainwater sampling sites and cumulative deposition of pesticides and metabolites within the study period
(10 Nov. 1999–2 Mar. 2000).
Sampling site Location and main crops of area Elevation Rainfall Pesticide deposition†
m‡ mm ␮g m⫺2
P1 pasture (soybean, corn, sugarcane) 805 785 423
P2 pasture (soybean, cotton, corn, sugarcane) 735 744 384
P3 city area (sporadic vegetable cultivation) 255 522 13.8§
P4 city area (sporadic vegetable cultivation) 270 662 13.6§
P5 town area (none) 195 556 24.7§
† Sum of all measured compounds.
‡ Above mean sea level.
§ Deposition without malathion (with malathion: deposition of 2111, 335, and 41.4 ␮g m⫺2 for Sites P3, P4, and P5, respectively).

October and November. In December, the application fan in rainwater at both sites (Table 6). We attributed
of endosulfan in cotton fields began, leading to continu- this finding in part to a higher persistence of the ␤
ous detection of this insecticide in rain (nearest applica- isomer in the atmosphere (Hoff et al., 1992). Yet, once
tion area: approximately 2 km to the south of Site P2, volatilized, the substantially lower Henry constant of
applied by plane). This period was accompanied by spo- the ␤ as compared with the ␣ isomer (Tomlin, 2000)
radic detections of monocrotofos, which is commonly would also favor the wash-out of ␤-endosulfan by rain-
applied to soybean. Profenofos, used in soybean and fall from the atmosphere. Although the distance be-
also cotton plantations, began to dominate the spectrum tween Sites P1 and P2 was more than 10 km, the pesti-
of deposited pesticides from the middle of January on- cide deposition pattern was similar and followed the
ward at both sampling sites. Yet, whereas at Site P1 regional application sequence of pesticides in the main
alachlor was detected frequently and at high concentra- cash crop cultures of the planalto study area (Fig. 4
tions (up to 0.67 ␮g L⫺1) in rainwater, it was only de- and 5). This finding suggests a large-scale dispersion of
tected at low concentrations (⬍0.07 ␮g L⫺1) in 28% of pesticide residues in the atmosphere of the highlands,
rainwater samples at Site P2. Vice versa, trifluralin was resulting in a homogeneous pattern of pesticides depos-
detected less frequently and at lower concentrations at ited at Sites P1 and P2, in spite of sampling site–specific
Site P1 in comparison with Site P2. As in stream water application history and precipitation differences. This
and sediment samples, ␤-endosulfan was detected more assumption has to be verified by future studies with a
frequently and at higher concentrations than ␣-endosul- grid-like sampling scheme in the planalto. The sum of
Table 6. Detection frequency, concentrations, and deposition rates of pesticides and metabolites in rainwater (sampling period 10 Nov.
1999–2 Mar. 2000).
Concentrations
Substance Positive detections Minimum Maximum Mean of detections Maximum deposition rate
% of samples ␮g L⫺1 ␮g m⫺2
Rainwater samples of the planalto, Sites P1 to P2 (n ⫽ 45)
Alachlor 48.9 0.006 0.672 0.105 43
Ametryn 2.2 – – 0.012 0.2
Atrazine 15.6 0.017 0.148 0.052 8.6
Chlorpyrifos 6.7 0.020 0.031 0.025 2.3
Cypermethrin 4.4 0.032 0.376 0.204 15
Desethylatrazine 6.7 0.004 0.016 0.009 0.5
␣-Endosulfan 51.1 0.014 0.322 0.065 37
␤-Endosulfan 77.8 0.013 0.722 0.131 108
Endosulfan-sulfate 71.1 0.005 0.147 0.040 23
Metolachlor 33.3 0.008 0.866 0.089 50
Monocrotofos 28.8 0.060 2.23 0.334 94
Permethrin (cis, trans) 2.2 – – 0.066 0.6
Profenofos 26.7 0.187 2.27 0.674 141
Simazine 4.4 0.081 0.140 0.111 4.2
Tebuconazole 8.9 0.017 0.175 0.078 4.7
Triazofos 4.4 0.091 0.207 0.149 3.3
Trifluralin 35.6 0.003 0.318 0.057 27
Rainwater samples of the lowlands, Sites P3 to P5 (n ⫽ 46)
Alachlor 13.0 0.014 0.025 0.018 3.4
Atrazine 4.3 0.018 0.030 0.024 0.9
Chlorothalonil 2.2 – – 0.001 0.1
Chlorpyrifos 6.5 0.008 0.015 0.012 2.5
␣-Endosulfan 8.7 0.004 0.014 0.009 1.2
␤-Endosulfan 54.3 0.008 0.057 0.020 7.7
Endosulfan-sulfate 58.7 0.004 0.036 0.009 3.2
Malathion† 39.1 0.016 27.6 3.69 2100
Metolachlor 15.2 0.007 0.020 0.016 3.4
Monocrotofos 2.2 – – 0.056 2.1
Profenofos 2.2 – – 0.073 1.2
Triazofos 2.2 – – 0.089 1.4
Trifluralin 8.7 0.009 0.036 0.020 4.7
† Vaporized in the Cuiabá city area (Sites P3 and P4) to control mosquitoes.
