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Caimito Mercurio
Caimito Mercurio
Caimito Mercurio
Abstract. During May–September 1999, several aquatic environmental samples were collected from
the village of Caimito, in the San Jorge River basin area, state of Sucre (Colombia), and analyzed
for total mercury (T-Hg). Mean T-Hg concentration in sediments from surrounded marshes was
0.155 ± 0.016 µg Hg/g. Low Hg concentrations were found in the phytoplanktivorous fish species
Prochilodus magdalenae (0.087 ± 0.01 µg Hg/g), while four-fold greater concentrations were found
in all the carnivorous species. In average, T-Hg concentrations for fish samples did not exceed the limit
consumption level (0.5 µg Hg/g). However, risk assessment based on the hazard index suggested that
the consumption of 0.1 kg per day of carnivorous fish could increase the risk of mercury poisoning
in local population.
1. Introduction
Environmental samples were collected from sites in the San Jorge river basin area
located near the village of Caimito (Figure 1) from May to September, 1999. Caim-
ito is located in Northwestern Colombia (8◦ 46 N and 75◦ 6 W). Fishing and agri-
culture are the major economic activities of people from this locality. Sediment
and fish samples were taken from the marshes of Aguas Claras and El Reparo.
These waterbodies were chosen based on their importance as source of fish for
human consumption and because they are located within 5 km far from the urban
area.
Sediments were collected by lowering an Eckman sampler from the two sides
of a boat. All samples were composites of two subsamples taken at each location.
Samples were stored in polyethylene bags and kept on ice during transportation.
In the lab, samples were freeze-dried to guarantee better homogeneity and analysis
reproducibility (Muhaya et al., 1998).
Fish were caught during fishing campaigns with local fishermen and included
several species from different trophic levels: the iliophagus Prochilodus magdale-
nae (Bocachico), and the carnivorous Ageneiosus caucanus (Doncella), Petenia
kraussi (Mojarra amarilla), Plagioscion surinamensis (Pacora), Sorubin lima (Blan-
quillo) and Hoplias malabaricus (Moncholo). After measuring length, fish were
eviscerated and transported on ice to the lab. Samples for analysis were obtained
from dorsal muscle dissected with plastic knives and analyzed wet.
Figure 1. Map of study area indicating the location of San Jorge river and its surrounded marshes.
MERCURY IN THE AQUATIC ENVIRONMENT 411
T-Hg analysis was performed by cold vapor atomic absorption spectroscopy after
acid digestion. Digestions of fish were performed for 3 h at 100–110 ◦ C and sedi-
ments at 90–95 ◦ C for 45 min using an acid mixture as previously reported (Sadiq
et al., 1991). Quality control procedures included the analysis of blank samples
and the standard reference material Dorm-2. The Hg concentration obtained for the
certified material was 4.1 ± 0.5 µg Hg/g (certified value = 4.6 ± 0.3 µg Hg/g).
The detection limit, defined as three times the standard deviation of the blank was
0.015 µg Hg/g. Organic matter in sediment was determined by using dichromate
oxidation with diphenylamine as indicator.
3. Results
Results of T-Hg analysis and organic matter in sediments from two marshes in San
Jorge river basin are shown in Table I. There were not statistical differences for
TABLE I
Statistics for T-Hg and organic matter content in sediments from San Jorge river basin
Total mercury (µg Hg/g, dry weight) Organic matter (%, dry weight)
Figure 2. Mercury concentration (µg/g, wet weight) for fish species from San Jorge river basin.
Hg concentrations in muscle from different fish species collected in San Jorge river
basin are shown in Figure 2. The lowest T-Hg concentrations were found in the
phytoplankton feeding species Prochilodus magdalenae (0.087 ± 0.010 µg Hg/g),
while the highest concentrations were found in the carnivorous species, which in
average had T-Hg concentration of 0.327 ± 0.01 µg/g. Consequently, a ratio of 4:1
existed between T-Hg levels in carnivorous and iliophagus species. A significant
statistical difference was found between Hg concentrations in fish for the different
species (ANOVA; P < 0.05), and when pooled data for carnivorous fish were
compared to Prochilodus magdalenae (t-test; P < 0.01). However, no statistical
differences in Hg levels were found among carnivorous species (P = 0.171). The
average Hg concentration for all the species was 0.247 ± 0.015 µg Hg/g (n = 99).
