Environment International 37 (2011) 435–442

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Environment International
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Health risks from large-scale water pollution: Trends in Central Asia

Rebecka Törnqvist a,⁎, Jerker Jarsjö a, Bakhtiyor Karimov b
a
Department of Physical Geography and Quaternary Geology, Svante Arrhenius väg 8C, Stockholm University, SE-106 91 Stockholm, Sweden
b
Institute of Water Problems of Uzbekistan Academy of Sciences, Fayzulla Khojaev Street 25A, Tashkent 700125, Uzbekistan

a r t i c l e i n f o a b s t r a c t

Article history: Limited data on the pollution status of spatially extensive water systems constrain health-risk assessments at
Received 17 March 2010 basin-scales. Using a recipient measurement approach in a terminal water body, we show that agricultural
Accepted 10 November 2010 and industrial pollutants in groundwater–surface water systems of the Aral Sea Drainage Basin (covering the
Available online 4 December 2010
main part of Central Asia) yield cumulative health hazards above guideline values in downstream surface
waters, due to high concentrations of copper, arsenic, nitrite, and to certain extent dichlorodiphenyltri-
Keywords:
Aral Sea
chloroethane (DDT). Considering these high-impact contaminants, we furthermore perform trend analyses of
Health risk their upstream spatial–temporal distribution, investigating dominant large-scale spreading mechanisms. The
Pollution ratio between parent DDT and its degradation products showed that discharges into or depositions onto
Irrigation surface waters are likely to be recent or ongoing. In river water, copper concentrations peak during the spring
Surface water season, after thawing and snow melt. High spatial variability of arsenic concentrations in river water could
Groundwater reflect its local presence in the top soil of nearby agricultural fields. Overall, groundwaters were associated
with much higher health risks than surface waters. Health risks can therefore increase considerably, if the
downstream population must switch to groundwater-based drinking water supplies during surface water
shortage. Arid regions are generally vulnerable to this problem due to ongoing irrigation expansion and
climate changes.
© 2010 Elsevier Ltd. All rights reserved.

1. Introduction understanding (e.g., Malmström et al., 2000, 2008; Jarsjö et al., 2005;
Shibuo et al., 2007; Jarsjö and Bayer-Raich, 2008; Destouni et al.,
Groundwater and surface waters that constitute an integral part of 2010a) is hampered, however, by the lack of clear field datasets and
the continental water cycle can transport and spread contaminants syntheses of large-scale contaminant spreading that can be used
from spatially limited industrial areas or mining areas to extensive for independent testing of various predictive models. In particular,
downstream regions. This is in addition to spreading of more diffuse observed changes need to be large enough to stand out from random
contamination, such as from pesticides distributed over agricultural fluctuations caused, for example, by weather conditions and geo-
fields. Water resources are affected by man-made pollution world- logical heterogeneity.
wide to such a degree that restoration to pristine conditions is not An example of severe human-induced changes in the continen-
achievable. In this context, health-risk assessments (e.g., WHO, 2006; tal cycling of water and dissolved substances is provided by the
U.S. EPA, 1989, 2006; Ma, 2000; Fryer et al., 2006; Törnqvist et al., deepening environmental, health and socioeconomic crisis in Central
2008) and ecological impact assessments (e.g., Schlüter et al., 2005) Asia (traditionally defined as the former Soviet Union states of
provide means for rational identification of unacceptable pollution Uzbekistan, Turkmenistan, Tajikistan, and Kyrgyzstan), which to
levels and appropriate remediation target levels. large extent coincides with the extensive Aral Sea Drainage Basin
For site-specific tailoring of effective remediation methods, one (ASDB) that also includes southernmost Kazakhstan and northern
must also assess how downstream pollution levels can change in Afghanistan (Fig. 1). The crisis is mainly due to the overexploitation of
response to different plausible upstream remediation measures, e.g., water resources caused by gigantic irrigation programs in the lower
source removal, land use change, and various water treatments. In arid region of ASDB during the Soviet era (Micklin, 2003; Glantz,
addition, climatic and other changes in ambient conditions may 1999). The overexploitation has led to a drastic drop in the river
influence pollution spreading. Hence, remediation assessments need discharge of the two main rivers into the Aral Sea causing its des-
to be underpinned by scientific understanding of dynamic flow and iccation, see Fig. 1. Groundwater flows have not decreased as much as
transport processes on relatively large scales. The current scientific surface water flows and have therefore become increasingly important
for the overall water budget in the Aral Sea vicinity in recent years
(Jarsjö and Destouni, 2004; Gascoin and Renard, 2005; Shibuo et al.,
⁎ Corresponding author. Tel.: +46 8 6747833; fax: +46 8 164818. 2006, 2007). The intensive agriculture in the region is also associated
E-mail address: rebecka.tornqvist@natgeo.su.se (R. Törnqvist). with extensive use of fertilizers and pesticides, which has polluted

