Thallium: A Hidden Health Hazard in China
Thallium: A Hidden Health Hazard in China
www.elsevier.com/locate/envint
Abstract
This paper illustrates a real environmental concern and draws attention to the fact that natural processes can mobilize thallium (Tl), a
highly toxic metal, which may enter the food chain as a ‘‘hidden health killer’’ with severe health impacts on local human population. Natural
processes may be exacerbated by human activities such as mining and farming, and may cause enrichment of Tl in the environment. In
geochemically anomalous areas with concentrated levels of Tl in the surface environment (bedrocks, waters, soils, and crops), such as the
Lanmuchang area in southwestern Guizhou Province, China, it is essential to establish base-level values and to pay heed to the geological
context of ‘‘natural contamination,’’ as high concentrations of Tl in bedrocks/ores (6 – 35,000 mg/kg) can lead to enrichment of Tl in the
aquatic system (0.005 – 1100 Ag/l in groundwaters and 0.07 – 31 Ag/l in surface waters) and soil layers (1.5 – 124 mg/kg). In sensitive areas
such as the Yanshang area of southwestern Guizhou, elevated natural levels of Tl from bedrocks may also cause higher concentrations of Tl
in the surface environment, and thus more attention must be paid to geoenvironmental management of human activities if socio-economic
catastrophes are to be avoided. Due to high uptake of Tl by crops, Tl can be transferred from soils to crops and remarkably concentrated in
food crops. Concentrations of 1 – 500 mg/kg Tl based on dry weight (DW) were determined in many food crops growing on Tl-contaminated
arable soils from the Lanmuchang area. The daily intake of 1.9 mg of Tl from consumed food crops was estimated for the local adult
inhabitant of Lanmuchang. Thus, Tl is regarded as a latent health hazard with potential risk of toxicity in humans within areas of ‘‘natural’’
contamination by Tl.
D 2003 Elsevier Ltd. All rights reserved.
Keywords: Thallium; Geoenvironment; Health hazard; Contamination; Chronic poisoning; Guizhou; China
0160-4120/$ - see front matter D 2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.envint.2003.10.004
502 T. Xiao et al. / Environment International 30 (2004) 501–507
et al., 2003). Thallium (Tl)’s role as a toxic health threat, mining activities as the cause (Zhou and Liu 1985; Zhang et
which mainly affects the central nervous system, causes al., 1998). High Tl concentrations in drinking water were
visual disorders (with failing eyesight or total blindness), found to be the principal cause of Tl poisoning. In the early
hair loss, and even death, and has been investigated exten- 1990s, the drinking water problem was resolved by piping
sively (Feldman and Levisohn, 1993; Meggs et al., 1994) Tl-free groundwater from outside areas, yet high quantities
but mostly within the context of industrial pollution of Tl (153 –2668 Ag/l) are still being detected in urines of
(Dolgner et al., 1983; Wells, 2001). Nevertheless, numerous the local population (Xiao, unpublished data). Thus, a
studies show the presence of Tl in ore deposits, rocks, soils, further study on the health impact of Tl on the local
water, and plants. Kuroko-type volcanogenic massive sul- population is urgently needed.
phide ores are known to carry significant Tl levels, with
much of the metal hosted by pyrite (Murao and Itoh, 1992).
Arsenical gold deposits may also display a Tl-enriched 2. Materials and methods
signature (Percival and Radtke, 1993), as may some Mis-
sissippi Valley-type Pb– Zn deposits (Leach et al., 1995). 2.1. Study area
Experiments with bioaccumulator plant species indicate
that, under favorable circumstances, plant tissues may The study area, centered on Lanmuchang, a small town
develop dry weight (DW) Tl contents of several tenths of with approximately 1000 inhabitants, was chosen for a pilot
1% (Leblanc et al., 1999). The importance of trace elements study for Tl’s potential impact on the environment and the
in soil for human health has been established for elements local inhabitants during both natural process and man-made
such as F, As, and Se, as well as heavy metals such as Cd, disturbance. The area presents a karstic topography, with a
Hg, and Pb (Abrahams, 2002). The analysis of Tl in soil has generally higher elevation in the northwest and lower
recently been discussed by Castle (2000). However, no elevation in the southeast. The average altitude is 1400 m
previous comprehensive study has provided evidence of above sea level, with a relative relief of 100– 200 m.