Although according to international standards these fish are suitable for human
consumption (Hg levels < 0.5 µg/g), increased frequency in fish consumption may
represent a risk for human health. The assessment of this risk for non-carcinogenic
effects has been usually characterized by the hazard index (HI) method (Jewett et
al., 2003; Chen et al., 2001; Burger et al., 2001; Tchounwou et al., 1996). HI is the
ratio of the potential exposure level to the substance or daily intake (DI) and the
level at which no adverse effects are expected or the oral Reference Dose (RfD) for
the chemical. If the HI is calculated to be less than 1, then no adverse health effects
are expected as a result of exposure. If the HI is greater than 1, then adverse health
effects are possible but it does not necessarily mean that these will occur. According
MERCURY IN THE AQUATIC ENVIRONMENT 413
TABLE II
Hazard indices for non-carcinogenic effects of T-Hg based on a fish consumption of 100 g
in San Jorge river basin
Mercury level range Hazard index
Fish species Trophic level (µg Hg/g, fresh weight) range
to the U.S. EPA, for non-carcinogenic toxic endpoints, the RfD is interpreted as the
concentration of a chemical that is “safe” to ingest on a daily basis over a lifetime.
The threshold encoded by the RfD value is particularly adequate for protecting
pregnant women due to the risk of neurological damage to the fetus. The RfD for
Me-Hg has been proposed to be 0.1 µg Hg/kg/day (U.S. EPA, 1998).
The DI of Me-Hg consumption can be calculated using the formula, DI =
C × I /W , where C is the Me-Hg mean concentration in fish (C = 0.90× T-Hg,
approximately, 90% of the T-Hg in these fish species has been found to be Me-
Hg, Johnson et al., 1998), I is the fish daily consumption (g/day), and W is the
mean weight of a normal adult (70 kg). The calculation of HI for a 100 g/day fish
consumption rate using both the minimum and maximum values of T-Hg found in
fish collected in the San Jorge river basin are shown in Table II.
Correlations between T-Hg concentration in fish muscle and fish length for each
species are presented in Figure 3. It is clear that for most species, there are no
relationships between fish length and T-Hg in muscle. When data from all the
species were pooled, a positive correlation between Hg content and fish length was
observed (R = 0.509, P < 0.001).
4. Discussion
The major goal of our research has been to determine the impact of gold mining in
the ecosystems in Colombia. In this regard, we have previously reported Hg concen-
trations in environmental and human samples in the gold mining area (Olivero and
Solano, 1998; Olivero et al., 1997, 1995). One particular concern has been to estab-
lish the mercury levels in those places surrounding the gold mining areas. Caimito
is located on the San Jorge river basin, with extensive metal mining upstream the
river, particularly nickel and iron containing rocks are disposed into the stream. In
addition, downstream this site, the basin floodplains interchange waters with Cauca
river that transports gold mining residues. In Colombia, metallic Hg is directly
414 J. OLIVERO-VERBEL ET AL.
incorporated into the water ecosystems and air from gold extraction processes, and
without any previous attempt to recover the metal. In contrast, in developed coun-
tries, such as the US, the sources of Hg are primarily atmospheric deposition from
combustion of Hg-containing fossil fuels and municipal waste (Pai et al., 1998).
Measurement of trace element concentration in bed sediment is necessary to have
a picture of the relationship between bedrock geology, bioaccumulation of elements
and land use (Wasserman et al., 2003; Subramanian et al., 2003; Beldowski and
Pempkowiak, 2003; Lindestrom, 2001; Roulet et al., 1998; Heiny and Tate, 1997).
Sediment T-Hg concentrations were similar between stations, as expected from
their proximity (see Figure 1 and Table I), and were almost twice those reported
as background in lakes and freshwater streams in Canada (Environment Canada,
1997). In South America, where many freshwater ecosystems have been impacted
by gold mining activities, the levels of T-Hg in sediments may vary in a great extent
depending on the proximity to the discharge (Table III). However, for some cases,
the levels observed in the San Jorge river basin are similar or greater to those found
in rivers contaminated by gold mining.
On the other hand, considering a Hg threshold not effect level of 0.174 µg/g as
recommended by Environment Canada (1997) for freshwater sediments, in average,
the levels of T-Hg in sediments from San Jorge river basin can not be considered
as contaminated. However, after input of the metal to freshwater ecosystems from
precipitation runoff and in situ methylation (Downs et al., 1998), Hg deposited on
the sediments can be ingested with particulate matter by benthic organisms or fish
on the water column and moves through the food chain mostly as methylmercury
(Watras et al., 1998).