 LAABS ET AL.: PESTICIDES IN SURFACE WATER, SEDIMENT, AND RAINFALL 1645

Fig. 4. Precipitation and concentrations of selected pesticides and metabolites in rainwater at Site P1.

pesticides deposited during the study period was about
400 ␮g m⫺2 at both sites (Table 5).
At least one pesticide was detected in 74% of rainwa-
ter samples (n ⫽ 46) of the lowlands. Yet, pesticide
concentrations were generally below 0.1 ␮g L⫺1, with
the exception of malathion, which was measured in con-
centrations up to 27.6 ␮g L⫺1 in rainwater of the Cuiabá
city area (Table 6). Two unknown substance peaks oc-
curred together with malathion in several rainwater
samples at Site P3 and were identified by full-scan spec-
tra as the insecticides carbaryl and fenitrothion (concen-
trations ⬎ 0.5 ␮g L⫺1). According to the city govern-
ment, malathion had been vaporized partly in mixtures
with carbaryl and fenitrothion during antimosquito cam-
paigns from January to February 2000 to control dengue
fever eruptions in the Cuiabá region. Due to the obvious

Fig. 5. Precipitation and concentrations of selected pesticides and metabolites in rainwater at Site P2.
1646 J. ENVIRON. QUAL., VOL. 31, SEPTEMBER–OCTOBER 2002
origin of carbaryl and fenitrothion from local applica-
tion in the public health sector, no further quantification
was attempted for these substances. Besides malathion,
␤-endosulfan and endosulfan-sulfate were the most fre-
quently detected compounds (⬎50% of samples), fol-
lowed by metolachlor, alachlor, trifluralin, and ␣-endo-
sulfan (⬎8% of samples). Generally, pesticide mean
concentrations and deposition rates were 5 to 10 times
lower than in rainwater samples of the planalto. Excep-
tions were malathion, due to local use, and the infre-
quently detected triazofos and chlorpyrifos, which were
detected in similar concentrations and frequencies as in
the planalto. Individual deposition rates during the moni-
toring period were lower than 10 ␮g m⫺2 for all com-
pounds, save for malathion. Endosulfan compounds were
detected in samples since the end of December at the
lowland sites, which coincides with their detection pattern
at the planalto sites. All other pesticides (except mala-
thion) were detected erratically throughout the study
period.
Since all frequently detected pesticides (e.g., endosul-
fan, trifluralin, metolachlor, alachlor) were almost ex-
clusively used in the planalto region, which is the nearest
intensively cropped region to the sampling sites at Cui-
abá and Barão de Melgaço, we deduced that the major-
ity of pesticides detected at Sitess P3 to P5 were trans-
ported in the atmosphere for at least 75 km before
deposition. The higher portion of endosulfan-sulfate
found in the lowland samples as compared with the
planalto rainwater samples (31.4 and 13.0%, respec-
tively, of the mean deposited sum of endosulfan com-
pounds) also pointed to a longer residence time of endo-
sulfan in the atmosphere before deposition in the
lowland samplers. The portion of deposited ␣-endosul-
fan in the lowlands (12.5% of the mean cumulative sum
of deposited isomers) was even smaller than in the plan-
alto (24.8%). Assuming a lesser persistence of the ␣
isomer in the atmosphere (Hoff et al., 1992), this finding
also relates to the longer transport time of endosulfan
in the atmosphere until deposition at the lowland sites.