natural contamination processes of Tl that may have serious The Tl mineralization within a metallogenetic belt in the
consequences for human health. Recognition of this prob- study area is associated with either independent Tl miner-
lem prompted a comprehensive investigation in a rural area alization (e.g., the Lanmuchang Hg – Tl– As deposit), gold
with Tl – Hg – As sulfide mineralization in southwestern mineralization (e.g., the Yanshang Au deposit), or hydro-
Guizhou Province, China (Fig. 1). In this rural area, symp- carbon accumulation (the Lanmuchang coal deposits) (Fig.
toms related to thallotoxicosis were detected in the early 1). The area exhibits a karstic topography and the deposits
1960s with 200 cases of Tl poisoning, resulting in a number show some similarities to epithermal Carlin-type dissemi-
of deaths. Most of the early investigations focused on local nated Au mineralization, hosted by strata of Permian to
Fig. 1. (a) Sketch map showing the study area and (b) Geological sketch map showing the Huijiabao anticline metallogenic belt in southwest Guizhou, China.
T. Xiao et al. / Environment International 30 (2004) 501–507 503
Triassic age. The local history of mining for coal and Table 1
Concentrations of thallium in various sampling media from the Lanmu-
mercury dates back to more than 350 years.
chang area
A detailed description of the local geology has been
Sampling media Numbers Tl concentrations
recently reported and published (Xiao, 2001; Xiao et al,
of samples Range Mean
2003a,b). Therefore, only a brief summary is provided here.
The Lanmuchang Hg – Tl –As deposit area is underlain by Rocks/ores Sulfide ores 9 100 – 35 000 4400
Permo-Triassic sediments and overlain by Quaternary allu- (mg/kg) Coals 2 12 – 46 29
Secondary minerals 3 25 – 1100 89
vium. The exposed rocks include limestones, argillites, and
Mine wastes 3 32 – 2600 136
coal seams. Thallium enrichment is associated with sulfide Altered host rocks 6 39 – 490 124
minerals of Tl – As –Hg with a reserve of about 500 metric Outcropping rocks 6 6 – 330 39
tons of Tl (Chen, 1989; Xiao, 2001). The deposit has a long Bedrocks in 3 0.06 – 0.2 0.16
mining history for Hg and coals, and it was mined for Tl in the background area
Waters (Ag/l) Deep groundwater 5 13 – 1100 62
1990s. Thallium is also present in coals. Sporadic artisanal
Shallow 15 0.005 – 0.75 0.04
mining of coal seams is undertaken by local residents to groundwater
augment their fuel supply for domestic heating. Thallium Well water 5 0.01 – 0.38 0.2
mineralization outcrops in the hills, where it is susceptible to Background 2 < 0.005 < 0.005
weathering and dispersion by natural processes. groundwater
Stream water 12 0.09 – 31 1.8
(base-flow regime)
2.2. Sampling and analysis Stream water 12 0.07 – 4.5 1.5
(flood-flow regime)
Extensive suites of rocks (46 samples), groundwaters and Soils (mg/kg) Soils in mine area 10 40 – 124 63
surface waters (58 samples), soils (38 samples), and edible Natural slope wash 2 20 – 28 24
materials
crops (47 samples) were collected and analyzed using
Alluvial deposited 12 14 – 62 31
sampling and analytical protocols established by the Geo- soils
logical Survey of Canada (Boyle and Xiao, 2003). Care was Undisturbed natural 5 1.5 – 6.9 4.2
taken to include sampling of old mine workings, mineral- soils
ized zones, and barren host rocks, as well as control samples Background area 3 < 0.2 – 0.5 0.3
Crops (mg/kg, Green cabbage 6 15 – 495 120
remote from the influence of mineralization. When sampling
DW) Carrot 1 22 22
vegetables and cereals, a corresponding soil sample was Chili 3 0.8 – 5.3 2.9
collected for correlation purposes. To further test for natural Rice 4 1 – 5.2 1.7
dispersion processes, another known mineralized area was Chinese cabbage 9 0.87 – 5.4 1.3
chosen at Yanshang, a site 6 km from Lanmuchang, which Corn 8 0.78 – 3.1 1.3
Background area 7 0.05 – 0.35 0.27
has no known mining tradition. All samples were deter-
mined for Tl and other metals by inductively coupled
plasma mass spectrometry (ICP-MS) at the Geological Thallium concentrations in the Lanmuchang area range
Survey of Canada (Ottawa, for rock and water samples), from 100 to 35,000 mg/kg in sulfide ores, and from 12 to
Norwest Laboratories (Edmonton, Canada, for soils), and 46 mg/kg in coals. Secondary minerals, produced by
Activation Laboratories (Ancaster, Ontario, for crops). De- weathering, contain 25– 1100 mg/kg, with 32 –2600 mg/
tailed information on sampling and analyis procedures has kg in mine wastes. Altered host rocks contain 39 – 490 mg/
been presented recently (Xiao et al., 2003a,b,c). The min- kg Tl, with 6 –330 mg/kg in outcropping rocks. Unaltered
imum detection limit for Tl by the above methods is 0.02 country rocks from the background area, barren of metallic
mg/kg in rocks/ores, 0.005 Ag/l in waters, 0.2 mg/kg in mineralization, contain only 0.06– 0.2 mg/kg Tl (Xiao et
soils, and 0.05 mg/kg in crop samples. Analytical precision, al., 2003b).
