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DOI 10.1007/s00128-017-2090-x
Abstract The aim of this study was to evaluate the dis- tribution of DDT and
metabolites in surface soils and soil profiles from two areas containing
deposits of obsolete pesticides in Belém, Amazon Region, Brazil. DDT and
metabolites were extracted by microwave assisted extrac- tion and analyzed by gas
chromatography with electron capture detection. Concentrations of total DDT in
surface soil samples ranged from 64.22 mg kg−1 in area 1 (A1) to
447.84 mg kg−1 in area 2 (A2). Lower levels were found in
soil profiles than at the surface (6.21–21.17 mg kg−1 in A1 and 36.13–113.66 mg
kg−1 in A2). pp’-DDT, pp′-DDE and pp′-DDD were detected in sediments at levels of
2.01, 0.96 and 0.35 mg kg−1, respectively. The ratio (DDE +DDD)/ ΣDDT was low
indicating the recent introduction of DDT to the environment in the two study
areas, through the volatilization and atmospheric deposition of the obsolete
pesticides.
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Bull Environ Contam Toxicol
had been recorded in the region, including Pará, wich had the highest malaria
incidence. In 1991, the Ministry of Health purchased about 3 tons of DDT (D’Amato
et al.
2002). However, in 1998, the use of DDT in public health campaigns was banned in
Brazil, and DDT and other pes- ticides stored in deposits throughout the country
were recognized as an environmental threat. There are exposed or potentially
exposed populations in 750 areas of Bra- zil, of which 128 are identified as former
pesticide depos- its, 64 are no longer pesticide deposits and are used for other
purposes, 23 are classified as suspected contamina- tion areas, and 41 are
classified as potentially contami- nated areas, with DDT and other pesticide
residues on- site awaiting appropriate disposal or storage (FUNASA
2013).
This study aims to evaluate the distribution of DDT and metabolites in surface
soils and soil profiles from two deposits of obsolete pesticides in Belém, Amazon
Region, Brazil. These deposits served as regional DDT distribution points for the
National Foundation of Health (FUNASA), and DDT waste is dispersed across the areas
in soil and stored in glass bottles, plastic bags, and pack- ages. We aim to verify
whether the DDT levels in the soil pose an environmental risk to the health of
adjacent populations.
Materials and Methods
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Bull Environ Contam Toxicol
was used as a DDT distribution point for communities near Belém, for which boats
are the main means of transport. A2 has two large deposits of obsolete pesticides,
the first containing glass bottles and the second containing plastic containers and
bags of pesticides. We collected six soil samples and four sediment samples in this
area along the Guajará Bay. Soil profiles were sampled at two different depths: 20–
50 cm and 50–100 cm. Soil and sediment sam- ples (1 kg) were collected from each
site using a stainless steel sampler. Equipment used for sample collection was
rinsed with hexane and acetone. The samples were packed in chemically clean
polyethylene bags and transported to the laboratory where they were immediately
stored. Soil and sediment samples were air-dried, sieved through 250 mesh stainless
steel sieves, and packaged and stored in amber glass bottles at −20°C for
laboratory analysis.
Analytical standards of pp′-DDT, pp′-DDE, pp′-DDD, op′-DDT, op′-DDE, and op′-DDD
were acquired from ChemService (West Chester, PA, USA). High purity rea- gents and
solvents (pesticide grade solvents) were obtained from Mallinckrodt (St. Louis, MO,
USA). Soil and sedi- ment samples (2 g each) were extracted by microwave assisted
extraction (MAE) using a Mars Xpress Xtraction (CEM Corporation, Matthews, NC,
USA), in 20 mL of n-hexane/acetone (8:2, v/v). The samples were heated to an
initial temperature of 30°C for 2 min, then gradually heated to 100°C (10°C min−1)
and left for 20 min. MAE used
800 W of power. After extraction, the samples were concen- trated to 2 mL in a
rotary vacuum evaporator. The organic extract from the chromatographic analysis was
purified on solid phase extraction cartridges packed with 2 g of deac- tivated
silica gel and 1 g of anhydrous sodium sulfate, and eluted with portions of hexane
and n-hexane/dichlorometh- ane (1:1, v/v). After elution, samples were concentrated
to
0.2 mL under N2 at a flow rate of 5 mL min−1, and the resi-
due dissolved in 1 mL eluted by n-hexane.