In comparison with studies on the contamination of
rainwater in agricultural areas of temperate regions, the
measured pesticide spectrum and concentrations com-
pare well with data reported from Europe (Dubus et
al., 2000; van Dijk and Guicherit, 1999). Yet, the most
frequently detected pesticides in these studies were her-
bicides (alachlor, atrazine, metolachlor, simazine, triflu-
ralin), whereas we detected in our study often insecti-
cides (endosulfan, monocrotofos, profenofos). This was
presumably due to the higher relative use of insecticides
in the study area, especially in cotton plantations, as
compared with the one in temperate regions. Racke et
al. (1997) summarized that the use of insecticides is
commonly more dominant in tropical than in temperate
agriculture. In part, insecticides were applied to cotton
fields by plane in the study area, which might also be
responsible for the high detection frequency of some
compounds (e.g., endosulfan) in our study.
The sum of pesticide deposition measured in our
study in the planalto within 3.5 mo was similar to maxi-
mum annual deposition rates of pesticides (up to 400 ␮g
m⫺2) found for one of the most developed agricultural
regions of Greece (Charizopoulos and Papadopoulou-
Mourkidou, 1999). Also, maximum concentrations and
individual deposition rates of some pesticides (e.g., met-
olachlor, alachlor) were in a similar range as reported
from Greece and the corn belt of the USA (Goolsby et
al., 1997; Hatfield et al., 1996).
For tropical environments, no data on pesticide depo-
sition with rainfall has been reported so far. Yet, the high
individual maximum deposition rates of the insecticides
endosulfan (sum of compounds: 168 ␮g m⫺2), profenofos
(140 ␮g m⫺2), and monocrotofos (94 ␮g m⫺2) within the
study period in the planalto demonstrate the need for
a further monitoring of these highly toxic insecticides
in the atmosphere of tropical environments. In particu-
lar, the impact of the pesticide deposition on stream–
wetland ecosystems (e.g., gallery forests) in the high-
lands, which are important for the development and
maintenance of high biodiversity in agricultural areas
(Wantzen, 2000), deserves further attention. It remains
to be investigated if the high deposition rates of insecti-
cides were mainly caused by their intensive use in the
planalto study area, or whether the volatilization of
these compounds is generally enhanced in tropical re-
gions as compared with temperate ones.
The deposition of typical cotton, soybean, and corn
pesticides was also proven in rainwater samples of the
lowlands, at least 75 km from the next application areas,
although at concentrations about 5 to 10 times lower
than in the planalto study area. This finding corrobo-
rated results of studies from temperate regions, where
van Dijk and Guicherit (1999) also found evidence for
the medium- to long-range transport of many pesticides.
Pesticides deposited at the highest loads at the lowland
sites (endosulfan compounds, trifluralin, metolachlor)
are known to be transported thousands of kilometers
in the atmosphere (van Dijk and Guicherit, 1999) and
have even been detected in remote arctic regions like
the Bering Sea (Chernyak et al., 1996). Consequently,
the intensive use of pesticides (and especially insecti-
cides) in the planalto might lead to the input of low,
but nevertheless ecotoxicologically relevant quantities
of pesticides by wet deposition to remote ecosystems
(van Straalen and van Gestel, 1999), such as the Panta-
nal. To give a rough estimate of the atmospheric pesti-
cide input to this wetland area (approximately 140 000
km2), we calculated, on the basis of our results (deposi-
tion of 20 ␮g m⫺2), a total of 2800 kg of pesticides
deposited in the Pantanal within the study period of 3.5
mo as a worst case. In view of the strong increase of
the pesticide-intensive cotton production in the state of
Mato Grosso, which has been the major cotton producer
in Brazil since 2000, a rising pesticide input to the Panta-
nal basin has to be expected.