determined by quality assurance/quality control procedures, The small karstic watershed of Lanmuchang (area about
using duplicates (at every 10th sample), reagent blanks, 3 km2) exhibits an enrichment of Tl level in groundwaters
internal standards (Rh solution) and international reference and related stream waters (Xiao et al., 2003a). This affords
samples (Ottawa 96, GBPG-1, OU-6, NBS-1663A, GSR-5, an excellent demonstration of the natural processes of Tl
CAL-5, etc.), was better than F 10%. dispersion, and the resultant impact on the local ecosystem.
The concentration of Tl in the water system decreases from
deep groundwater to stream water to shallow groundwater.
3. Results Thallium shows high levels (13 – 1100 Ag/l) in deep
groundwater within the Tl-mineralized area, decreasing
3.1. Thallium dispersion in the Lanmuchang area with distance away from the mineralized area to back-
ground levels ( < 0.005 Ag/l). The occurrence of Tl in the
The analytical data for Tl in various geological media water system is dictated by Tl mineralization, water – rock
from the Lanmuchang area are listed in Table 1. interactions, and hydrogeological conditions. Thallium
504 T. Xiao et al. / Environment International 30 (2004) 501–507
Table 3
Environmentally safe limits for thallium
Tl Sources
Drinking water 2 Ag/l USEPA (2003)
Arable soils 1 mg/kg CCME (2003)
World land plants 0.008 – 1.0 Kabata-Pendias and
mg/kg (DW) Pendias (1992)
World edible plants 0.03 – 0.3 Kabata-Pendias and
mg/kg (DW) Pendias (1992)
Fig. 2. Concentrations of Tl in (a) green cabbages and (b) Chinese cabbages World average daily intake 2 Ag/day Sabbioni et al. (1984)
vs. Tl concentrations in soils. Oral reference dose 0.056 mg/day RAIS (2003)
T. Xiao et al. / Environment International 30 (2004) 501–507 505
The high concentrations of naturally occurring Tl in the 4.2. Geoenvironmental management concern
Lanmuchang area, as well as lower concentrations in the
Yanshang area, show that Tl disperses into waters, soils, This study illustrates a real environmental concern
and, ultimately, crops at levels that are above the health related to land use and human health in areas containing
guidelines set by many countries (Tables 1– 3). This disper- high concentrations of Tl in soils associated with the
sion is not necessarily related to mining activities at Yan- natural occurrence of Tl-rich sulfides and coals, with or
shang; in contrast to Lanmuchang, it has seen no mining without mining activities. Thallium contamination in rocks
activity. Groundwater-related Tl transfer processes affect the and soils, and underground and surface drainage patterns
ecosystem through contamination of water supply and should be critical parameters for proper land use and
arable soil, diffusing up the food chain to pose an undoubted health-related environmental planning and regulation. This
threat to human health. research in Guizhou and earlier interesting studies have
The endemic studies of Li (1963) and Zhou and Liu identified the capacity of certain plants to superaccumulate
(1985) indicated the prevalence of thallotoxicosis in the Tl (green cabbage in the present case), so even a value
Lanmuchang area in the period between 1960 and 1970, slightly higher than the accepted Canadian guideline (1
which was attributed to increased farming in the mined area. mg/kg) for Tl in arable soils can be a risk factor for such
However, these studies did not detect the widespread plants, if consumed.
dispersion of Tl beyond the immediate environments of Proper land management practice should not necessarily
mine workings. Drinking water showed high Tl concen- be restricted to mining activities, and procedures such as
trations, which were thought to be the major agent of Tl the use of mine tailings for terracing should be banned.