MERCURY IN THE AQUATIC ENVIRONMENT 415
TABLE III
Mercury levels in freshwater sediments from some South America countries
Monitoring Sediment (µg Hg/g,
Country place dry weight) Remarks Reference
Argentina Upper Negro River(0.8–3.4) – upper 10 Chlor-alcali plant Arribere et al. (2003)
(Alto Valle) cm layer
Northern (2.8–13.7) – next 10
Patagonia cm lower layer
Lake Nahuel Huapi0.261 ± 0.033 Upper 4–10 cm Ribeiro-Guevara
Nahuel Huapi na- Mercury enriched et al. (2002)
tional park, in the suspended
Patagonia load
Brazil Lavras do Sul 0.140–0.207 Local background Pestana and Formoso
concentrations (2003)
Acre and Purus 0.042 – bottom Without artisanal Brabo et al. (2003)
rivers and some 0.060 – suspended mining activity
tributaries Acre
State, Western
Brazilian
Amazon
Rondonia Amazon Up to 19.8 Gold mining Pfeiffer et al. (1989)
region Tributary forest
rivers
Bento Gomes river 0.089 Gold mining Hylander et al.
basin (2000)
Pantanal 0.033 Remote floodplain Hylander et al.
lakes (2000)
Duas Bocas lake 0.105–0.209 Gold mining Daveé-Guimaraes
Pracuuba lake 0.056–0.126 et al. (1999)
Tartarugalzinho 0.058–1.058
river
Colombia San Jorge river 0.155 ± 0.016 50 km from gold This study
basin Mojana mining
region
South of Bolivar 0.140–0.355 Gold mining Olivero and
Solano, (1998)
Ecuador Puyango basin <0.04–0.344 Gold mining (data Ministerio de
Siete basin <0.04–29.70 for 1998) Energia y Minas,
Gala basin <0.04–3.10 Ecuador (1999)
Nambija basin 0.072–5.94
Ponce Enrı́quez 0.1–13 Gold mining Appleton et al.
area (2001)
Guyana Mazaruni river 0.077 ± 0.143 Gold mining Miller et al. (2003)
Essequibo river 0.042 ± 0.064
Suriname Brownsweg area 0.103–0.150 Gold mining Gray et al. (2001)
TABLE III
(Continued)
Venezuela Manzanares river 0.06 Gold mining Shrestha and Ruiz de
(Sucre State) Quilarque (1989)
Roscio district 0.12–129 Gold mining Shrestha and Ruiz de
(Bolivar State) Quilarque (1989)
Hg concentrations in fish were greater than in bed sediments, and the higher
T-Hg concentrations were found in the carnivorous species. The absence of corre-
lation between fish length and T-Hg content for particular species may be in part due
to size homogeneity among collected specimens. However, carnivorous fish often
have greater size and mercury levels than phytoplanktivorous or iliophagus species
(Barbosa et al., 2003; Cizdziel et al., 2002), and that might explain the signifi-
cant correlation observed between T-Hg and fish length when all the species were
pooled.
Data presented here evidenced that Hg levels found in fish from San Jorge river
basin are in average below the 0.5 µg Hg/g, the maximum Hg concentration that
should be present in fish used for human consumption according to the World Health
Organization (WHO, 1990). However, other studies have recommended that a level
of 0.3 µg Hg/g should be adopted, particularly in countries where rates of fish
consumption are high (Dickman and Leung, 1998). Hg concentrations found in
carnivorous species were greater than 0.3 µg/g. Although these levels were lower
than those reported for gold mining sites in Brazil (Barbosa et al., 2003; Malm,
1998; Bidone et al., 1997a,b), consumption of these species should be as minimal
as possible. As shown in Table III, based on a conservative consumption rate of fish,
the use of the HI approach suggested that people that eat any of the analyzed fish
species, in particular carnivorous, may be exposed to a potential human health risk.
Risk management strategies that would help to minimize the effects associated with
mercury poisoning should include permanent mercury monitoring in vulnerable
groups such as pregnant women and children, control on mercury discharges on gold
mining sites and search for alternative protein sources different from contaminated
fish.
Fishing is one of the most important economic activities for people from Caimito.
Most of the population eat fish frequently, and although Prochilodus magdalenae is
the main fish species in the diet of the population (Figure 4), carnivorous species are
also present. Therefore, it is not surprising that Hg in fish is influencing the presence
of T-Hg in hair among people from this locality (Olivero et al., 2002). This fact,
together with the HI date presented here, should encourage the evaluation of possible
neurological damage associated with mercury poisoning by local government.
Another point of interest arising from this work is that a particular species
seems to be the less harmful for human consumption. In view of the low T-Hg
concentrations detected for Prochilodus magdalenae, the most important freshwater
MERCURY IN THE AQUATIC ENVIRONMENT 417
Acknowledgments
The authors are grateful to the UNESCO-Regional Office for Science and Tech-
nology for Latin America (ROSTLAC), Montevideo (Uruguay) for funding part
of this research. We are also grateful to Universidad de Cartagena, Colombia,
Beatris Solano, Adolfo Consuegra, and the population from Caimito for their
cooperation.
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