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Department for
international Development
This report is an output from a project funded by the UK Department for International Development (DFID). The
views expressed in this report are not necessarily those of the DFID.
DFID classification
Subsector: Geoscience
Theme: G2 Identify and ameliorate minerals-related and other geochemical toxic hazards
Project title: Mitigation of mining-related mercury pollution hazards.
Project Reference: R6226
Bibliographic reference:
J D Appleton and MW William, 1998. Mitigation of mining-related mercury pollution hazards: Project Summary Report.
British Geological Survey, Overseas Geology Series Technical Report WC/96/55, Keyworth, Nottingham, UK.
Cover illustration: Artisanal miner using mercury to amalgamategold in alluvial heavy mineral concentrate, Mainit, eastern
Mindanao, Philippines.
This report summarises the objectives, results and relevance to sustainable development of a
study of the environmental impacts of mining-related mercury (Hg) contamination. The purpose
of the research is to help mitigate the health and ecological hazards associated with artisanal gold
mining. The research was carried out during the period 1 April 1995 to 31 December 1998 as part
of the UK Department for International Development (DFID) Engineering Division Technology
Development and Research (TDR) Programme concerned with the theme: "Identification and
amelioration of minerals-related and other toxic hazards". This programme forms part of the
British Government's provision of aid to developing countries.
Mercury has been widely used in the mining industry since Roman times for the amalgama-
tion and concentration of gold and silver. The total global release of Hg into the environment
through this process prior to 1930 has been estimated as over 260,000 t, after which emissions
declined with the introduction of cyanidation processing technology. In the 1970's high gold
prices triggered a major artisanal gold rush in many countries of the Southern Hemisphere, possi-
bly involving more than 10 million people. The attendant resurgence in the use of Hg for Au
processing which occurred at this time has continued largely unabated to the present day, and
may currently account for 10% of the total anthropogenic emissions of Hg into the global envi-
ronment. The amalgamation process requires the use of 2 to 3 tons of mercury for each ton of
gold recovered. Small-scale miners produce thousands of tons of gold each year so environmental
contamination by mercury release is of considerable concern.
A number of developing countries in Africa, Asia and Latin America have experienced a rapid
growth of the small-scale gold mining sector during the last two decades. This has reached huge
proportions on the island of Mindanao, in the Philippines, where more than 100,000 people have
been engaged in largely uncontrolled artisanal mining. There was a requirement in the Philippines
in particular, for a detailed evaluation to be carried out of the environmental impact on both the
miners and local communities of mercury contamination derived from mining. Smaller magnitude
artisanal mining had also developed in southern Ecuador. As good collaborative links had been
established with organisations in the Philippines and Ecuador that were able to provide both lo-
gistic and scientific support, these two contrasting examples of artisanal gold mining were se-
lected as case study areas in which to fulfil the project objectives: -
1. Provision of a generic protocol for monitoring the sources and fates of contaminant mercury
in gold mining regions.
2. Assessment of human and ecotoxicological impacts of mercury pollution and calculation of
humadenvironmental risk thresholds.
3. Promotion of improved methods of gold recovery with applicability to the artisanal sector.
4. Design and implementation of practical legislation for abatement of mining-related mercury
contamination.
It was originally intended to restrict monitoring and impact assessment studies to mercury con-
tamination associated with small-scale gold mining. However, the main collaborating organisa-
tion in the Philippines, the Mines and Geoscience Bureau (MGB) was obliged to reappraise its
priorities in the light of widespread media reports of human mercury poisoning in an area of for-
mer cinnabar mining on the island of Palawan. In response to a directive from the Philippines
President, the MGB commissioned an inter-agency investigation into the Palawan mercury scare,
and a formal request for the diversion of BGS-DFID funds from Mindanao to Palawan was re-
ceived by BGS. Although falling strictly beyond the remit of TDR project R6226 (which is pri-
marily concerned with Hg contamination associated with artisanal gold mining), the request was
considered by BGS and DFID to constitute a strong case for demand-led TDR expenditure. Ac-
cordingly, a preliminary investigation of the extent of the Palawan Hg problem was carried out in
collaboration with the UK Institute of Terrestrial Ecology (ITE).In view of the paucity of geo-
1
chemical, ecotoxicological or epidemiological data depicting the extent and magnitude of Hg
hazards in central-eastem Palawan, the principal objectives of the study were to: -
Establish the spatial extent, magnitude and temporal trends of Hg deposition in the marine
environment of Honda Bay.
0 Assess the risk posed to inhabitants of the Sitio Honda Bay jetty and the cinnabar mine local-
ity as a consequence of living on a mine-waste substrate.
Assess the extent of Hg bioassimilation and attendant toxicological stress in marine biota
(fish and shellfish) at various localities in Honda Bay.
11
A range of changes to gold processing procedures used by small-scale miners would reduce
the amount of mercury contamination. These include:
(a) Improved sluice box design and increased use of effective gravity separation methods (such
as the shaking table) might reduce the use of mercury on sluices. This could be achieved by
demonstration of the financial benefits of increased gold recuperation and hence the amount
of income generated.
(b) Development of a retort system which retains the Hg but produces a higher quality gold
product uncontaminated by Fe and As (which reduces the value of the Au). In Ecuador, for
example, small-scale gold processors frequently have retorts but they are rarely used. It is not
entirely clear whether artisanal miners do not use the retorts because (1) they are suspicious
that they are losing some of the gold in the retort, (2) the processing takes longer or (3) the
product is lower quality and less marketable. If 80-90% of Hg loss is related to burning off
the mercury from amalgam then the biggest effort should clearly be put into improving this
aspect of the process. Some NGOs have tried this approach but, in general, this appears to
have been unsuccessful. There is clearly a requirement for further educational campaigns de-
signed to demonstrate the positive health and economic aspects of using retorts.
(c) Increasing the use of cyanidation in an environmentally acceptable way would reduce the
need for amalgamation. This would require better control on the location of cyanidation
plants and management procedures.
(d) Perhaps the greatest potential for reducing environmental impact would be through the adop-
tion of an effective system of co-operative production. This should lead to better management
of mineral processing plants with reduced environmental impact while still leaving the means
of production in the hands of the poorer sector of the population. In theory it should permit a
more effective and economical production system to be adopted through upsizing production
systems and providing access to capital for larger investments (e.g. shaking tables and effi-
ciently run cyanidation plants).
V
tivities (e.g. in Bolivia and Ecuador). Pollution control is achieved through waste assessment pro-
cedures such as Environmental Impact Analysis and Environmental Audits but also includes envi-
ronmental standards for exploration, mineral extraction, and processing. In Ecuador, there are
additional standards applicable to the artisanal sector. In many developing countries, enforcement
is generally extremely restricted and is almost totally concentrated on the larger polluters.
It had been anticipated that recommendations for maximum permissible environmental mer-
cury levels in the Philippines would evolve from the biological and human impact assessments
and that these would be incorporated into new legislative controls on the small-scale mining sec-
tor being prepared by the MGB at the time the project started. As the authority responsible for the
control of mining activities and related environmental impacts, the MGB needed to formulate
legislation to regulate mercury usage in small-scale mining activities with the aim of preventing
further damage to the environment and human health. In the event, the new Philippines mining
laws were pushed through much faster than had been envisaged, effectively precluding BGS’ in-
volvement in this aspect of the project programme. Insufficient information has been compiled
through the current project to establish maximum permissible environmental levels (based on im-
pact assessmenddose response data).
Legislative approaches have serious limitations, especially as a mechanism for controlling the
small-scale, artisanal mining sector. The use of legislation to control working conditions among
artisanal miners is commendable in theory but somewhat unrealistic within the context of most
artisanal gold mining operations. Legislation for the artisanal sector is in many respects futile as
such activities usually operate beyond the law. For example, at Diwalwal in the Philippines, up to
100,OOO people work a world class gold deposit which is officially held by four major interna-
tional companies. In the absence of the political will to enforce the law, legislative controls will
be ineffective. Having a legislative framework does not necessarily mean that it will be adhered
to.
vi
CONTENTS
2. MERCURY CONTAMINATION
2.1 Chemistry of mercury
2.2 Toxicity and human exposure
2.3 Mercury contamination
2.4 A chemical time bomb ?
4. WORK PLAN 5
5 . COLLABORATIVEFRAMEWORK 6
14. TAKE-UP 57
15. ACKNOWLEDGEMENTS 57
16. REFERENCES 57
1
2. MERCURY CONTAMINATION
2. I Chemistry of mercury
Mercury has a density of 13.53 g/cm3 and an unusually low melting point of -38.9"C. It is distinguished from
all other metals by its persistence in a liquid state under most surface-environment conditions. Mercury pos-
sesses three oxidation states (MO- M+2)of which Hg2+compounds and elemental Hg are most common.
