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Organochlorine pesticides in the ambient air of Chiapas, Mexico
Henry Alegria
a,
*, Terry F. Bidleman
, Miguel Salvador Figueroa
a
Chemistry Department, California Lutheran University, 60 West Olsen Road, Thousand Oaks, CA 91360, USA
b
Centre for Atmospheric Research Experiments, Meteorological Service of Canada, 6248 Eighth Line, Egbert, ON L0L 1N0, Canada
c
Area de Biotecnologia, Facultad de Ciencias Quimicas, University Autonoma de Chiapas, Carretera a Puerto, Madero Km. 2, Tapachula, Chiapas, Mexico
Received 26 January 2005; accepted 5 August 2005
Elevated levels of several organochlorine pesticides were found in the ambient air of southern Mexico.
Abstract
Organochlorine (OC) pesticides were measured in the ambient air of Chiapas, Mexico during 2000
e
2001. Concentrations of some OC pes-ticides (DDTs, chlordanes, toxaphene) were elevated compared with levels in the Great Lakes region, while those of other pesticides were not(hexachlorocyclohexanes, dieldrin). While this suggests southern Mexico as a source region for the former group of chemicals, comparably highlevels have also been reported in parts of the southern United States, where their suspected sources are soil emissions (DDTs, toxaphene) andtermiticide usage (chlordane). Ratios of
p,p
#
-DDT/
p,p
#
-DDE and
trans
-chlordane/
cis
-chlordane/
trans
-nonachlor (TC/CC/TN) in Chiapas sug-gest a mixture of fresh and weathered sources, while congener profiles of toxaphene suggest emission of old residues from soils. This is sup-ported by air parcel back trajectory analysis, which indicated that air masses over Chiapas at the time of sampling had previously passed overareas of continuing or recent use of some OC pesticides as well as areas of past use.
Ó
2005 Elsevier Ltd. All rights reserved.
Keywords:
Organochlorine pesticides; Persistent organic pollutants; Mexico; Air
1. Introduction
Despite being banned for years or even decades in Canada,the U.S. and most European countries, many organochlorine(OC) pesticides such as DDT compounds (DDTs), hexachlor-ocyclohexanes (HCHs), chlordanes, dieldrin and toxaphenecontinue being detected in the ambient air on regional andcontinental scales (Jaward et al., 2004; Shen et al., 2004,2005; Van Drooge et al., 2002). In North America, for exam-ple, OC pesticides commonly occur in air and water in theLaurentian Great Lakes on the Canada
e
U.S. border (Buehleret al., 2001; Cortes and Hites, 2000; Hoh and Hites, 2004;James et al., 2001; Jantunen and Bidleman, 2003; Marvinet al., 2004; Shen et al., 2004, 2005), in snow and glacialice in western Canada (Blais et al., 1998; Donald et al.,1999) and in the Canadian Arctic air (Halsall, et al., 1998;Hung et al., 2002, 2004). An unresolved question is whetherOC pesticides detected in these environments are due to recy-cling from local soils or originate from areas of current or veryrecent use.Many OC pesticides are known to persist in the environ-ment long after their application and have also been shownto be susceptible to long-range atmospheric transport. Conse-quently, both old and new sources may account for the OCpesticides detected in North America. In order to distinguishbetween these contributions, we have been studying the Cen-tral America
e
Mexico region to determine its significance asa source region to North America (Alegria et al., 2000).This region has been characterised by high OC pesticide usagein both agriculture and for disease vector control (Castilloet al., 1997; Leonard, 1990; Mora, 1997). Many OC pesticidescontinue to be used or were used until just recently. Mexico
* Corresponding author. Tel.:
C
1 805 493 3767; fax:
C
1 805 493 3392.