For quantitative analysis, we used the CP 3800 gas chromatograph with electron
capture detection (GC-ECD)
(Varian, Palo Alto, CA, USA) equipped with Workstation
5.0 software to process the chromatographic data. A fused silica capillary column
(30 m ×0.32 mm internal diameter,
0.25 µM film thickness; CP SIL-8CB, J & W Scientific, Folsom, CA, USA) was used to
separate the analytes. The temperature was ramped to 150°C in 1 min, and then from
150 to 250°C in 5 min (6°C min−1). The N2 (99.999%) car- rier gas had a flow rate
of 1.2 mL min−1. The injector was
operated in the splitless mode at 250°C. The detector tem- perature was 300°C.
We performed blank analyses to test for interference in the samples, carried
out recovery tests in triplicate on fortified samples and standard reference
material (SRM
1944 NIST, Gaithersburg, MD, USA), and analyzed the results according to the method
described above for ana- lytical quality control. Soil and sediment were fortified
at
50 µg g−1 of pesticide mixture (op′- and pp′-DDT, DDE,
DDD). The results for the fortified samples and standard reference materials ranged
from 83.2% to 94.6% and 73.5% to 88.7%, respectively, which was within the
acceptable limit for chromatographic tests (70%–120%). We calculated calibration
curves by external standardization with correla- tion coefficient (r) ≥0.99. The
method detection limit was determined to be three times the signal produced by the
signal-to-noise ratio obtained at the baseline of the chroma- togram, and ranged
from 0.01 to 0.05 µg g−1. Results were expressed on a dry weight (dw) basis.
Statistical analyses were performed using Statistica software 7.0. Arithmetic mean,
standard deviation, and maximum and minimum val- ues were determined.
Tables 1 and 2 show the average concentrations of total DDT (Σ =op′ +pp′ −DDT, DDE,
DDD). The soil was sam- pled in two very heterogeneous areas, and contamination in
A2 was higher than the amount of obsolete pesticides in the
aStandard deviation
7.67 ±6.66 (1.1–18.51)
2.43 ±2.13 (n.dc–5.32)
5.41 ±3.66 (0.85–10.32)
1.53 ±0.81 (0.64–2.81)
2.81 ±2.77 (n.d–7.41)
0.71 ±0.49 (n.d–1.31)
2.46 ±2.88 (0.63–7.55)
0.76 ±0.75 (n.d–1.98)
1.61 ±1.34 (n.d–3.14)
0.55 ±0.33 (n.d–0.8)
1.21 ±1.38 (n.d–3.6)
0.2 ±0.27 (n.d–0.65)
21.17
6.21
bValues minimum and maximum
cNot detected
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Bull Environ Contam Toxicol
Profile soil
(50–100 cm)
74.89 ±115.57 18.85 ±26.63 11.43 ±11.30 5.57 ±12.06
2.27 ±3.21 0.65 ±0.97 113.66 (1.25–303.15) (0.24–
71.24) (n.d–28.15) (n.d–30.15) (n.d–8.38)
(n.d–2.12)
18.52 ±21.66 11.76 ±12.00 2.83 ±3.27 2.31 ±4.83
0.42 ±0.55 0.29 ±0.54 36.13 (0.12–52.35)
(0.62–32.14) (n.d–8.55) (n.dc–12,2) (n.d–1.23)
(n.d–1.35)
Sediment 2.01 ±0.85 0.96 ±0.73 0.35 ±0.58
– – –
3.32
(1.35–3.20) (0.31–1.92) (0.03–1.23) –
– –
aStandard deviation
bValues minimum and maximum
cNot detected
area would suggest. In A1, the total DDT concentration in the surface soil ranged
from 28.43 to 141.32 mg kg−1, with a mean of 64.22 mg kg−1, and in A2 it ranged
from 4.45 to
1887 mg kg−1, with a mean of 447.84 mg kg−1. Villa et al. (2006) found lower values
than these in the surface soil and soil profiles of obsolete insecticide deposits
in Várzea Grande, Brazil. Additionally, they collected samples at three
different times and the detected DDT values declined over time. In similar studies
conducted in areas of obsolete pesticides in Pakistan, Ahad et al. (2010) found
high lev- els of DDT (247–9157 mg kg−1) and Alamdar et al. (2014) found lower
levels, ranging from 77 to 21,200 ng g−1.