Mercury is among the rarest of naturally occurring elements, with an average abundance in the earth's crust
of 0.08 pg/g (Greenwood and Earnshaw, 1984). It is characteristically enriched in acid relative to mafic igne-
ous rocks (average 0.08 pg/g in granites and 0.01 pg/g in basalts), with concentrations frequently one to two
orders of magnitude higher in argillaceous and organic-rich sedimentary rocks (Wedepohl, 1978). The principal
economic ore mineral is cinnabar (HgS), from which Hg is recovered by flotation and subsequent roasting of
the crushed ore to yield HgO and ultimately free mercury. Mercury occurs in the atmosphere as a result of the
natural degassing of the earths crust through the release of volcanic gases and evaporation from the oceans.
Many activities of man account for substantial releases of mercury into the environment. One of these is the
mining and smelting of mercury. In particular, the dumping of mine tailings or process wastes into lakes and
rivers has resulted in the high levels of mercury in these bodies of water, as well as in sediments and biota.
Hg in uncontaminated freshwater systems ranges from 5 to 50 ng/l rising to 0.1-60 mgA in geothermal wa-
ters (Fergusson, 1990) and 0.2 to 10.0 mg/l in mining contaminated surface waters (Pfeiffer et al., 1989; 1991).
At moderate or high redox potentials, inorganic Hg is predominantly stabilised as Hg(OH)2 at pH>6, while at
lower pH, HgOH' or chloro-complexes predominate depending on the ambient concentration of chloride. Free
Hg2+forms a stable dissolved phase in acid waters at redox potentials of around 0.5V whilst free Hg and HgS
phases are stabilised at redox potentials of <0.3V across a wide pH range.
Mercury is a very persistent contaminant. In the metallic form it may persist in sediments for many years.
Inorganic Hg in sediments is usually strongly adsorbed onto mineral particles and is not readily bioavailable.
Methylation of inorganic Hg in lake, river and stream sediments is a key stage in the transfer of Hg into aquatic
biota. Aerobic or anaerobic bacteria present in sediments are commonly involved in the methylation process
with the highest rates of methylation occurring at relatively low redox potentials of +100 - -200 mV. The
methyl species formed is strongly pH dependent, with methyl mercury ((CH3)Hg) most common under acid
conditions and dimethyl mercury ((CH&Hg) in alkaline systems. The alkyVmethy1 species of Hg commonly
constitute 0.5-3% of the total dissolved Hg in natural waters.
Relatively small amounts of inorganic mercury are methylated by bacterial activity and may enter the food
chain in this organic form, or even as inorganic Hg2+salts. Mercury also accumulates in the food chain and so
can be concentrated in higher organisms, especially in fish which may be an important human food source.
2
across Europe, North America and parts of south-east Asia. Whereas most mercury contamination previously
resulted from hydrocarbon combustion and manufacturing processes in industrialised regions (Tables 1 and 2),
significant quantities of mercury are now released into the environment as a result of its use for amalgamation
by small scale gold producers.
Table 1. Current global mercury additions to the biosphere (excluding the atmosphere) from natural and anthropogenic
sources (adapted from Lacerda and Salomons, 1998)
Table 2. Current global mercury emissions to the atmosphere from natural and anthropogenic sources (adapted from
Lacerda and Salomons, 1998)
Mercury has been used in gold and silver mining since Roman times and it is estimated that mercury released
to the biosphere due to this activity may have reached over 260,000 t from 1550 to 1930 (Table 3), when mer-
cury amalgamation was replaced by the more efficient cyanidation process. The 1970s gold-rush, sparked off
principally by high gold prices, involved more than 10 million people in all continents and most of these were
in the developing countries of the southern hemisphere. The mercury amalgamation process is used as a major
technique for gold production in South America, China, Southeast Asia and in some African countries. It is
estimated that mercury loss to the environment from amalgamation may be as much as 460 tonnes per year
(Table 4). Gold mining is presently responsible for approximately 10% of the global Hg emissions from an-
thropogenic sources. Much of the estimated 300,000 tonnes of mercury released to the environment as a result
of gold and silver mining during the last 500 years is still important in the global mercury Hg cycle insofar that
it is susceptible to remobilization from abandoned mine waste and other land contaminated with mercury.
Table 3. Estimated annual and total emissions to the environment from historic gold and silver production (adapted from
Lacerda and Salomons, 1998)
3
Table 4. Estimated emissions of mercury to the environment from present-day gold mining areas (adapted from Lacerda
and Salomons, 1998)
Gold mining area Year production started Annual emissions Total emissions
(ty i ’ ) (ty r-’1
Amazon, Brazil 1979 180 3000
Mindanao, Philippines 1985 26 200
Rio Puyango, Peru 1987 3 23
Canada 1976 0.5 10
COCO, Colombia 1987 30 240
Pando, Bolivia 1979 7-30 300
N. Sulawesi, Indonesia 1988 10-20 120
Dixing, China 1992 120 480
Guyanesa Shield, Venezuela 1988 40-50 360
The amalgamation process requires the use of about 2 tons of mercury for each ton of gold recovered. Small-
scale gold miners produce thousands of tons per annum so environmental contamination by mercury release is
of considerable concern in many less developed countries. The most serious contamination occurs in Brazil
where it is estimated that the annual release of mercury into the environment is approximately 180 tonnes
which constitutes more than 80 % of total anthropogenic mercury emissions in Brazil. Approximately 136
t.yr(-1) of mercury from gold mining sources is emitted directly to the atmosphere.
4
areas in Ecuador. However, in August 1995, the main collaborating organisation in the Philippines, the Mines
and Geoscience Bureau (MGB) was obliged to reappraise their priorities in the light of widespread media
reports of human mercury poisoning in an area of former cinnabar mining on the island of Palawan. In response
to a directive from Philippines President Fidel Ramos, the MGB commissioned an inter-agency investigation
into the Palawan scare, and a formal request for the diversion of BGS-DFID funds from Mindanao to Palawan
was received by BGS in September 1995. Although falling strictly beyond the remit of TDR project R6226
(which is primarily concerned with Hg contamination associated with artisanal gold mining), the request was
considered by BGS and DFID to constitute a strong case for demand-led TDR expenditure. Accordingly, a
preliminary BGS-MGB investigation of the extent of the Palawan Hg problem was sanctioned in December
1995, and executed with assistance from the UK Institute of Terrestrial Ecology (PE). In view of the paucity
of geochemical, ecotoxicological or epidemiological data depicting the extent and magnitude of Hg hazards in
central-eastem Palawan, the-principal objectives of the study were:-
1. Establish the spatial extent and magnitude of Hg contamination within the sediments of Honda Bay
2. Evaluate temporal trends of Hg deposition in the marine environment, with particular reference to flux
adjustments associated with the onset of mining and the construction of the Sitio Honda Bay jetty.
3. Assess the risk posed to inhabitants of Sitio Honda Bay jetty and the PQMI mine locality as a consequence
of living on a mine-waste substrate and hence the need to re-house the people at a less contaminated site.
4. Assess the extent of Hg bioassimilation and attendant toxicological stress in marine biota (fish and shell-
fish) at various localities in Honda Bay, and appraise the significance of Sitio Honda Bay as a contaminant
source for biota.
5. Assess alternative potential sources of Hg exposure (e.g. potable water)
6. Prepare recommendations for remedial action, if appropriate.
4. WORK PLAN
A work programme incorporating the following five major phases was designed to address the project objec-
tives :
Phase 1 : Collation of existing data and bibliographic review. A thorough bibliographic review was carried
out at the beginning of the project in order to obtain relevant background information on monitoring protocols
and for the human and ecotoxicological impact assessment. The review was updated prior to compilation of
this report.
Phase 2: Design and testing of monitoring protocol to identify mercury sources, transport pathways and
fates. Monitoring in each of the selected case study areas was performed to quantify (1) the magnitude and
extent of mining related mercury contamination in drainage sediments and water, and (2) the ultimate fate of
mercury contamination. At the project outset, Eastern Mindanao was jointly identified by staff of the BGS and
the Philippines Mines and Geosciences Bureau (MGB) as an appropriate focus for research due to the exten-
sive gold-rush which has occurred in the region during the last two decades, with widespread utilisation of Hg
for gold amalgamation. The sampling campaigns in the Ponce Enriquez and Nambija areas of Ecuador were
executed as precursors to more comprehensive environmental monitoring scheduled under the World Bank
funded PRODEMINCA project, sub-component 3.1 (Monitoreo de 10s impactos ambientales, socio-
economicos y sobre la salud, relacionados con las actividades mineras). In the Honda Bay (Palawan) case
study, monitoring covered both the terrestrial and marine environments.