0160-4120/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envint.2010.11.006
436 R. Törnqvist et al. / Environment International 37 (2011) 435–442

Fig. 1. The Aral Sea drainage basin (black solid line) with the Amu Darya river delta (dotted line) south of the sea, in which Mejdurechye Reservoir is located. Location of sampling
sites for surface water and groundwater, main irrigated areas (outlined in grey; Global Map of Irrigation Areas, Siebert et al., 2005), the extent of the Aral Sea in 2005 (filled blue) and
in 1960 are shown. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

water and soils. From a scientific viewpoint, the large magnitude of difficulty is addressed by interpretation of novel measurements
observed environmental change within the ASDB provides unique in the downstream Mejdurechye reservoir that due to the last
opportunities for testing hypotheses regarding large-scale effects of decade's acute water scarcity in effect has replaced the Aral Sea as a
various contaminant transport processes. terminal water body and main recipient of pollutants from major
Elevated concentrations of organochlorine pesticides and toxic groundwater–surface water systems of the ASDB. We identify the
metals, including arsenic, have been observed in human blood, milk, most hazardous contaminants (from a human health perspective)
hair and urine of the population living in the ASDB (Atanyiazova et al., from this hydrological focal point and synthesise data on their
2001; Jensen et al., 1997; Erdinger et al., 2004). Maternal and infant distribution in upstream water systems of the largest sub-basin of the
mortality, delay in growth and puberty of children, liver and digestive ASDB, namely the Amu Darya drainage basin. We investigate in
system disorders, allergic problems and diseases related to bacterio- particular spatial and temporal trends along hydrological pathways,
logical status of water and soils have significantly increased in this and differences between different hydrological systems (river water,
region compared to 1960, prior to the ecological decline (Elpiner, reservoir water and groundwater). More generally, the analyses aim
1999; Zetterström, 1999). Locally produced animal foodstuff has been at revealing large-scale effects of physical and chemical processes that
found to provide an important exposure pathway for persistent govern the spreading of persistent toxic contaminants.
organic pollutants in Karakalpakstan in Uzbekistan (Muntean et al.,
2003). Furthermore, consumption of local, untreated water is 2. Site description and methods
common in the lower ASDB. In Karakalpakstan for instance, only 20
to 30% of the rural population have access to piped water and 25% of 2.1. Site description
the population use water from irrigation channels as their key water
source (Small et al., 2003). It is plausible that pollutant exposure The ASDB is an endorheic basin of 1,874,000 km2, which comprises
through drinking water can considerably contribute to main health two principal rivers that discharge into the Aral Sea; the 2400 km long
problems. For example, several compounds have been found to Amu Darya river and the 2500 km long Syr Darya river, see Fig. 1. Amu
exceed World Health Organisation (WHO) drinking water standards Darya river discharge constitutes a major part (about 70%) of the
in groundwaters and surface waters of the drainage basin, such as renewable water resources within the ASDB. Meltwater from snow
nitrogen compounds, copper, lead, chromium and uranium (Crosa and glaciers in the Pamir mountains is a main source for the river
et al., 2006a; Froebrich et al., 2006; Kawabata et al., 2006; Friedrich, discharge, which causes flow peaks between April and September
2009). (Froebrich, 2004). The average Amu Darya discharge before the large-
We here investigate health hazards related to water-borne, basin- scale expansion of the irrigation system was 78 km3 year−1 (Crosa
scale spreading of multiple persistent pollutants, including pesti- et al., 2006a). However, because the Amu Darya river basin contains
cides and toxic metals. When such large scales are considered, a main most of the irrigated areas in the ASDB, today's river discharge varies
difficulty is that the spatial coverage of surface water and groundwa- between 0 and 1 km3 year−1 (Oberhänsli et al., 2009).
ter measurement points becomes limited. Not least the groundwater Through extensive use of fertilizers, pesticides and herbicides,
system is relatively unavailable to detailed measurement. This toxic chemicals have been spread over the agricultural fields, including
 R. Törnqvist et al. / Environment International 37 (2011) 435–442 437