E-mail address:
Ó
2005 Elsevier Ltd. All rights reserved.doi:10.1016/j.envpol.2005.08.007Environmental Pollution 140 (2006) 483
e
491
has historically been a significant consumer of DDT. DDTwasused in agriculture and for disease vector control in many partsof the country. Chiapas was the last state in Mexico legally al-lowed to use DDT for agriculture and was one of the largestusers for disease vector control. High levels of DDT and itsmetabolites have been found in human milk and adipose tissuefrom the state of Veracruz (Waliszewski et al., 2001). Con-sumption of DDT in Mexico for both agriculture and publichealth applications was 8
e
9 kilotonnes (kt) year
ÿ
1
in 1971
e
1972, declined to 3
e
4 kt year
ÿ
1
from 1974 to 1981 andreached a minimum of about 0.5
e
1 kt year
ÿ
1
from 1982 to1984. From 1985 to 1991, DDT use increased to 1.5
e
2.5 kt year
ÿ
1
(Lopez-Carrillo et al., 1996). The use of DDTfor public health declined from 1.4 kt in 1993 to less than0.3 kt in 1999 (NACEC, 2004). Under the North American Re-gional Action Plan (NARAP), Mexico agreed to phase outDDT by 2002, but reported complete phase-out in 2000(Anonymous, 2001). In 1997, Mexico restricted the use of chlordanes to urban applications as a termiticide. Under theNARAP for chlordanes, Mexico ended their use in 2003(Moody, 2003).Toxaphene was legally used in the Mexico
e
Central Amer-ica region until the 1990s (Carvalho et al., 2003; Castillo et al.,1997). Cumulative usage in Mexico (Li and Macdonald, 2005)and Nicaragua(Rodezno, 1997) has been estimated at 71 kt
and 79 kt, respectively. This represents approximately 15%of total usage in the U.S., estimated at 490 kt between 1947and 1986 (Li, 2001). Consequently, the region may representan important source of atmospheric contamination for NorthAmerica.In 1995
e
1996, concentrations of OC pesticides were mea-sured in air at two locations in Belize, Central America, an in-land one in Belmopan and a coastal one in Belize City(Alegria et al., 2000). Results indicated that concentrationsof some OC pesticides at the inland location were significantlyelevated compared to levels measured in the Great Lakesregion (e.g. DDTs, dieldrin and aldrin), supporting the hypoth-esis that Central America is a source region for North Amer-ica. In addition, the elevated levels of some presumablybanned OC pesticides suggests that they are still being usedin the Central America region. To investigate further thesource region hypothesis, this study was carried out insouthern Mexico, historically the largest user of OC pesticidesin the region, to measure their concentrations in ambient air.
2. Experimental
2.1. Sampling collection and preparation
Air samples were collected from the roof of a private resi-dence (10 m) located about 5 km from Tapachula, Chiapas,a city of approximately 250,000 inhabitants located in anarea of large-scale agricultural production in the state of Chia-pas (Fig. 1). This residence is fairly new (
!
10 years old) andwas never treated with chlordanes (termiticides), according tothe owner. Sampling was carried out for 24 h every 14 daysfrom August 2000 to June 2001. Samples were collectedwith a high-volume sampler in which
w
500 m
3
air was drawnthrough a 10-cm diameter glass fibre filter followed by a poly-urethane foam (PUF) trap consisting of two 8.0-cm diameter
!
7.5-cm thick plugs. Filters and PUFs were stored in a freez-er until analysed. Ambient temperatures during the samplingperiod ranged from approximately 299 to 308 K (26
e
35
C).Filters and PUF plugs were soxhlet-extracted together over-night (16 h) with petroleum ether. Prior to extraction, PUFplugs were fortified with a mixture containing 20 ng each of
a
-HCH-d
6
,
13
C
10
-heptachlor
exo
-epoxide (HEPX),
13
C
10
-
trans
-nonachlor (TN) and
13
C
12
-dieldrin, and 100 ng of
p,p
#
-DDT-d
8
which served as surrogates for assessing methodrecoveries for each sample. Extracts were concentrated by ro-tary evaporation, blown down with a gentle stream of nitrogenand exchanged into
iso
-octane. Extracts were cleaned up and
Fig. 1. Sampling location (Tapachula, Chiapas, Mexico).484
H. Alegria et al. / Environmental Pollution 140 (2006) 483
e
491
fractionated on a column of neutral Al
2
O
3
(1 g, 6% deactiva-tion with H
2
O) overlain with 1 cm anhydrous Na
2
SO
4
. Thecolumn was pre-eluted with 10 mL dichloromethane followedby 10 mL petroleum ether. Extracts were applied in
w
1 mLisooctane and the column was eluted with 15 mL 5% dichloro-methane/petroleum ether. The eluate was concentrated by ni-trogen blow-down and solvent-exchanged into isooctane.Volumes were adjusted to
w
1 mL and
13
C
10
-PCB105 wasadded as an internal standard just prior to analysis.
2.2. Analysis
OC pesticides (except toxaphene) were quantified by gaschromatography
e
electron capture negative ion mass spec-trometry (GC-ECNI-MS) on an Agilent 6890GC-5973 MS de-tector with a DB-5 capillary column (J&W, 60 m
!
0.25 mmi.d., 0.25
m
m film thickness). Total toxaphene was quantifiedon a Hewlett
e
Packard 5890 GC-5989B MS Engine, usingthe same type of column, as the sum of the 7-Cl, 8-Cl, and9-Cl homologues. The detectors in both instruments were op-erated in the selective ion-monitoring mode to enhance sensi-tivity. Specific details for the monitored ions and operatingconditions can be found elsewhere (Alegria et al., 2000; Jantu-nen et al., 2000).