Phase 3: Human and ecotoxicological impact assessment. The likely toxicological significance of mercury
contamination was evaluated by comparing monitoring data with relevant water and sediment quality thresh-
olds for human health, drinking water, aquatic biota and shellfish. In Palawan, the extent of mercury bioas-
similation and attendant toxicological stress in marine biota (fish and shellfish) was assessed. The impact of
mercury contamination on the local inhabitants in the Honda Bay area of Palawan and the Tagum area of
Mindanao was evaluated through determination of mercury in hair samples.
Phase 4: Evaluation of alternative gold recovery methods. Recommendations for improving the efficiency
of fine gold recovery evolved from a comprehensive literature review. Gravity separation was recommended as
an efficient alternative to mercury amalgamation for the concentration of fine gold. A simple BGS-designed
gravity separator was constructed and tested under laboratory conditions using Au-bearing material (ore) col-
lected from three sites in the Philippines. Following design modifications, the gravity separator was tested
under field conditions and donated to the Philippines MGB as a model for the development and construction of
full-scale production equipment.
5
Phase 5: Recommendationsfor environmental control legislation relating to mercury pollution. It had been
anticipated that recommendations for maximum permissible environmental mercury levels in the Philippines
would evolve from the biological and human impact assessments (Phases 2 and 3) and that these would be
incorporated into new legislative controls on the small-scale mining sector being prepared by the MGB at the
time the project started. It was also intended to recommend that the Governments of other developing countries
afflicted by the impacts of small-scale gold mining should adopt these standards. Recommendations for in-
creased restriction of amalgamation andor alluvial mining in environmentally sensitive areas (such as localities
in which discharges potentially affect economically important fisheries in Ecuador, for example) were planned
to be made to government authorities where appropriate and where substantiated by monitoring data (Phase 2).
Practical (i.e. attainable and enforceable) legal standards for environmental mercury levels and discharges need
to be complemented by the inclusion of monitoring guidelines within all new legislation. In the event, the new
Ecuadorian and Philippine mining and environmental protection regulations and laws were pushed through
much faster than had been envisaged, effectively precluding BGS’ involvement in this aspect of the project
programme.
A summary of the case studies that comprise Phases 2-4 of the workplan together with their associated out-
put (Technical reports) are summarised in Table 5.
5. COLLABORATIVE FRAMEWORK
All aspects of the research programme were co-ordinated and managed by the BGS. Specialist support for the
ecotoxicological impact assessment studies in Palawan was provided by the Institute of Terrestrial Ecology
(RE), a component body of the UK Natural Environment Research Council (NERC). Field investigations in
the Philippines were carried out in close collaboration with the Philippines Department of Environment and
Natural Resources (Mines and Geoscience Bureau), the Puerto Princesa Hospital, Palawan and the University
of the Philippines. Access to small-scale mining and processing operations was facilitated through the co-
operation of the mine and processing-plant owners. In Ecuador the principal collaborators were CODIGEM
(Corporacidn de Desarrollo e Investigacidn Geolbgico-Minero Metalrirgica), DINAPA (Departamento Na-
cional de Proteccidn Ambiental), DINAMI (Direccidn Nacional de Mineria) and the Swedish consultants of
the World Bank PRODEMINCA project. Advice of the significance of mercury levels in humans was provided
by toxicologists from Guy’s and St Thomas’ Hospital, London.
6
6. MINING RELATED MERCURY CONTAMINATION
6. I Philippines
Figure 1. Location of artisanal gold mining areas in eastern Mindanao, Philippines (inset map shows the location of the
main map area within the Philippines; dashed box indicates area of Figure 11; small filled circles indicate sampling sites on
lower sector of Agusan River)
The major gold mining localities of Mainit and Diwalwal are located within the mountainous East Min-
danao Ridge from which deeply incised rivers flow north and west into the low-lying gently undulating terrain
of the Agusan-Davao trough to the west. The Mainit gold locality includes at least eight epithermal Au and
three porphyry Cu prospects situated in the upper reaches of the Manat River catchment, plus an alluvial min-
ing area some 5-10 km downstream. Au is recovered by sinking trenches into active stream alluvium (Plate l),
into which sluice boards are emplaced. The heavy mineral residues on the sluice boards are subsequently
removed and refined in a prospecting pan, with the addition of Hg to amalgamate gold (Cover illustration).
7
At Diwalwal (Plate 2), a world-class gold deposit was discovered by casual prospectors in 1983. At the height
of the Diwalwal gold rush, the locality was occupied by over 100,OOO small-scale miners, but has since de-
clined to approximately 50,000 as a consequence of major landslides in 1985 and 1988. The artisanal mining
sector has control of one of the world’s most important gold occurrences while major mining companies are
unable to gain access to the deposit (Guardian, UK, February 28, 1998). The mining area lies in the headwaters
of a series of minor tributaries of the Mamunga River (known locally as the Naboc River), which subsequently
joins the Agusan River (Figure 1) The gold veins are worked via a series of adits and drives, and the ore is
crushed at co-operative rod mills. Much of the processing activity during the 1980s involved amalgamation. In
the early 1990s, a centralised carbon-in-pulp (CIP) lime-cyanide leaching plant was established. The extrac-
tion-plant’s efficiency was claimed to give better than 95% recovery. Mercury, often present in older discarded
tailings which are now being bought in and reprocessed by the CIP operators, is recovered at various stages in
the processing and sold back to the miners for re-use. The recovery efficiency for mercury is not known. The
total ‘official’ gold production for each of the last 10 years was of the order of 0.5 million oz (DENR, unpub-
lished data). Actual production is conservatively estimated to be more than twice this figure giving a total gold
production over the last 10 years of about 280 t. Assuming half the production involved amalgamation, this
implies that nearly 300 t of mercury will have been used of which approximately 10% (30 t) will have been
discharged to the rivers.
Mining of placer deposits was initiated at Gango in 1960, but underground working of high-grade narrow
vein systems started as recently as 1988. A minor gold rush into the locality was witnessed at this time, and a
community of approximately 1400 was dependent on small-scale mining in 1990. Gold production in 1990 was
estimated at 153 g/day, with 18 rod-mills operative for the processing of ore. Until the late 1980s, gold was
amalgamated by the direct addition of Hg during milling in a tromol mill (James, 1994) after which the resi-
dues were discarded. More recently, small-scale CIP cyanidation plants have been developed locally, and are
utilised on a co-operative basis. On account of the low-recoveries attained by amalgamation, tailings previously
treated in this manner (and hence containing Hg-residue) are now being widely reprocessed by CIP operators.
-
6. I .2 Mercury mining Palawan
Cinnabar mining and tailings disposal in Honda Bay, Palawan, Philippines (Figure 2) led to reports of human
mercury poisoning. Three villages located in the low-lying coastal area bordering on Honda Bay were reported
to be at risk. Mercury, mainly in the form of cinnabar (mercury sulphide, HgS) had been extracted principally
at a mine operated by the Palawan Quicksilver Mining Inc. (PQMI) located 3 km inland from Honda Bay from
1953-1976. Ore was extracted from an open pit and in excess of one million tons of tailings from the PQMI
roasting plant was discarded along the Honda Bay coastline during the 1960s, and was ultimately used for the
construction of a 400 m long jetty, Sitio Honda Bay (Figure 2), which provided a landing point for the fuel
tankers which supplied the PQMI ore-roaster. Following the closure of the mine in 1976, a substantial commu-
nity (approximately 200 inhabitants) settled on the Sitio Honda Bay jetty, mainly engaging in fishing.
Figure 2. Location of Sitio Honda Bay (SHB) Jetty, Palawan and sampling locations (grey diamonds) visited during the
MGB Explorer gravity coring survey of Honda Bay in September 1995. Stations 2,7,9 and 25 (black diamonds) were
subsequently re-sampled by BGS for high-resolution downcore Hg analysis. (PQMI = former Palawan Quicksilver Mining
Inc. cinnabar mine).
8
6.2 Ecuador
In Ecuador, mercury pollution from gold mining, both within and along the coastal margin of the Western
Cordillera, has attracted considerable concern with respect to downstream pollution, especially of the economi-
cally important coastal shellfish production areas north of Machala. An important DFID-SIDA-World Bank
funded "Mining and Environment" programme was initiated in 1994 with the objective of developing and
expanding an "environmentally responsible" minerals sector. The gold mining sector in Ecuador provides
employment for a large number of people, the majority of whom are artisanal miners.
6.2. I Nambija
The major development of the informal mining sector in southern Ecuador took place in the 1980s in Nambija
where up to 20,000 people adopted relatively inefficient mining and mineral beneficiation processes which
involved the widespread use of mercury amalgamation. This resulted in extensive environmental degradation.
The gold occurrences and associated mining settlements of Nambija and Campanilla lie approximately 25
km east of the southern Ecuadorian town of Zamora at an altitude of approximately 1800 m (Figure 3). Gold
occurs principally in quartz-carbonate veins and stringers that follow NE-trending faults within a N-S trending
skarnfield of Jurassic age. Gold mineralization appears to be associated with a later phase of hydrothermal
activity that is focused along pre-existing structural trends within the skamified rocks. Common accessory
phases include magnetite, sphalerite and chalcopyrite.