dichlorodiphenyltrichloroethane (DDT), γ-hexachlorocyclohexane that HFs above 1 indicate potential health risks. The reference
(γ-HCH), arsenic and copper. Surplus irrigation water evaporates concentration is a substance-specific concentration below which the
or returns to the rivers, which results in downstream accumulation risk for adverse health effects is very low, given a lifetime intake of
of agrochemicals and salt in the rivers (Crosa et al., 2006b). Fur- water at the reference concentration (Fryer et al., 2006; WHO, 2006).
thermore, during the Soviet era significant mineral deposits were The HF quantifications given here are based on drinking water
found within the ASDB. For instance, metals recovered from today's guideline values from WHO (2006), see Table 1. Guideline values from
mining industry in Uzbekistan include cadmium, copper, lead and the U.S. Environmental Protection Agency (U.S. EPA, 2006) can differ
uranium (Clark and Naito, 1998). As a consequence of the well- from the WHO-values, due to quantification uncertainties and
developed mining industry, a main pollution source in ASDB is acid different assumptions regarding for instance body weight (WHO
mine drainage, which generally contains high metal concentrations, assumes 60 kg and U.S. EPA assumes 70 kg) and the relative source
including also elevated arsenic concentrations (see e.g. Smedley and contribution for substances that mainly are likely to come from food
Kinniburgh, 2002; Duker et al., 2005). (WHO assumes 10% and U.S. EPA assumes 20%). For chromium,
The Amu Darya river delta (Fig. 1) is a recipient of water-borne fluoride, mercury, and γ-HCH, the two standards differ by a factor two
pollutant flows from the main part of ASDB due to its physical location or more (Table 1). We then report to which extent resulting
far downstream in the basin. The delta is situated in an arid climate differences in HF impact interpretations and conclusions.
zone. Temperatures range from 45 °C in summers to −30°C in winters Possible health hazards of several co-existing dissolved contami-
(Nezlin et al., 2004), the average precipitation is 133 mm year−1 and nants can be quantified through the addition of the mixture's
the potential evaporation varies between 1200 to 1600 mm year−1 substance-specific HFs. This yields a cumulative hazard factor
(Schutter and Dukhovny, 2003). It is thus entirely dependent on (CHF = ∑HF), which with its assumed additive toxic effects provides
runoff routed through rivers and canals from upstream areas. From a a relevant first-order estimate of aggregated toxicity, at least in the
water balance — vulnerability perspective, it therefore shares absence of more detailed data on interactions between the compo-
characteristics with, e.g., the Nile delta in Egypt, and the Eufrat–Tigris nents of the considered mixture (WHO, 2006; U.S. EPA, 1989). CHFs
marshes in Iraq. The Amu Darya delta and associated irrigation canal were calculated for the mixture of substances measured at each of the
systems cover approximately 40,000 km2, which is almost double the four sampling campaigns performed during 2007 and 2008 in
size of the Nile delta. The Amu Darya river is, since about a decade, Mejdurechye reservoir.
water depleted before reaching even the former shoreline of the Aral
Sea. The Mejdurechye reservoir, having an area of about 180 km2 and 2.3.2. Statistical analysis of trends along the Amu Darya river
a maximum depth of 4 m (see the Supplementary information for a For the substances that predominantly contributed to elevated
more detailed description), is one of the largest water bodies in the CHFs in the Mejdurechye Reservoir, statistical analyses were
delta and has in effect become a new terminal water body of the delta. conducted of available monthly river monitoring data from the period
between 1998 and 2002 at Termez, Tuyamuyn, Nukus and Kziljar
2.2. Sampling and experimental methods gauging stations (Nasrulin and Zahidova, 2002; Fig. 1). The analysed
dataset comprised in total four substances and 680 observations. In
Concentration measurements of 13 different substances were a series of statistical tests the substance-specific data were further
conducted in the Mejdurechye reservoir waters during sampling grouped into (1) four categories according to location (e.g., all
campaigns in July and October 2007, and in May and July 2008. Termez-data in one category), (2) a maximum of 20 categories
Sampling procedures, measurement locations (Fig. S1), analysis according to location and year (e.g., all Termez-data from 2002 in
methods (Table S2), instruments (Table S2), detection limits (Table one category), and (3) a maximum of 16 categories according to
S2) and further references are given in the Supplementary information. location and season (categorising December to February as winter,
March to May as spring, June to August as summer, and September
2.3. Interpretation methods to November as autumn). A total of 84 category pairs were tested
for whether or not the difference in the category mean values was
2.3.1. Hazard factors (HFs) and cumulative HFs (CHFs) statistically significant, using the Smith–Satterthwaite two sample
We express health risks through hazard factors (HFs), by dividing two tail test for populations with unknown and unequal variances at a
measured concentration levels with a reference concentration, such 95% confidence level. The test approximates a t-distribution with a