In this study, we found that DDT and metabolites in surface soil decreased with
increasing depth, indicating a low vertical mobility of DDT in soil. This may
reflect the low organic matter content typical of deeper soils. DDT concentrations
were higher in the 20–50 cm soil profiles than in the 50–100 cm soil
profiles. In A1, total DDT concentrations ranged from 2.58 to 50.53 mg kg−1,
with a mean of 21.17 mg kg−1, in 20–50 cm soil profiles, and from 0.64 to 12.87 mg
kg−1, with a mean of 6.21 mg kg−1, in 50–100 cm soil profiles. In A2, total DDT
concentra- tions ranged from 1.49 to 403.19 mg kg−1, with a mean of
113.66 mg kg−1, in the 20–50 cm soil profiles. Values were
lower in the 50–100 cm soil profiles, ranging from 0.74 to
107.82 mg kg−1, with a mean of 36.13 mg kg−1. A study of soil profiles in Tianjin,
China, obtained similar results (Wang et al. 2006). Other studies found lower DDT
con- centrations. Falandysz et al. (2001) found low DDT con- centrations in the
Polish cities Katowice (110 ±89 ng g−1) and Krakovia (260 ±620 ng g−1). DDT and its
metabolites were detected in soil in Beijing, China, with total DDT levels ranging
from 0.03 to 1282 ng g−1, with a mean of
68.14 ±189.46 ng g−1 (Yang et al. 2010). In Mexico, Mar- tínez et al. (2012)
measured DDT and DDE concentrations
in outdoor and indoor soil and dust in three communities in Chihuahua. They found
higher concentrations of DDT than DDE, indicating a recent use of DDT. A study of
the level of DDT in soil and dust in five communities in Chiapas found
concentrations of 0.002 to 26.980 mg kg−1 and n.d to
2119.00 mg kg−1, for soil and dust, respectively. (Martínez-
Salinas et al. 2011). In Monterrey, a non-endemic region of malaria in which DDT
was seldom used in the past, lev- els of DDT, DDE, and total DDT in soils were
lower than those found in this study (Orto-Garcia et al. 2015).
There have been few studies on contamination by DDT in the Amazon region, despite
the location’s widespread use of DDT to fight malaria, which is endemic to the
area. Torres et al. (2002) found DDT concentrations in soil near the Tapajós and
Madeira Rivers between 281–1224 ng g−1 and 4–123 ng g−1, respectively. Saldanha
et al. (2010) measured DDT levels in residential and forest soils and found that
residential soils, where DDT was used indoors to fight malaria, had higher DDT
levels than forest soils.
Residues of pp′-DDT, pp′-DDE, pp′-DDD, op′-DDT, op′-DDE, and op′-DDD were
detected in 91%, 100%, 54%,
45%, 63%, and 36% of samples, respectively. The con- centration of pp′-DDT was
highest in all samples (Figs. 2,
3). This was expected, because commercial DDT consists mainly of pp′-DDT (75%),
followed by op′-DDT (15%) and then pp′-DDE (5%) (Alamdar at al. 2014). Although pp
′- DDT can contaminate environments through drifting and direct application, it
does not penetrate easily into ground- water. The persistence of DDT in soil
depends on factors such as temperature, humidity, and soil type. DDT evapo- rates
and degrades faster, and is less persistent, in tropical regions than in cold
regions (ATSDR 2005).