Artisanal mining at Nambija and the neighbouring Campanilla settlement are focused within the Q. Calixto
and Q. Cambana sub-catchment areas, both of which form headwater tributaries of the Rio Nambija. The drain-
age is deeply incised with channels to interfluve relief averaging 800 m. Climatic conditions are temperate,
with an average diurnal range of 9-20°C and annual precipitation of approximately 2000 mm.
Exploitation of alluvial and bedrock gold from Nambija can be traced to pre-colonial times (Navarro, 1986),
however the present-day settlement was established as a consequence of a gold rush during the 1980s (Lither-
land et al., 1994). Gold-bearing skarn pockets are worked via a series of adits. Beneficiation is carried out
primarily within the major river valleys, where a series of sluices have been constructed to process milled ore.
Smaller-scale alluvial mining operations, mostly dependent on mercury amalgamation as a beneficiation
method, have been developed at several locations downstream of the main artisanal settlement within the
Quebrada Calixto and throughout the mid- and lower reaches of the Rio Nambija. Progressively falling pro-
duction during the 1990s has prompted a decline in the Nambija population and the community currently
numbers approximately 8,000.
I J.,
Figure 3. Location of the Ponce Em'quez and Nambija artisanal gold mining areas, Ecuador.
9
6.2.2 Ponce Enriquez
The Ponce Enriquez mining district (Figure 3) was developed by artisanal miners during the mid-l980s, al-
though the number of people involved and the social and environmental impacts are correspondingly less than
at Nambija. It has been estimated that more than 2,000 people live in the Ponce Enriquez mining settlements of
which about 1000 are involved in mining the Bella Rica sector.
Most of the gold and associated minerals in the high temperature hydrothermal vein mineralisation are ex-
tracted by hard rock mining methods and the gold is concentrated gravimetrically following grinding in Chilean
mills (trupiches).Gold is recuperated from heavy mineral concentrates by amalgamation, either in tromol mills
(Plate 3) or from gravity concentrates. Cyanidation plants (Plate 4) have recently been installed at various sites,
principally adjacent to the Rio Siete, to treat gravity tailings.
7. I. I Drainage surveys
Sample sites were selected to obtain information on the magnitude and extent of downstream dispersion of Hg
and other contaminants derived from mining and mineral processing activities. Filtered stream water, stream
bottom sediment and heavy mineral concentrate samples were collected at each site.
Wuter (w)
Stream water pH, temperature, Eh and conductivity were determined in the field using appropriate temperature-
compensated electrodes and meters. Water samples for chemical analysis were filtered through 25 mm diame-
ter, 0.45 pm Millipore (TM) cellulose acetate membranes into 30 ml Sterilin tubes or into acid-washed 30 ml
HPDE bottles (NalgeneTM).The suspended particulate load of the mining contaminated rivers was very high at
some sites and this caused severe problems with water filtration at some sites. Coarse prefilters were used,
ahead of the normal 0.45 mm cellulose disks, on all obviously turbid samples and the filters retained for analy-
sis in the Upper Agusan case study. At each site, the suite of water samples collected included: - (a) 30 ml
spiked with 1% v/v HN03(Analytical Grade) for determination of major and trace cations (including K, Na,
Ca, Mg, Sr, Cd, Ba, Si, Fe, P, B, V, MO,Al, Be, Zn, Cu, Pb, Li, Zr, CO, Ni, Y, La, Cr) by inductively-coupled
plasma emission spectrometry (ICP-ES) and, for the Ponce Enriquez samples, high precision hydride genera-
tion A A S analysis of As, (b) 30 ml unacidified water for Sod, NO3 and C1 analysis by ion chromatography and
(c) 30 ml spiked with 0.3 ml conc. HN03 + 0.3 ml 0.2 vol.% K2Cr07for total Hg analysis by Cold Vapour
Atomic Fluorescence Spectroscopy (CVAFS). Blank water samples, made using distilled water (provided by
the BGS laboratories) and appropriate aciddreagents, were submitted in blind fashion to the BGS ICP-ES and
CVAFS laboratories in conjunction with field samples. Results for these blanks confirmed that there was no
detectable background enhancement caused by the addition of aciddreagents to the field samples with respect
to the elements of major interest to the present survey: As, Cd, Cu, and Hg.
On Palawan, Total Hg analyses were conducted following pre-treatment of one aliquot with a brominating
agent to oxidise all organo-mercury compounds to inorganic species. The difference between the Hg value
recorded for this sub-sample and that for the corresponding non-brominated aliquot was assumed to constitute
10
organo-Hg. For both aliquots, the oxidant preservative (K2Cr07) was reduced using a dilute solution of
NH2.0H.HCl immediately prior to analysis.
Mercury analyses of stream bottom sediments and HMC were carried out by CVAFS, using 1 g milled sub-
samples digested at 4 0 ° C in aqua regia. SPM samples were dried and the sediment digested with the cellulose
filter membrane in aqua regia at 4 0 ° C and Hg determined by CVAFS. The practical CVAFS limit of determi-
nation for Hg in solid samples is 0.02 mgkg. Multi-element analysis of bottom sediment and SPM samples was
carried out by ICP-AES using an aliquot of the aqua regia digestate. For bottom sediments collected during the
Nambija survey and the Mindanao pilot study, major oxide and trace metal characterisation was carried out by
X-ray fluorescence (XRF) analysis of 12 g pellets made following disaggregation, ignition of organic matter
and milling of sediment to e63 mm.
In the Nambija survey, heavy mineral concentrates were visually examined in the field to establish the presence
of metallic Hg-Au amalgams and additional features of environmental significance. No quantitative analyses
were performed on these samples.
11
The magnitude of within-site variance of contaminant concentrations is compared with temporal variation
related to (1) changes in water flow and (2) variations in the fluxes of soluble and suspended contaminants,
including both mercury derived from amalgamation processing as well as other potentially harmful contami-
nants derived from ore processing including As and Cu. The relationship between within-site, between-site and
temporal variance is important in any assessment of the relative merits of the sample media for detecting and
mapping the extent and magnitude of contamination.
Table 6. Analytical data for sample pairs taken at the same site, Ponce Em’quez area, Ecuador (Appleton et al., 1996)
12
Thus, in theory, stream bottom sediments should be subject to the least short-term temporal variation in
contaminant concentrations, although major changes in contaminant fluxes are likely to affect concentrations in
this sample type.
In the Ponce Enriquez area, there is some evidence of short-term temporal variation in the contaminant load
of water and suspended particulate matter. This would, of course, be expected, as the release of overflow water
from the mineral processing and cyanidation plants is not constant. As sampling was executed over a period of
days, fluctuations in the load of suspended particulate matter reflect the level of discharges from grinding and
processing plants at the time of sampling (see Figure 4). Such fluctuations are also mirrored in contaminant
concentrations in both the river water and in the SPM. At 8 km above the shrimp ponds on the Rio Siete, for
example, there is a peak of SPM load which is also reflected most strongly by As and Cu in SPM, as well as
As, Cu and Na in water. The peak is not seen in the bottom sediment or HMC contaminant concentrations (see
also Figs. 13 and 14).
6
5 1
P
a
0
0 2 4 6 8 10 12 14 16 18
Mstrnca above shrlmp ponds (lon)
Longer term temporal variations may be evaluated at five sites in Mindanao (two from the Mainit and three
from the Diwalwal mining areas) which were sampled in November 1995 and February 1996. At all sites, Hg
in BS and HMC increased from November to February whereas Hg in water was the same or slightly lower,
apart from one site where the Hg concentrations had reduced from 2906 to 0.86 ppb (Figure 5a-d). No SPM
data are available for these sites. Increased Hg in bottom sediment and heavy mineral concentrates suggests
that the amount of Hg contamination had increased over the period of 4 months. Substantially higher concen-
trations in HMCs suggest that much of the Hg is in metallic form or Au-Hg amalgam. Sampling in February
took place after a period of very heavy rains which may have resulted in much mercury contaminated material
from tailings dumps being washed into the drainage system, thereby increasing contaminant levels in bottom
sediments. C1, Na and SO4 at the two Mainit sites are an order of magnitude higher in the February samples
compared with the November samples (Figure 5d). This implies that at the time of sampling in February, the
rainfall component of the surface drainage water flow was lower compared with the flux from the hot springs at
Pantukan. No marked season variations in rainfall characterise Eastern Mindanao that is subject to periods of
very heavy rainfall after which both contaminant and base flow signatures in water and SPM will be strongly
diluted. ~ ~~~~~ ~ ~~~~~
. .