Table 1
Guideline values for drinking water quality from WHO (2006) and U.S. EPA (2006) as well as main adverse health effects related to excess intake of the considered substances (Howd
and Fan, 2008; WHO, 2006). When the two standards differ by a factor two or more for a certain substance, the guideline value is marked in bold.

WHO U.S. EPA Health effects (Howd and Fan, 2008; WHO, 2006)
[μg L−1] [μg L−1]

Nitrate, NO-3 50 000 44 000 Shortness of breath and blue baby syndrome for infants
Nitrite, NO-2 200 (long-term exposure) 3300 Shortness of breath and blue baby syndrome for infants
3000 (short-term exposure)
Chromium tot, Cr 50 100 Allergic problems
Arsenic, As 10 10 Skin damage and circulatory system problems; increased risk of lung, bladder or skin cancer
Fluoride, F- 1500 4000 Bone fluorosis
Copper, Cu 2000 1300 Gastrointestinal effects, liver and kidney damage
Lead, Pb 10 15 Children: delay in physical and mental development; Adults: kidney damage
Cadmium, Cd 3 5 Kidney damage
Mercury, Hg 6 2 Kidney damage
Manganese, Mn 4000 – Neurological effect
Nickel, Ni 70 – Allergic effect
DDT 1 – Liver cancer
DDD 1 – Liver cancer
DDE 1 – Liver cancer
γ-HCH 2 0.2 Liver and kidney problems
438 R. Törnqvist et al. / Environment International 37 (2011) 435–442