poisoning (Zhou and Liu, 1985). Although drinking water However, it is also important to note that without proper
with Tl contents below international limits (2 Ag/l) in both knowledge of the base-level values of Tl (and also other
the well waters (0.01 – 0.38 Ag/l) and the Tl-free piped toxic metals) in rocks, waters, and soils, and their disper-
groundwaters ( < 0.005 Ag/l) (Tables 1 and 3) is now being sion patterns, unsafe practices can compound the problem
supplied, Tl levels in urines of local villagers are still quite of Tl dispersion and increase the risk to the biosphere.
high, ranging from 153 to 2668 Ag/l (Xiao, unpublished Potentially hazardous activities include foundation excava-
data). These urinary Tl levels are several orders of magni- tions, agricultural expansion based upon irrigation with
tude higher than the world urinary Tl levels of < 1 Ag/l for waters tainted with Tl, lining of irrigation channels with
‘‘nonexposed’’ humans (Brockhaus et al., 1981; Minoia et rocks containing Tl minerals, and artisanal mining of coal
al., 1990; CDC, 2003). seams in terraced hillsides.
Local villagers in the Lanmuchang Tl mineralized area Although proper nutrition can offset or retard Tl poison-
consume the crops growing in the Tl-contaminated soils ing in Lanmuchang (Xiao, 2001), it still needs strict mon-
during the entire year. Chinese cabbage, green cabbage, and itoring for the geoenvironment to safeguard the health of the
chili are often freshly consumed, whereas corn and rice are population. Simple solutions for immediate implementation
consumed after air drying. The yield of Tl in vegetables include elimination of the planting of green cabbage, a
from fresh to dried samples was determined by dividing the species that hyperaccumulates Tl. Although the scope of
dry weight by the fresh weight. Thus, using the values of this study did not permit an assessment of the human intake
dry yield, consumption amounts of fresh vegetables, and dry of Tl through livestock, it is inevitable that animals fed with
cereals, the amount of Tl from each crop type consumed by local crops and other plants may also transfer Tl to humans.
the local villagers can be quantitatively estimated. Accord-
ingly, the average daily intake of Tl by villagers of the 4.3. Impact beyond the study area
Lanmuchang area through consumption of locally planted
crops has been estimated at 1.9 mg per person (Xiao et al., Thallium deposits are rare in nature. However, the
2003c). The calculated average human ingestion rate of Tl occurrence of Tl in a number of hydrothermal ore deposits
(given a mean adult body weight of 70 kg) is up to 27 Ag/ and alteration zones is a well-established fact and the
kg/day in the Lanmuchang area, 50 times the ingestion rate presence of Tl has been used as tracer for geochemical
of the metal (0.04 mg/day) in people of Tl-free background exploration (Ikramuddin et al., 1983). For instance, hydro-
area. This high ingestion rate of Tl is 1000 times higher than thermal precipitates in the Rotokawa geothermal system of
the world average daily intake (2 Ag/day) as indicated by New Zealand have Tl levels as high as 5000 mg/kg (Krupp
Sabbioni et al. (1984), and also far above the element’s and Seward, 1987). The Allchar Sb –As – Tl deposit in the
‘‘oral reference dose’’ of 0.056 mg/day (RAIS, 2003). This former Yugoslavia also boasts of an extremely high natural
clearly indicates that Tl in the contaminated soils related to Tl content (Percival and Radtke, 1994), as does the Len-
natural Tl mineralization is being readily transferred to the genbach Pb –Zn – As – Ba –Tl in Switzerland (Hofmann and
506 T. Xiao et al. / Environment International 30 (2004) 501–507
Knill, 1996). Some Chinese iron sulfide deposits and Pb – 40203010 (to T. Xiao), and the Chinese Academy of
Zn deposits also show high Tl levels (Chen et al., 2001). Sciences KZCX2-105 (to C.-Q. Liu). We thank Dr. Conrad
From the pilot study in the Lanmuchang area (with high Grégoire and Mr. Peter Bélanger (Geological Survey of
baseline values of Tl) and the Yanshang area (with low Canada) for arranging and undertaking the analyses. Dr.
baseline values of this element), it is clear that Tl can be Ruth Alcock and two anonymous reviewers are acknowl-
dispersed beyond a mineralized zone, and its abundances in edged for their critical comments and suggestions, which
water, soils, and crops can rise above the permissible levels have improved the manuscript considerably.
to a health-threatening extent. Thallium is associated with
hydrothermal mineralization in many mining areas of the
world, in quantities similar to Lanmuchang or Yanshang,
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