. . 1
Figure 5. Temporal variation in (a) Hg and (b) C1 in river water; (c) Hg in bottom sediment and (d) Hg in heavy mineral
concentrates for the Diwalwal and Mainit mining areas, Mindanao, Philippines.
13
Concentrations of Cu in water samples tended to be lower in samples collected in a period of high rainfall and
river flow (March-April) compared with samples collected in the drier month of July in the Ponce Enriquez
area (Figure 6) although other elements demonstrated a less consistent relationship reflecting the high temporal
variance in contaminant fluxes in water. Hg and Cu in bottom sediments collected at the same sites for differ-
ent sampling programmes agree quite well in the both Ponce Enriquez (Figure 7) and Zaruma (Figure 8) areas.
However, other elements showed very disparate concentrations reflecting the large differences in contaminant
concentrations resulting from fluctuations in the amounts of finely ground sulphide minerals deposited from
the outflow water of the mineral processing plants. Replicate sampling at the same site on the same day indi-
cates low within-site variance. However, replicate sampling at the same site at different times clearly results in
greater variance in contaminant concentrations for some contaminants in both water and bottom sediments.
0 1 2 3 4 5
BGS
Figure 6. Cu in river water collected in high flow (March 1996) and low flow (July 1996) conditions, Ponce Enriquez,
Ecuador.
10000
0
8000
& 6000
4000 I 0
0 5000 10000
BGS
Figure 7. Hg and Cu in bottom sediments collected at the same sites (GIMP 1995 and this study, July 1996); Ponce En-
riquez.
I
0 0.5 1 1.5 2 2.5 3 3.5
1996
Figure 8. Hg in bottom sediments collected at the same sites in 1995 (Maldonado, 1995) and 1996 (this study); Zaruma,
Ecuador.
14
7.2.3 Downstream dispersion of contamination from artisanal gold mining areas
In the case study areas, sampling was carried out in drainage catchments directly impacted by contemporary
mining together with hydrochemically appropriate control stations within unmined tributaries. The most obvi-
ous indicator of mining activity is the grey, highly turbid nature of the rivers draining the mining areas, in
contrast to the clear waters of undisturbed streams. In the Ponce Enriquez area, Ecuador, large volumes of
gravity tailings which contain very high concentrations of copper (chalcopyrite) and arsenic (arsenopyrite), in
addition to being contaminated with mercury, are stored on the steep slopes of the Bella Rica mining sector.
The tailings dumps are prone to erosion by heavy rainfall that washes the material into the Rio Siete and Estero
Guanache drainage systems (see Figure 12 for Ponce Enriquez drainage plan). Most of the surface drainage
water in the area, including the Rio Siete, is very turbid due to the high load of very fine-grained gravity tail-
ings. Acid mine drainage with attendant iron oxide precipitation is less common (Plate 5). Suspended particu-
late matter loads of up to 6.2 g/1 were recorded during the present survey, decreasing to 1.0 g/l in the Rio Siete
at the Pan-American highway and 0.02 g/1 immediately above the shrimp ponds (Figure 4). Similar grey, highly
turbid waters characterise rivers in Mindanao where logging and other physical disturbance also causes turbid-
ity, though this is usually buff-brown in colour due to eroded soil.
Water
In the two case study areas in Ecuador, mobilisation of Hg in the aqueous phase is negligible and even in the
much larger Diwalwal artisanal mining area in Mindanao, Hg in filtered samples, although locally extremely
high, has a relatively short downstream persistence, probably as a result of dilution and adsorption. In the
Ponce Enriquez area, Hg exceeded the detection limit (0.02 pgA) in only two filtered stream water samples
from the Rio Siete that drains the main mining and mineral processing area of Bella Rica. The background
range for fresh (unpolluted) waters is 0.005 to 0.05 pg/l; thus none of the water samples from the Rio Siete exceed
this range. Hg in stream water below this anomalous site decreases to ~ 0 . 0 2pg/l within a distance of 2 km.Recent
working of alluvial gravels at one site gave rise to the only high Hg value in filtered water (0.9 pg/l). Generally,
low Hg concentrations in filtered river water also characterise the Nambija area with occasional higher concentra-
tions of up to 0.1 pg/l reflecting local influx of contamination (Figure 9). The only strongly anomalous value
(2.84 pg/l) in the Gango area (Mindanao) was recorded in outflow water from a CIP plant where the high Hg
concentration can probably be ascribed to the presence of Hg in the processing feed, much of which has previ-
ously been subjected to treatment by amalgamation. The chemistry of Au-Hg amalgams in cyanic solutions
requires further investigation, but initial indications are that Hg is effectively mobilised following the forma-
tion of AuCN complexes from formerly amalgamated Au. Regulations and guidelines to control the Hg hazard
associated with CIP discharges from plants treating tailings previously subjected to amalgamation processing
may therefore be warranted.
100
I" I
0 1 1 , ~ ' --4
, , ,\,-/
0 01
Figure 9. Distribution of Hg in bottom sediment and water in rivers draining the Nambija and Campanilla artisanal gold
mining areas, Ecuador.
As would be expected, much higher concentrations occur in rivers draining the major Diwalwal gold mining
area reaching a maximum concentration of more than 2000 pg/l immediately below the mining area but de-
15
clining rapidly to about 5 pg/l some 10 km downstream and to 0.1 pg/l near the confluence with the Agusan
River. Thus Hg in water at Diwalwal is much higher than typical concentrations of Hg in waters polluted by
mining and mineral processing activities in North and South America which fall in the range 0.2 to 13 p d l
(Pfeiffer et al. 1989, 1991; Lacerda and Salomons, 1998). Sulphate produced as a consequence of the oxidation
of sulphide minerals associated with the gold mineralisation dominates the ionic balance, especially at Ponce
Enriquez and Nambija. Elevated levels of NOs in stream and river water collected close to the mining settle-
ments of Diwalwal, Bella Vista (Ponce Enriquez) and Nambija reflect high inputs of organic material (sewage)
and eutrophication. TOC is also elevated in the immediate vicinity of Diwalwal but levels return to background
a couple of kilometres downstream. High Hg solubility is attributed to a substantial humic organic loading to
the drainage (emanating from an artisanal settlement of approximately 50,000 inhabitants) and the consequent
incorporation of Hg2+into soluble organo-metallic complexes. The formation of Hg-CN complexes in cyanic
drainage water may also be significant. The determination of TIC, TOC, humic organics, CN’ in water would
aid the interpretation of Hg concentration in filtered water. At some sites in Mindanao and Ecuador, Na derived
from CIP plant effluent is the dominant cation.
Suspended prticulate matter (SPM), bottom sediment and heavy mineral concentrates
Hg concentrations in drainage sediment are a function of deposition and inwash of Hg formerly mobilised as
vapour during ‘torching’ of amalgams (Lacerda and Salomons, 1998) as well as Hg inputs derived from tailings
from amalgamation processing of gold concentrates and tromol mills. Hence, the highest concentrations are
observed closest to these operations in all the study areas with particularly high concentrations observed espe-
cially close to ongoing or recent processing of alluvial gravels.
In the Ponce Enriquez area, for example, Hg in suspended sediments, stream bottom sediments and heavy
mineral concentrates range from 0.01 to 9.61 mgkg, 0.1 to 13 mgkg and 0.01 to 5.0 mgkg, respectively.
Slightly higher concentrations characterise bottom sediments in the Nambija area (Table 7 and Figure 10). The
level of Hg contamination is much higher in the artisanal gold mining areas of Eastern Mindanao where maxi-
mum values of 34 mgkg, 40 mgkg and 62 mgkg have been recorded in bottom sediment, suspended sediment
and heavy mineral concentrates, respectively (Table 7). Much lower concentrations occur in the smaller Bango
and Mainit mining areas, Mindanao (Figure 11). Background concentrations in uncontaminated areas typically
range from 0.1 - 0.4 mgkg in bottom sediments whereas in other mining contaminated regions Hg ranges up to
7.4 mgkg in N. Carolina (Callahan et al., 1994) and 25 mgkg in Brazil (Lacerda and Salomons, 1998; Reuther,
1994).
4kn
I I
Figure 10. Distribution of Hg in bottom sediment in rivers draining the Nambija and Campanilla artisanal gold mining
areas, Ecuador.
16
Downstream variation of Hg in stream bottom sediments at Ponce Enriquez is erratic ranging from 3 mgkg
immediately below the main Bella Rica mining and mineral processing area to 3 mgkg some 15 km down-
stream of Bella Rica, at a site which is only 2 km upstream of the eastern margin of the commercially important
shrimp ponds (Figure 12). Hg in suspended sediments and heavy mineral concentrates decrease more progres-
sively over the same transect (Figs. 12 and 13). Hg in suspended sediments decreases by a factor of nearly 100
over a distance of 15 km, suggesting that the contaminant load at the time of sampling was low. However, the
relatively high Hg concentration (3 mgkg) in stream bottom sediment 15 km below Bella Rica suggests that
the average level of contaminant transfer may have been higher, presumably during periods of higher rainfall.