degree of freedom estimated from observed sample variances Table 2

(Johnson, 2000). The proportion (in percentage) of significant differences in means for HFs for individual
substances (As, Cu, F− and NO− 2) between (1) the stations within the measurement
period 1998–2002, (2) the stations within years, (3) the station within seasons, (4) the
2.3.3. Analysis of HFs in different water systems of the basin years within locations, and (5) the seasons within stations.
The following sites and water systems were considered in the Arsenic, Copper, Fluoride, F- Nitrite,
basin analysis (see Fig. 1 for locations): (i) reservoir water samples As Cu NO-2
from two measurement points in Tuyamuyn Hydroengineering
Variation between locations:
Complex (THC) (conducted in April 2003, mean values of three to (1) Within the measurement period 67 0 33 50
five measurements per substances are reported for nitrate, nitrite, (2) Within years 32 16 11 5
copper, cadmium, chromium, manganese, nickel and lead; Crosa et al., (3) Within seasons 19 19 16 19
(4) Variation between years:
2006b), (ii) river water samples from Darganata (conducted in April
Within locations 12 0 28 0
2003, mean values of three to five measurements per substances are (5) Variation between seasons:
reported for nitrate, nitrite, copper, cadmium, chromium, manganese, Within locations 6 31 0 19
nickel and lead; Crosa et al., 2006b), Termez, Tuyamuyn downstream
of THC, Nukus, and Kziljar (average of 60 measurements per
substance between 1998 to 2002 for nitrate, nitrite, fluoride, arsenic, downstream Nu and Kz stations, and a lack of overlap between all other possible station
mercury, copper, chromium, manganese, nickel and lead; Nasrulin combinations, which yields the statistical outcome presented in Table 2. There is hence
a clear upstream–downstream difference in mean arsenic HFs (Fig. 2a). Nitrite HFs also
and Zahidova, 2002), (iii) drainage water samples from Bukhara show a considerable spatial variation (Table 2, column 4). Table 2 furthermore shows
(conducted in April 2003, mean values of three to five measurements that the spatial variations of arsenic and nitrite HFs are strong relative to annual
per substance of nitrate and nitrite; Crosa et al., 2006b) and Kungrad (Table 2, row 4) and seasonal (Table 2, row 5) variations.
and Nukus–Chimbay–Kegeyeli–Bozatau, the latter hereafter abbrevi- The overall results for copper showed no significant differences in mean HF values
between measurement locations (Table 2, column 2, row 1). Some spatial differences
ated to Nukus (conducted in the winters of 1999 and 2000, mean
exist within individual years and seasons (column 2, rows 2 and 4). However, the most
values of occasional measurements of nitrate and nitrite; Kurbanbaev pronounced variation in copper HFs is the seasonal one, yielding statistically significant
et al., 2002), and (iv) 14 groundwater sampling locations within a differences in 31% of the considered cases (column 2, row 5 in Table 2). Fig. 2b shows
distance of 45 km from the Amu Darya river, including Chalish, that relatively low copper HFs during summer and autumn at the four measurement
Dusenbay, Yangibazar, and Buzkala (mean values of three measure- points contribute to this statistical outcome. Finally, fluoride HFs show both annual
(column 3, row 4 in Table 2) and spatial (column 3, row 1 in Table 2) variations. Fig. 2c
ments per location and substance of copper, chromium and lead; shows that there is an underlying trend of annually increasing fluoride HFs between the
Froebrich et al., 2006). The samples were taken in formations with years 1999 and 2002.
hydrogeological characteristics that can allow considerable water
withdrawals for, e.g., drinking water supply. In addition, we compare
3.2. HFs in different water systems of the basin
resulting main trends in HFs of groundwater and surface water from
the Amu Darya drainage basin with results synthesised from the Syr Fig. 3 shows comparisons between mean HFs for river and reservoir water in the
Darya drainage basin from groundwater or surface water measure- Amu Darya drainage basin (shown to the right of the vertical lines in Fig. 3) on the one
ments in Amanotkel (river water; Bosch et al., 2007), Zhalangash hand, and drainage water (Fig. 3a) and groundwater (Fig. 3b and c), on the other hand
(shown to the left of the vertical lines in Fig. 3). The measurement stations of the river
(groundwater; Bosch et al., 2007) and Kazalinsk (river water and
and reservoir waters are ordered considering surface water flow directions, from the
groundwater; Chiba et al., 2006). station furthest upstream (Termez) to the station furthest downstream (Mejdurechye
Reservoir 3). In analogy, the drainage water stations are ordered from upstream Bukhara
3. Results and discussion to downstream Kungrad (Fig. 3a, left side) and the groundwater stations are ordered
from upstream Chalish to downstream Dusenbay (Fig. 3b and c, left side). The mean
3.1. Trends along the Amu Darya river groundwater flow directions were taken from estimates of Johansson et al. (2009).
The HFs for nitrate and nitrite in river water were below one and did not indicate a