Over time, DDT is converted to DDE through oxida- tive dechlorination caused by
aerobic bacteria action, or to DDD in anaerobic conditions (Hitch and Day 1992;
Bidlan
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Bull Environ Contam Toxicol
pp'- DDE
pp'- DDT
Solo Superficial
0 50
100
Contribuição %
Fig. 3 Contribution (%) of DDT and metabolites in soil and sediment. (Area A2)
Sedimento Superficial
Solo perfil (50-100 cm) Solo Perfil (20-50 cm)
op' - DDD op' - DDE op' - DDT pp'- DDD pp'- DDE
pp'- DDT
Solo Superficial
0 50 100
Contribuição %
and Manonmani 2002). We found levels of pp′-DDE, the main metabolite of pp′-DDT, to
be higher than pp′-DDD in both surface and profile soils, indicating aerobic
conditions. The ratio (DDE +DDD)/∑DDT was higher than 0.5, indi- cating long-term
degradation of DDT to DDE and DDD. This suggests an older source of environmental
DDT, while a ratio (DDE +DDD)/∑DDT lower than 0.5 would indi- cate a recent source
(Hitch and Day 1992).
In this study, the ratio of (DDE +DDD)/∑DDT in A1 was 0.52 in surface soil and
0.48–0.52 in soil profiles. The ratio in A2 was 0.27 in surface soil and 0.29–0.42
in soil profiles. This lower ratio indicates a slow degradation of DDT to DDE and
DDD as well as a recent introduction of DDT to the area, which may endanger people
in nearby res- idential areas through volatilization and atmospheric depo- sition
of the DDT.
The National Environment Council of Brazil (CON- AMA) mandated maximum values for
DDT, DDD, and DDE in residential and industrial soils of 2 and 5 mg kg−1,
3 and 7 mg kg−1, 1 and 3 mg kg−1, respectively (CONAMA
2009). This study found concentrations higher than the legal limits.
Residues of pp′-DDT, pp′-DDE and pp′-DDD were found in 100% of the sediment
samples, with levels of 2.01,
0.96 and 0.35 mg kg−1, while residues of op′-DDT, op′- DDE, and op′-DDD were not
detected. These results indi- cate DDT sources in Guajará Bay, which harbors
several species of Amazonian fish used as food. Additionally, some points along the
river are used as recreation areas. High levels of DDT in sediments can be
attributed to the prox- imity of Guajará Bay to A2, which is highly contaminated
with DDT. The ratio (DDE +DDD)/∑DDT is 0.39, which indicates a recent introduction
of DDT into the sediments of Guajará Bay. Levels of DDT found in sediments in this
study were higher than in studies by Wasswa et al. (2011), who studied
organochlorine residues in 117 sediment sam- ples collected in four bays of Lake
Victoria; Cheng et al. (2014), who studied sediment samples on the Tibetan pla-
teau; and Alonzo-Hernandez et al. (2014), who conducted a study in the Gulf of
Batabanó, Cuba. Souza et al. (2008) found DDT levels between 10.61 and 37.40 ng g−1
in Gua- nabara Bay, Rio de Janeiro, Brazil. A study by Torres et al.
(2002) of sediments from Madeira and Tapajós Riv- ers in the Amazon Region found
DDT levels of 0.8 and
57.5 ng g−1, respectively.
DDT levels in the sediments found in Guajará Bay are above the upper limits
prescribed by CONAMA (2012), which are 3.54–8.51 µg kg−1 (DDD), 1.42–6.75 µg
kg−1
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Bull Environ Contam Toxicol
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toxic effects of DDT on human health and the environment and require remediation.
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