PASIAN
BATAAN
MAlNlT
PANTUKAN 0 5xm
U
,12566' ,12616
Observation of Hg-Au amalgam particles in heavy mineral concentrates indicates that much of the Hg disper-
sion is in an inorganic state, especially in the highly siliceous and aluminous, apparently low TOC, sediments
17
of the Nambija and Ponce Enriquez areas (Appleton et al., 1996; Williams and Orbea, 1997). Bottom sediments
in both these locations are dominated by recently deposited, finely ground tailings material from the mining
operations (Plate 6) which have been mechanically transported along the river bed or deposited from material
transported in suspension (SPM). High concentrations of Hg in suspended particulate matter (SPM) indicate
that Hg adsorbed onto mineral surfaces will make a significant contribution to the Hg load of bottom sedi-
ments.
In some areas, there is a close correlation between Hg in SPM and water and also between Hg in BS and
HMC (Figure 15 and 16).
I I I
I
L-
t
Shrimp ponds \
,
- .-.,
.
,-----___I
8.
.------ ,-_---I
--
I ,
- 3km
-%-
Shrimp
\
\
\
10-15 mg/kg
0 5.0 - 9.9 mg/kg
0 -
2.0 4.9 mgncg
0 0.5- 1.9 mgkg
0 c0.5mykg
Figure 13. Downstream dispersion of contaminants in bottom sediment and heavy mineral concentrates, Rio Siete, Ponce
Enriquez.
18
+SWFe(%)
~~~ 1
0.1
0.01
0 2 4 6 8 10 12 14 16
Distance below BeWa Wca (krn)
Figure 14. Downstream dispersion of contaminants in suspended particulate matter (SPM), Rio Siete, Ponce Enriquez.
100
* *
0.001 J
0.01 1 100 loo00
w-Hs (PPm)
Figure 15. Relationship between Hg in SPM and water, Upper Agusan, Mindanao.
1 00
+ ***
***
0.01 4
**
0.001
0.01 0.1 1 10 100
19
SPM, water and HMC whereas Hg in bottom sediments declines much less steeply maintaining a relatively
high concentration of about 20 mgkg for nearly 15 km (Figure 17). Extremely high concentrations of Hg in
solution, reaching a maximum of 1539 ppb, decline rapidly to 7 ppb in the first 5 kilometres below Diwalwal as
a result of the combined effects of dilution, sorption onto SPM and bottom sediment and volatilisation. The
bulk of the contaminant load is in the SPM, being a factor of loo0 times more than the Hg in solution. It is
assumed that Hg is either fine particulate Hg or more likely is sorbed onto silt and clay particles. Historic
contamination is indicated at those sites where Hg in water and SPM are extremely low whereas high levels
occur in the bottom sediment. The last sample site on the Mamunga River is actually within the floodplain of
the Agusan River, which possibly explains why Hg in bottom sediment falls so dramatically at this point where
contaminated sediment from Diwalwal is diluted by the relatively uncontaminated sediments in the Agusan
River. Hg in SPM and water decline progressively downstream in the Agusan River although Hg is bottom
sediment increases slightly at the next sample site 50 km downstream before declining gradually over the next
70 km (Figure 18). It is possible that Hg is enhanced as a result of adsorption onto organic matter in the bottom
sediments within the relatively slow-flow regime of this section of the Agusan drainage basin. Alternatively,
Hg may be slightly enhanced as a result of historic contamination. The downstream dispersion pattern on the
Manat-Agusan River system below the much smaller Pantukan and Mainit mining areas declines steeply over
the first 20 km before rising sharply below the confluence with the Mamunga River which introduces high
levels of contamination from the Diwalwal area (Figure 19).
The relationship between Hg in bottom sediment with Hg in SPM and HMC provides some indication of the
downstream sedimentation processes. Hg in bottom sediment accumulates as a result of direct sorption from
solution and by sedimentation of SPM derived from mineral processing activities. The ratio between Hg in
bottom sediment compared with SPM and HMC increases progressively in both the Mamunga-Agusan drain-
age system in Mindanao and the Rio Siete in Ecuador (Figs. 20 and 21). HMC Hg, mainly in the form of parti-
cles of Au-Hg amalgam, is generally high close to the source of contamination, as it is heavy and not readily
transported by the river. In the Rio Siete area, HMC is generally less than Hg in bottom sediment suggesting
that much of the Hg is adsorbed onto fine mineral particles derived from mineral processing rather than as
discrete particles of Au-Hg amalgam. Adsorption onto organic matter may be a factor, although no TOC data is
available to assess this. At the time of sampling, which was characterised by relatively low river flow, SPM in
these low flow conditions tends to decline fairly rapidly downstream as the water becomes clearer as a result of
sedimentation. In contrast, the Hg concentration in bottom sediment declines less rapidly downstream reflect-
ing more extensive contamination created during periods of maximum river flow and also the adsorption, over
a long period, of Hg onto bottom sediments. It is assumed that the ratio between Hg is bottom sediment and
SPM would not increase so rapidly downstream at times of maximum flow as the relatively heavy SPM con-
taminated with Hg would be transported further in a more dynamic hydraulic regime. Thus the relatively high
concentrations of contaminants in bottom sediment in the Rio Siete some 2 km above the shrimp ponds indi-
cates that contaminated sediment is carried further during periods of high flow. In the Rio Siete, the BS/SPM
ratio for Hg is significantly higher for Hg compared with As, Cu and Fe (Figure 21) reflecting the differences
in specific gravity of contaminant particles. In addition, the amplitude of fluctuations in both element and ratio
dispersion patterns is greatest for Hg reflecting the generally low concentrations as well as the likely erratic
distribution of Hg-rich particles within the bottom sediment.
4 W=1539ppm
50
40
30
t”
20
10
0
0 4 8 12 16 20 24
aStwm (km) below Diwalwal mining mntre
Figure 17. Downstream dispersion of Hg in the Mamunga River below the Diwalwal mining region.
20
1000
100
10
2 1
0.1
0.01
0.001
0 20 40 60 80 100 120 140 160
Distance (km) below Diwalwal mining area
Figure 18. Downstream dispersion of Hg in the Mamunga and Agusan Rivers below the Diwalwal mining region.
Figure 19. Downstream dispersion in the Manat-Agusan river system below the Pantukan-Mainit mining areas
100
10
0.1
0 10 20 30 40 50 60 70 80 90 100 110
Figure 20. Relative concentrations of Hg in bottom sediment (BS), suspended particulate matter (SPM) and heavy mineral
concentrate (HMC) in the Mamunga-Agusan drainage system
21
0
0 2 4 6 8 10 12 14 16
Figure 21. Relative concentrations of Hg, As, Cu and Fe in bottom sediment (BS) and suspended particulate matter (SPM)
in the Rio Siete, Ponce Enriquez area.
15
0
0 2.000 4,000 6,000 8,000 10,000
Umber of peopb actively invoked in gold e x t r u l i n
Figure 22. Relationship between estimated number of people actively involved in gold extraction and the level of Hg
contamination in bottom sediment (BS). (D: Diwalwal; P: Ponce Enriquez, Ecuador; N: Nambija, Ecuador; G: Gango)
22
Table 7. Summary statistics for Hg in sample media compared with estimated number of people involved in
gold mining and processing
MINING
AREA Diwalwal, Gango, Nambija, Ponce Enrfquez,
Mindanao Mindanao Ecuador Ecuador
Note: BS = bottom sediment; W = river water; SPM = suspended particulate matter; na = no data available; nd = not detected
Mercury concentrations in bottom sediments and river water are generally higher than those recorded from
Brazil, especially at Diwalwal. For example, near PoconC in the Mat0 Grosso area where about 5000 workers
have been employed in 130 gold mines since the 1980s, Hg reaches a maximum of only 160 ng/l in filtered
water and 198 ng/g (Tumpling et al., 1995) to 1.85 mgkg (Rodrigues and Maddock, 1993, 1997) in bottom
sediment. In the Camaquii River Basin, Rio Grande do Sul state, Brazil, an area of abandoned gold working
where mercury had been used extensively for amalgamation, sediment concentrations average 0.15 mgkg with
a maximum of 0.43 mgkg (Pestana et al., 1997). These values are low compared to corresponding values for
some other gold mining areas in the Amazon basin ( ~ 0 . 0 1- 12.9 pg/l in water and ~ 0 . 0 to
2 19.8 pg/g in sedi-
ments; Lacerda and Salomons, 1998). Malm et al. (1990) reported much higher sediment concentrations of up
to 157 mgkg Hg in the Madeira River, Brazil where Hg had been use extensively for amalgamation in gold
mining. However, data for numbers of people involved in mining and mineral processing are not readily avail-
able for these areas so the amount of Hg contamination in relation to mining activity can not be compared to
the data for the present study. However, the generally low levels of Hg contamination in the Amazon drainage
system where over 600,000 workers are reported to be involved in small scale gold production (Lacerda and
Salomons, 1998) compared with values recorded in the Philippines and Ecuador, where much smaller numbers
of miners are involved, may reflect the more mountainous topography in these two countries compared with the
mature topography of the Amazon region. Dispersion in a fluvial environment would tend to be greater in fast
flowing rivers.