In the terminal surface water recipient of water-borne pollution in the Amu Darya health risk, whereas drainage water from Nukus had a nitrite HF close to 3 (Fig. 3a).
river basin, the Mejdurechye reservoir, the four recent (2007–2008) measurement Furthermore, the Mejdurechye reservoir water is associated with significantly higher
campaigns showed that the concentrations of cadmium and nitrite from time to time nitrite HFs (close to 4; Fig. 3a, right side) than upstream river waters of Amu Darya. The
exceeded WHO's health-risk based guideline values (Table S1). Copper, fluoride, γ-HCH HFs for fluoride, arsenic, mercury and copper were less than one in the sampled river
and arsenic concentrations were just below their respective guideline values, whereas and reservoir waters of the lower Amu Darya drainage basin (Fig. 3b, right side). The
nitrate, mercury, lead and chromium concentrations were well below their guideline highest HFs in the river-reservoir system were observed for fluoride (HF = 0.4) and
values. Furthermore, during the 2007–2008 campaigns, DDT and its degradation products copper (HF = 0.2) in the Mejdurechye reservoir water. The arsenic HF was also slightly
were detected for the first time since at least 2002. The CHF for the Mejdurechye reservoir, higher in the Mejdurechye reservoir than in upstream river waters. Of the four
expressing combined toxic effects of the measured substances, was approximately 1 in substances shown in Fig. 3b, copper is the only one that reportedly has been subject to
the two 2007-campaigns, 0.03 in May 2008, and 9 in July 2008. Different combinations measurement in groundwater. The results show that copper HFs in groundwater are
of substances contributed to elevated CHFs (i.e., CHF ≥ 1) on different measurement about two orders of magnitude higher than in river water and one order of magnitude
occasions; in July 2007 copper, fluoride and arsenic dominated, whereas nitrite, fluoride higher than in reservoir water (Fig. 3b, left side). The temporal and spatial variations of
and copper dominated in October 2007, and cadmium and nitrite dominated in July 2008 copper HFs in the river water of the Amu Darya delta are much smaller than that
(see further Table S1 in Supplementary information for detailed Mejdurechye measure- compared with the standard deviation values of Fig. 2b, which indicates that there is a
ment results). The WHO long-term exposure reference concentration was used for nitrite systematic difference between copper HFs in groundwater and river water. Fig. 3b also
when calculating CHFs. shows that the copper HFs in groundwater increase along the groundwater flow
For four of the top five substances contributing to the Mejdurechye CHFs in 2007 and direction, from Chalish to Dusenbay.
2008 (arsenic, copper, fluoride and nitrite), monthly measurement data from the stations Fig. 3c (left side) shows that chromium, lead, manganese and nickel concentrations
Termez (Te), Tuyamuyn (Tu), Nukus (Nu) and Kziljar (Kz) located along an extensive in the THC reservoir waters and the upstream river water at Darganata are hazardously
upstream stretch of Amu Darya river were available from a previous period (1998–2002). high with HFs between 1 and 5. HFs for chromium in reservoir waters are however
Considering these four high HF substances, Table 2 shows the percentage of significantly lower than 1 if the higher U.S. EPA guideline value is used. This is the only substance for
different ensemble mean HF values between categories, when categorising data according which the choice of reference concentration standards affects whether the HF value
to location (rows 1, 2 and 3), year (row 4), and season (row 5) of measurement. exceeds 1 or not. Notably, Fig. 3c (right side) demonstrates exceptionally high HFs for
The difference in mean arsenic HFs between locations (1) Te–Tu, (2) Te–Nu, (3) chromium (up to 280) and lead (up to 65) in groundwater samples from Chalish,
Te–Kz, (4) Tu–Nu, (5) Tu–Kz, and (6) Nu–Kz, was found to be statistically significant in Yangibazar, Dusenbay and Buzkala. These groundwater values are about four orders of
four out of these six cases, yielding a percentage of 67, as shown in column 1, row 1, of magnitude higher than mean HFs for chromium and lead at the river measurement
Table 2. The two location pairs that did not show statistically different mean values stations between the THC and the Mejdurechye reservoir. Moreover, although we in
were (1) Te–Tu and (6) Nu–Kz. This result can be understood by considering Fig. 3c for illustrative purposes plot results from only 4 out of 14 groundwater sampling
underlying ensemble mean HFs and standard deviation values for Te, Tu, Nu and Kz, locations of Froebrich et al. (2006), the other 10 sampling locations (in the Amu Darya
plotted in Fig. 2a. The figure shows a considerable overlap in range (mean ± one delta within a distance of 45 km from the Amu Darya River) had equally high
standard deviation) between the upstream Te and Tu, stations, as well as between the groundwater HFs for chromium and lead (intervals of 120–280 and 20–70,
 R. Törnqvist et al. / Environment International 37 (2011) 435–442 439