2.3. Quality control
Recovery experiments were carried out two ways. First,surrogates were added to PUF plugs prior to extraction. Aver-age recoveries of these surrogates were:
a
-HCH-d
6
56
G
5%,
p,p
#
-DDTd
8
102
G
8%,
13
C
10
-HEPX 72
G
12%,
13
C
10
-TN 90
G
5%,
13
C
12
-dieldrin 76
G
4%. Second, six clean PUF plugswere spiked with a mixture containing the target pesticidesand treated as samples. Average recoveries for the secondmethod agreed with the first method, being greater than 70%for all pesticides except for
a
-HCH (60
G
5%). Calibrationstandards were also routinely run with each batch of samples.Front and back PUF plugs were analysed separately to as-sess breakthrough of gas-phase OC pesticides. Breakthroughwas significant only for
a
-HCH,
g
-HCH and heptachlor.
a
-HCH on the back PUF averaged 78% of the front PUF value(42
e
100%);
g
-HCH averaged 44% (29
e
76%); and heptachloraveraged 62% (38
e
77%). Results for these three pesticidesare reported as the sum of both PUF traps.Three field and three laboratory blanks were run. No peaksmatching the target compounds were found on blank PUFs, solimits of detection (LOD) for each pesticide were calculatedby finding the lowest detectable concentration of the pesticideinjected on the analytical instrument (instrumental detectionlimit, IDL) and calculating the limit of detection as: LOD
Z
(average IDL)
C
(3
!
standard deviation). LODs rangedfrom 0.06 pg
m
L
ÿ
1
(
trans
-chlordane) to 7 pg
m
L
ÿ
1
(
p,p
#
-DDT). These LODs correspond to 0.1
e
14 pg m
ÿ
3
for a nomi-nal air volume of 500 m
3
and a final extract volume of 1000
m
l. The quantitation limit for total toxaphene(24 pg m
ÿ
3
) was based on the lowest concentration of techni-cal toxaphene standard employed (12 pg
m
L
ÿ
1
).
3. Results and discussion
3.1. Air concentrations of pesticides in Chiapas
Table 1gives the concentrations of target OC pesticides inair in Chiapas, Mexico. Because of the wide range of concen-trations, both arithmetic (AM) and geometric (GM) meanswere calculated. GMs were lower than AMs.
3.1.1. DDTs
Concentrations of total DDTs, sum of
p,p
#
-DDT
C
o,p
#
-DDT
C
p,p
#
-DDD
C
o,p
#
-DDD
C
p,p
#
-DDE
C
o,p
#
-DDE(
S
DDT) ranged from 351 to 1548 pg m
ÿ
3
, although most val-ues were in the upper range (11 of 18 samples had concentra-tions above 900 pg m
ÿ
3
and only 2 samples hadconcentrations below 600 pg m
ÿ
3
). AM and GM concentra-tions were 997 and 927 pg m
ÿ
3
, respectively. These high con-centrations are typical of other tropical regions with ongoinguse of DDTs (Larsson et al., 1995; Ngabe and Bidleman,1992).The ratio of
p,p
#
-DDT/
p,p
#
-DDE is generally used as an in-dicator of aging of DDTs. This ratio calculated from meanconcentrations was 1.06 based on AM and 1.02 based onGM concentrations; the ratio was
O
1 for half of the samples(Table 1).Shen et al. (2005)deployed passive air samplers
(PAS) across North America during 2000
e
2001 (see below)and reported ratios of
p,p
#
-DDT/
p,p
#
-DDE
Z
0.94 in Tapa-chula and 1.3 in Chetumal, Mexico, 1.2 in Belmopan, Belize,and 5.8 in Costa Rica. The Mexico and Belize ratios agreewell with our results in Tapachula, while the Costa Rica com-position indicates a greater input of fresh DDT. Ratios of
p,p
#
-DDT/
p,p
#
-DDE in the ambient air of the U.S. and Canada aregenerally
!
1, but occasionally exceed 1 (Aulagnier and Pois-sant, 2005; Cortes and Hites, 2000; Harner et al., 2004; Park et al., 2001; Shen et al., 2005). The
p,p
#
-DDT/
p,p
#
-DDE
w
1 in Tapachula is consistent with a mixture of contributionsfrom recent usage and old DDT residues.
3.1.2. HCHs
Average concentrations of HCHs were:
a
-HCH AM
Z
27 pg m
ÿ
3
, GM
Z
22 pg m
ÿ
3
and
g
-HCH AM
Z
76 pg m
ÿ
3
, GM
Z
72 pg m
ÿ
3
. The ratios of
a
-HCH/
g
-HCHbased on AM and GM concentrations were 0.38 and 0.31.This ratio in technical HCH ranges from about 4
e
a
-HCH/
g
-HCH found here in-dicates the continued use of lindane (pure
g
-HCH) in the re-gion. The ratio of ~0.3 found here is consistent with resultsfrom a 2000
e
2001 passive air sampling campaign in the re-gion in which
a
-HCH/
g
-HCH
Z
0.16 in Tapachula and0.46 in Chetumal, Mexico, 0.18 in Costa Rica and 0.27 in Bel-mopan, Belize (Shen et al., 2004).The high proportion of
a
-HCH on the second PUF trap in-dicates the possibility that there may have been some break-through through both PUF traps and consequentlyincomplete collection and underestimated air concentrations,which would alter the true ratio of
a
-HCH/
g
-HCH. However,the agreement of our ratio of
w
0.3 with ratios in the region
485
H. Alegria et al. / Environmental Pollution 140 (2006) 483
e
491
of 00
perticides in air
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