For comparison, bottom sediment concentration of about 2.5 mgkg have been recorded in the Carson River
50 km downstream of the Comstock load historic Au-Ag mining area where an estimated 7000 short tons of Hg
were released to the Carson River between 1860 and 1900 (Lechler et al, 1997). Higher concentrations of Hg
are associated with mercury mines of Monte Amiata in Italy (228 mgkg), Suplja Stena near Belgrade, in for-
mer Yugoslavia (up to 6000 mgkg) and Idrija near Ljubljana, Slovenia (up to 1000 mgkg falling to 5-300
23
mgkg some 5 km downstream of the mine and smelter; Gosar et al. 1997). Mine spoil mercury concentrations
of >loo0 mgkg decline to only 8 mgkg some 4 km downstream of cinnabar mine in Palawan (Williams et al.,
1996). These lower values in Palawan may reflect the smaller size and shorter life of the Palawan Hg deposit
compared to the Idrija mines which produced 105,000 tonnes over a period of 500 years (Gosar et al., 1997). In
comparison, pollution of rivers by other industrial processes has produced average and maximum sediment
concentrations of 20 mgkg and 157 mgkg, respectively, in the Elbe River (Wilken et al., 1990), and 0.7 to 20
mgkg in sediments contaminated by effluent from a chlor-alkali plant near Rio de Janeiro, Brazil (Moriera and
Pivetta, 1997).
Extremely high concentrations of As and Cu characterise the drainage systems in the Ponce Enriquez area
because of the large amounts of arsenopyrite and chalcopyrite associated with the gold mineralisation. In con-
trast to both Ponce Enriquez and mining localities characterised by acid drainage, conditions downstream of
Nambija, Diwalwal and Gango (Table 7) are the predictable function of a low toxic trace element component
within the mineralised assemblage (and hence the process waste) coupled with a strongly-buffered regime
which inhibits mobilisation of metals such as Pb, Zn and Cu.
1o()oo -I
l_ll.."ll-.l*."...l.lll.llll.l..l..l lll~*l-."..l---
+Bottom sedimnt
+w
f-
cn
100
1 -
0 1 2 3 4
Distance (km)
Figure 23. Downstream dispersion of Hg from tailings piles (0 km) to the sea (4 km) in Tagburos River, Palawan.
24
7.3.3 Marine sediment: Honda Bay
A study of the geochemistry of sediments in close proximity to Sitio Honda Bay (Benoit et al., 1994)provided
evidence that the Hg concentration of the jetty substrate, constructed of mine waste, may be higher than previ-
ously envisaged (up to 560 mgkg). A substantial Hg flux into the marine environment was indicated by the
prevalence of distinct gradients in surficial sediments southward and eastward from the jetty. An inverse rela-
tionship between distance from source and the percentage of Hg held as cinnabar was also demonstrated (using
a series of leach-tests), and interpreted as consistent with the transformation of detrital sulphides to more reac-
tive (methyl) Hg phases during transport.
A preliminary survey of Hg in marine sediment in 1995 by the MGB involving sediment coring at 12 sites
(Figure 2) revealed Hg concentrations in the global background range (c40 pgkg) in the surficial 10 cm of
sediments at most offshore stations, with no significant downcore variation. Coastal sediments routinely
yielded similar values, although enrichment by approximately an order of magnitude (approximately 400
pgkg) was recorded at the mouth of the Tagburos River.
Marine sediment cores were used to assess spatial and temporal trends of Hg deposition in Honda Bay. The
average Hg concentration in surficial sediment at offshore sampling stations throughout the study area was
found to be approximately 40 pgkg, and is thus within the global background range. Detailed re-sampling of
selected cores (sampling stations 2, 7,9 and 25, Figure 2) showed evidence of Hg enrichment at or near the
sediment-water interface, most conspicuously in core 2 in which a two-fold increase of concentration to a
maximum of 95 pgkg occurs within the uppermost 5 cm (Figure 24). While such concentration adjustments
occur in sediments deposited during the last 10 - 50 years, it is unlikely that mining or any anthropogenic
activity is the causal factor. The role of mining can be specifically discounted, given the location of this coring
station in the un-mined basin of Puerto Princesa Bay. In all analysed cores, total organic content (as defined by
LOI) was found to increase significantly in the uppermost 2-4cm. Preferential incorporation of Hg into this
organic sediment fraction thus provides the most plausible explanation.
0
q-O 0./@
5 9
0
10 0
A 9
4PI
15 0
T
CORE 7
fi 20 O
\
0
/.
25
0
I
30
10 20 30 40 50 6070 80 90 10 20 3040 50 60 70 80 90 10 20 30 40 50 60 70 80 9(1 10 20 30 40 50 6070 80 90
Concentration (pg/g)
Figure 24. Downcore Hg profiles through the upper 26 cm of sediment at selected Honda Bay coring stations.
-
7.3.4 Sitio Honda Bay geochemical and mineralogicalresults
Earlier studies (Benoit et al., 1994)indicated Hg concentrations of 560 mgkg in the waste used to construct the
Sitio Honda site and led to the proposal that the 200 residents should be re-settled as the structure was consid-
ered too contaminated for human habitation. Geochemical and mineralogical analyses of mine waste from the
Sitio Honda Bay jetty structure (Plate 8) were undertaken to establish the total concentration and bioavailabil-
ity of Hg. Profiles through the waste characteristically display a depthward reduction of Hg concentration, from
surficial values of up to 340 mgkg to basal concentrations of c40 mgkg. It is notable that garden topsoil at one
site holds a high Hg concentration (179 mgkg) relative to most analysed samples of Sitio Honda Bay mine-
waste. This soil was imported specifically for use as an uncontaminated matrix for growing garden vegetables.
It is possible that organic matter in this soil has assimilated Hg from the underlying waste, with potentially
important implications for it's long term utility for domestic vegetable production.
25
Gravimetric partitioning of Hg in waste samples indicated that only 2-35% of Hg is held in the heavy min-
eral fraction. This implies that cinnabar within the waste must be predominantly fine-grained and prone to
rapid weathering. Any cinnabar originally present in waste forming these horizons must, therefore, have been
comprehensively degraded and the Hg repartitioned into clays, and this is confirmed by the high Hg (up to 550
mgkg) in the fine fraction of the tailings. Microprobe analysis of the e20 pm fraction indicated that the Hg in
the clay-dominated assemblage is primarily held as an inorganic impurity in (or sorbed to) hydrous Fe oxide
phases such as goethite and ferrihydrite. The solid-phase speciation of Hg in the e2mm fraction of the waste is
dominated by inorganic non-sulphide Hg-phases (generally constituting >90% of the total Hg mass balance).
Seaward adjustments to the Hg totaVHgS ratio as reported by Benoit et al. (1994) may be caused by gra-
vimetric sorting of cinnabar and secondary Hg carriers in the fine-silt and clay size range following the erosion
of waste from the jetty by wave action. These phases are of typically low bioavailability. Human Hg exposure
through particulate inhalation or hand-mouth ingestion is therefore considered unlikely to be significant.
8. I Water quality
8.1.1 Mercury
Of the artisanal gold mining and the mercury mining case studies, the Diwalwal area is characterised by ex-
traordinarily high concentrations of Hg in water (approximately 2000 pgA) which decreases to about 5 pg/l
some 10 km downstream, which is still a very high concentration. Whereas the river water in the immediate
vicinity of Diwalwal is extremely turbid and not abstracted for drinking, 10 km downstream the water is no
longer turbid and is used by the local inhabitants for routine domestic purposes. With a Hg load of 5 pgA in
solution, this is clearly a significant health hazard. Such high values clearly exceed both the WHO Drinking
Water Guideline value and the USEPA Water Quality Criteria for the Protection of Aquatic Life (Table 8). In the
other areas studied, Hg in river water is below these water quality criteria and the Human Health Criteria (car-
cinogenic risk from consumption of aquatic organisms) so have no toxicological significance.