a)

b)

c)

Fig. 2. Hazard factor (HF) ensemble mean (filled circles) and standard deviation (error bars) for: a) arsenic in Termez, Tuyamuyn, Nukus and Kziljar during 1998–2002, b) copper in
Termez, Tuyamuyn, Nukus and Kziljar grouped according to season, and c) fluoride in Termez, Tuyamuyn, Nukus and Kziljar grouped according to years. See Fig. 1 for sample site
location.

respectively). The 10 sampling locations also had as high groundwater HFs for copper fluoride and cadmium; see section 3 of the Supplementary information). Notably, the
(interval of 1–4.5) as the 4 locations illustrated in Fig. 3b. groundwater concentrations of these three substances are unknown in the Amu Darya
A synthesis of groundwater (gw)–river water (rw) measurement results from the river basin due to lack of measurements (or, at least, lack of publically available
adjacent Syr Darya drainage basin (Bosch et al., 2007; Chiba et al., 2006) furthermore measurement results).
showed that the highest HFs were associated with groundwater (like in the Amu Darya
river basin). Specifically, of the 13 substances considered here, the following had 3.3. Possible sources and large-scale spreading mechanisms of key substances
relatively high HFs in water systems of the Syr Darya drainage basin: arsenic, 0.9 (gw)
and 0.2 (rw); fluoride, 0.7 (gw) and 0.4 (rw); nitrate 4.9 (gw) and 0.1 (rw); and Water samples from the 2007–2008 measurement campaigns in Mejdurechye con-
cadmium 0.7 (gw) and 0.6 (rw). Three of these substances were also included among tained concentrations of the banned pesticides γ-HCH, DDT and degradation products
the top HF substances in surface waters of Amu Darya during 2007–2008 (arsenic, of DDT (dichlorodiphenyldichloroethane (DDD) and dichlorodiphenyldichloroethylene
440 R. Törnqvist et al. / Environment International 37 (2011) 435–442

a)

b)

c)

Fig. 3. Mean HFs in: a) drainage water and river water for nitrite and nitrate, b) groundwater, reservoir and river water for fluoride, arsenic, mercury and copper, and c) groundwater
reservoir and river water for cadmium, chromium, manganese, nickel and lead. Reservoir water sample locations are underlined. Values below the horizontal solid lines indicate
samples with concentrations below the detection limits (DL) and thereby of low HFs. Locations are categorised according to upstream to downstream mean surface waters and
groundwater flows, i.e., from left to right in the figure. Abbreviations: Res. THC = Tuyamuyn Hydrological Complex Reservoir, Res. Mejdu. = Mejdurechye Reservoir. See Fig. 1 for
sample site location.

(DDE)), which is notable since levels of these pesticides have been below the detection between DDT, DDD and DDE (e.g., assuming equal retardation), sources of old DDT from
limit in Mejdurechye reservoir measurements since 2002. These elevated concentrations before the ban would yield rD b 1 in water, which is significantly lower than observed.
constitute a break from the trend of significant decrease that has prevailed in the entire Hence, if this simplifying assumption would be valid, the detected DDT could not
Amu Darya delta since at least 1987 (Karimov et al., 2005). The average ratio of parent DDT possibly result from subsurface transport of old DDT. The simplifying assumption can
concentration and sum concentration of the degradation products DDE and DDD be relaxed by the consideration of differences in retardation between DDT and its
(hereafter denoted rD; this ratio hence becomes lower as the plume ages and degrades) degradation products, with the partition coefficient Kd being higher for DDT (log
was equal to 4.8 for the 2007 and 2008 campaigns in the Mejdurechye reservoir Kd = 4.8) than for DDE (log Kd = 2.7) and DDD (log Kd = 2.9) (Walters and Aitken,
(Supplementary information, Table S1). 2001), implying higher retardation and slower transport of DDT than DDE and DDD.
The time span between the DDT ban in the Soviet Union (in 1973; Zhulidov et al., In comparison with the equal retardation case, these retardation differences can
2000) and the 2007–2008 measurement campaigns is longer than the half-life of contribute to decreases in rD at downstream observation points, since low DDT
DDT in soil (15 years; Howard, 1991). Neglecting differences in transport properties concentrations would prevail for longer times due to its higher retardation. Whereas
 R. Törnqvist et al. / Environment International 37 (2011) 435–442 441