CONCLUSIONS
Our pilot monitoring study showed evidence of the
distribution of a broad spectrum of pesticides in the
northeastern Pantanal basin. Of the 32 substances inves-
tigated (29 pesticides, 3 metabolites), 10 compounds
 LAABS ET AL.: PESTICIDES IN SURFACE WATER, SEDIMENT, AND RAINFALL
were never detected in environmental samples: cyanaz-
ine, ␤-cyfluthrin, ␭-cyhalothrin, deltamethrin, dimetho-
ate, heptachlor, lindane, methyl-parathion, parathion,
and quintozene. The other 22 substances were detected
at least once, leading to an overall pesticide detection
frequency of 68% in surface water samples (n ⫽ 139),
87% in rainwater samples (n ⫽ 91), and 62% in sediment
samples (n ⫽ 26). Pesticide concentrations encountered
in streams, rivers (⬍0.1 ␮g L⫺1), and sediments (⬍10
␮g kg⫺1) were generally low when compared with stud-
ies from temperate regions. However, in planalto rain-
water substantial insecticide (endosulfan, profenofos,
monocrotofos) and herbicide (metolachlor, alachlor, tri-
fluralin) concentrations were found, leading to a high
pesticide deposition rate in this region. In the lowlands,
at about 75 km distance from the next application areas,
maximum pesticide concentrations in rainwater were
about 5-fold, and deposition was about 10-fold lower than
in the planalto. Pesticides of higher detection frequency
and/or persistence in our study region were triazines
(atrazine, simazine, ametryn), acetanilides (alachlor,
metolachlor), trifluralin, and endosulfan compounds
(especially ␤-endosulfan and endosulfan-sulfate). Some
organophosphorus pesticides (e.g., monocrotofos, pro-
fenofos, triazofos) showed higher peak concentrations
in environmental samples but were rarely detected out-
side the application regions, presumably due to their
low persistence. The absence of pyrethroids (e.g., delta-
methrin, permethrin, cypermethrin, ␭-cyhalothrin) in
environmental samples (with the exception of two cyp-
ermethrin–permethrin detections in rainwater) is attrib-
uted to their favorable physico–chemical properties (oc-
tanol–water partitioning coefficient ⬎ 40 000; vapor
pressure ⬍ 2.5 ⫻ 10⫺3 mPa at 25⬚C) and their low appli-
cation rates (⬍100 g ha⫺1). Formerly used organochlo-
rine pesticides (lindane, p,p⬘-DDT, quintozene) could
not be detected any more in water samples, and only
p,p⬘-DDT and p,p⬘-DDE were found at low concentra-
tions in sediments.
In comparison with studies from the midwestern USA
(Goolsby et al., 1997), maximum concentrations in rain-
water and deposition rates of pesticides were in a similar
range or higher for individual compounds in the planalto
area. However, measured river water concentrations of
pesticides were substantially lower in our study area
than in the midwestern USA (Pereira and Hostettler,
1993). This discrepancy gives rise to the speculation that
in the studied tropical area the atmospheric input of
pesticides to ecosystems might be more relevant than
in temperate regions. We may propose that this is either
caused by higher volatilization rates of pesticides after
application or by an accelerated pesticide degradation
in terrestrial and aquatic environments of the tropics,
or by both. Clearly, pesticide dynamics in tropical eco-
system compartments are not yet sufficiently investi-
gated to prove general differences in pesticide fate be-
tween tropical and temperate regions.
ACKNOWLEDGMENTS
This research was part of the SHIFT program (Studies on
Human Impact on Forests and Floodplains in the Tropics),
1647
supported by the German Bundesministerium für Bildung und
Forschung (BMBF Project 01LT0003/7), the Brazilian CNPq
and the Brazilian IBAMA. The authors thank Carlos A.
Schneider and Bernd Reizner for assistance during the sam-
pling period.
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