this reasoning is relevant in many cases, there are exceptions for which retardation contain substance concentrations that are orders of magnitude higher
differences can contribute to increases in rD. Such events (that hence can mask the
than WHO drinking water guideline values. This implies that such
true age of old spills; making them appear more recent) are however limited in space
and/or time, see the Supplementary information for details. Notably, the Mejdurechye groundwater-based drinking water can be associated with severe
reservoir receives pollutants from large upstream areas and has been monitored during health risks, clearly above corresponding surface water risks. In
relatively long periods of time. addition, in the Amu Darya delta, pressures are high on switching
Overall, it therefore appears unlikely that old DDT can explain the high rD found in from surface water-based drinking water supplies to groundwater-
the Mejdurechye reservoir. A plausible alternative explanation would be that the DDT
leakage is relatively recent. Since the half-life of DDT is short in surface water (1 year;
based supplies (Rakhmatullaev et al., 2010), as a consequence of
Howard, 1991), it cannot have been in contact with surface water for any prolonged surface water shortage that already has led to the desiccation of the
periods of time, before detection in the Mejdurechye reservoir. This limits plausible Aral Sea. Current results suggest that such a change of water supply
DDT sources to illegally used stockpiles, recent leakage from storage sites and systems (i.e., from surface water sources to groundwater sources)
atmospheric deposition. Similarly high rD-values have for instance been reported in the
could, apart from possibly decreasing groundwater levels due to
Pearl River Delta waters in South China, indicating ongoing DDT use after China's 1983
ban (Guo et al., 2009). insufficient recharge, imply a considerable worsening of health risks.
In the ASDB, main sources of copper contamination are located at the ground The surface water shortage is furthermore expected to become more
surface, or in the near-surface environment. Sources include copper mine tailings and severe in the near future due to continued irrigation expansion in the
agricultural fields, where fertilizers (of e.g., copper sulphate) and pesticides (e.g., upstream part of the Amu Darya drainage basin, and ongoing climatic
copper hydroxide; Zhang et al., 2004) are used. In the most downstream river gauging
station of Amu Darya (the Kziljar station; located close to the Mejdurechye reservoir
changes (Dukhovny et al., 2007; Milly et al., 2005; Shibuo et al., 2007;
inlet), copper HFs peak during the spring, when precipitation is high. It is primarily Destouni et al., 2010b). Analogously, polluted groundwater may
elevated copper concentrations in March that contribute to the statistically significant increasingly become the only remaining water source as in many
correlation between season and copper concentration. A plausible explanation for this arid areas of the world, since surface water discharges are expected
correlation is that copper may accumulate in upper soil layers when conditions are dry,
to decrease globally in arid areas, in response to projected global
and mobilise during early high-precipitation events of the growing season, as a result of
leaching and/or soil erosion. Zhang et al. (2004) for instance referred to this mechanism irrigation increase (e.g., due to population growth and increasing
as a plausible explanation for observed peaks of dissolved copper in drainage water living standards; Rockström et al., 2009) and projected climatic
from agricultural fields in St. Lucie County, Florida. It can also explain some ob- changes (Intergovernmental Panel on Climate Change, 2007).
servations of Bordalo et al. (2001) in Bangpakong River, Thailand. The lower Amu Darya
region contrasts to the study areas of Zhang et al. (2004) and Bordalo et al. (2001)
through its lower winter temperatures (below 0 °C), its more extensive irrigation, and
Acknowledgements
its arid climate with precipitation events mainly limited to winter and early spring
(Sorrel et al., 2007). The present results specifically show that copper concentrations This study was funded by the Swedish International Development
peak after thawing and snow melt, and that concentrations decline in the summer Cooperation Agency (SIDA). The work has been carried out within the
season despite considerable water re-routing to irrigated fields. Nitrite concentrations
Bert Bolin Centre for Climate Research, which is supported by a
of the lower Amu Darya river were also higher during spring than summer; co-
variations between copper and nitrogen compounds also exist under different ambient Linnaeus grant from the Swedish Research Council (VR) and the
conditions as reported by, e.g., Zhang et al. (2004) and Bordalo et al. (2001). Swedish Research Council for Environment, Agricultural Sciences and
Surface water systems are generally not affected by natural arsenic, unless there Spatial Planning (Formas). We gratefully acknowledge constructive
are geothermal sources (Smedley and Kinniburgh, 2002). Our results show that, in the discussions with Jochen Froebrich, Centre for Water and Climate
presence of superficial arsenic sources of human origin (from agriculture and possibly
mining), arsenic can leach to surface waters to such an extent that considerably
(CWK), Wageningen University & Research centre — Alterra, The
contributes to CHFs in drinking water. Since previous studies on arsenic leaching from Netherlands, including interpretation feedback on past groundwater
cotton fields additionally have shown that vertical arsenic migration is very limited measurement campaigns in the Amu Darya delta region.
even under irrigation (Reedy et al., 2007), it is likely that leaching into surface water
systems constitutes a main transport pathway for anthropogenic arsenic (in contrast to
Appendix A. Supplementary data
natural arsenic). The high spatial variability of arsenic concentrations in river water
along Amu Darya is furthermore consistent with findings summarized in Smedley and
Kinniburgh (2002) of spatially limited arsenic contamination in surface waters around Supplementary data to this article can be found online at
known superficial sources (mining tailings). High arsenic values in downstream ASDB doi:10.1016/j.envint.2010.11.006.
river water stations could therefore signal its presence in the top soil of nearby
agricultural fields.
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