8. I .2 Arsenic
Whereas the WHO Drinking Water Guideline (10 pgA) and the EC Directive Maximum Admissible Concen-
tration in Drinking Water (50 pg/l) are clearly exceeded in several instances in the Ponce Enriquez area, the
maximum water safety level for aquatic life (400 pg/l; Fergusson, 1990) is exceeded in only one sample. No
samples exceed the value of 3000 pg/l As adopted by the UK-DOE (NRA, 1994) to comply with the EEC
Shellfish Waters Directive (79/923/EEC) but the more stringent USEPA Water Quality Criteria for fresh water
(190 pg/l) is exceeded at five sites (Appleton et al., 1996). Marine invertebrates and fish usually contain high
concentrations of arsenic in the range of about 1 to 100 mgkg dry weight (Neff, 1997) with wet weight con-
centrations for prawns typically being in the range of 1 to 18 mgkg (mean 5 mgkg; Sadiq et al., 1995). The
arsenic is largely in the form of organoarsenic compounds of which arsenobetaine is the major component.
Fortunately, although organoarsenic compounds are bioaccumulated by human consumers of seafood, the
arsenic is mostly excreted. Furthermore, the arsenic is mainly arsenobetaine which is neither toxic nor carcino-
genic to mammals (Neff, 1997). The USEPA human health criterion (fish consumption) value of 0.0175 pgA is
difficult to understand as the average concentration of arsenic in the Ocean is 1.7 pg/l (Neff, 1997). There is
reported to be a potential human health risk (based on 10-6risk for carcinogens) associated with the consump-
tion of fish or shrimps living in waters with As concentrations >0.14 pg/1 (Table 8). This level is clearly ex-
ceeded in the lower reaches of the Rio Siete immediately above the shrimp farms but its toxicological
significance is not clear. A detailed study of arsenic in the shrimps and fish both in the lower reaches of the Rio
Siete and adjacent shrimp ponds may help to determine the toxicological significance of the high concentra-
tions of arsenic in the river water as well as in the SPM and bottom sediments (see section 8.2.2, below).
26
8. I .3 Copper
In the Ponce Enriquez area, copper in nine water samples exceeds the EEC Directive Guide Level for Drinking
water (100 yg/l) and 5 samples exceed the WHO Drinking Water Guideline (2000 pg/l). A sample taken about
3.5 km upstream of the shrimp farms on the Rio Siete contained 807 pgA which significantly exceeds the UK-
DOE standard (10 yg/l) adopted to comply with the EC Shellfish Waters Directive (79/923/EEC; NRA, 1994) and
also the USEPA Freshwater Criteria for the Protection of Aquatic Life (11 pg/l; Table 8). If the temporal varia-
tions related to changes in contaminant fluxes and hydraulic regime are common, then higher concentrations may
sometimes occur near the shrimp farms. More detailed monitoring is required to verify the level, frequency and
duration of high contaminant fluxes in stream water. All Nambija, Diwalwal and Gango, water samples analysed
during this study yielded Cu and As values which are compliant with WHO standards for potable water (Table
8).
Table 8. Comparison of potentially harmful element concentrationsin filtered water samples from 2 km (MA-28) and 4 km
(MA-30) above the Rio Siete shrimp farms (Ponce Enriquez) with maximum concentrations in the Ponce Enriquez, Nam-
bija, Diwalwal and Gango artisanal mining areas and Water Quality Criteria (concentrationsin &I)
Footnotes:
na = not available; nd = not detected
I EPA Section 304 (a) Criteria for the Protection of Aquatic Life from Priority Toxic Pollutants (US Cleanwater Act, February 5, 1993;
Part 131-Water Quality Standards, Sec. 131.36 proposed amendment April 1995). The criteria refer to the inorganic form only. Fresh-
water aquatic life criteria vary with total hardness and pollutant’s water effect ratio (WER). Values quoted here correspond to total
hardness of 100 mgA and a WER of 1.O
2
Criteria maximum concentration (CMC) = the highest concentration of a pollutant to which aquatic life can be exposed for a short
period of time (I-hour average) without deleterious effects.
Criteria continuous concentration (CCC) = the highest concentration of a pollutant to which aquatic life can be exposed for an ex-
tended period of time (4 days) without deleterious effects
UK-DOE “I” (imperative) values recommended for compliance with EC Shellfish Waters Directive (791923EEC) (NRA, 1994)
’ Human health ( 10-6risk for carcinogens) for consumption of aquatic organisms living in waters. For 10” risk, move decimal point one
place to the right.
If the CCC exceeds 0.012 pgfl more than once in a 3 year period in the ambient water, the edible portion of aquatic species of concern
must be analysed to determine whether the concentration of methyl mercury exceeds the FDA action level of 1.O mgkg.
27
8.2 Sediment quality’
8.2.1 Mercury
In the Diwalwal area maximum values of 34 mgkg and 40 mgkg have been recorded in stream bottom sedi-
ment and suspended sediment and similar maximum values have been recorded in the other case study areas
(Table 9). In the Ponce Enriquez area, the relatively high Hg concentration (3 mgkg) in stream bottom sedi-
ment 15 km below Bella Rica implies that the average level of contaminant transfer was higher historically,
probably during the previous period of high rainfall. The bioavailability of Hg in stream bottom sediments in
the lower reaches of the Rio Siete, immediately above the shrimp farms, merits further investigation as Hg
exceeds the Toxic Effect Threshold for the Protection of Aquatic Life (Table 9). The Toxic Effects Threshold
is exceeded over a lengthy section of the Mamunga River and also along short sections of river draining the
Nambija and Gango areas. In the nearshore zone of the Sitio Honda Bay site, Hg in the top layer of marine
sediment is unlikely to be a significant toxicological hazard (Williams et al., 1996).
High concentrations of Hg in bottom sediments is a long term source of contamination which may be dis-
persed by high flow rates and also progressively release Hg through methylation processes. Such contamination
has been referred to as a ‘Chemical Time Bomb’ (Lacerda and Salomons, 1998; see also Section 2.4 above).
Table 9. Comparison of potentially harmful element concentrations in suspended particulate matter (SPM) and stream
bottom sediments (BS) from above the Rio Siete shrimp farms (MA-28) at Ponce Em’quez with maximum concentrations
in the Ponce Em’quez, Nambija, Diwalwal and Gango areas and Sediment Quality Criteria for Protection of Aquatic Life
(concentrations in mgkg).
SPM BS BS BS BS
No effects Minimal Toxic MA28 Max. MA28 Max. Max. Max. Max.
threshold effects effects
threshold threshold
As 3 7 17 957 22626 7258 46049 34 11 333
Cd 0.2 0.9 3 2 18 12 24 3 <3 c3
cu 28 28 86 387 6437 2912 9134 409 67 188
Hg 0.05 0.2 1 0.1 9.61 3 13 34 34 0.13
Pb 23 53 170 123 1061 175 666 42 65 1078
Zn 100 150 540 108 743 347 924 23 1 114 1211
Note: SPM = suspended particulate matter; BS = bottom sediment; Sediment Quality Criteria for Protection of Aquatic Life (Environ-
ment Canada, 1992 quoted in MacDonald, 1994).
8.2.2 Arsenic
All arsenic concentrations in stream bottom sediments in the Rio Siete exceed the Sediment Quality Criteria
(Toxic Effects Threshold) for the Protection of Aquatic Life by a factor of up to 2700 (Table 9). It should be
realised that very high As concentrations (possibly up to loo0 mgkg) would occur naturally in this area of
arsenical mineralisation. The other areas are characterised by much lower concentrations and the threshold is
exceeded by a significant margin only at Gango.
8.2.3 Copper
Copper in the <150pm fraction of stream bottom declines gradually from 9,134 mgkg in the headwaters of the
Rio Siete to 2912 mgkg at a site immediately above the shrimp farms (Table 9). In the corresponding sus-
pended sediment samples, copper concentrations decrease from 6437 mgkg to 387 mgkg. All copper concen-
trations in stream bottom sediments in the Rio Siete exceed Sediment Quality Criteria (Toxic Effects
1
It should also be taken into account that contaminant concentrations in all case study areas were determined in the fine (c150pm)
fraction of bottom sediment whereas Sediment Quality Criteria are concentrations in unsieved sediment. Most of the contaminants will
tend to be concentrated in the fine fraction as a result of adsorption onto fine particles, clay minerals and organic material.
28
Threshold) for the Protection of Aquatic Life by a factor of up to 106 (Table 9). As with arsenic, high ‘natural’
levels would have characterised the area prior to the initiation of mining activities.
8.2.4 Cadmium
Cadmium in stream sediment at the site immediately above the shrimp farms on the Rio Siete exceed Sediment
Quality Criteria (Toxic Effects Threshold) for the Protection of Aquatic Life by a factor of 4 reaching a maxi-
mum of 16 in the headwaters of the Rio Siete (Appleton et al., 1996). Pb and Zn in stream sediment from the
lower section of the Rio Siete are either lower, or do not significantly exceed, the Sediment Quality Criteria for
the Protection of Aquatic Life (Table 9).
29
The impact of mercury contamination on the local inhabitants in the Honda Bay area of Palawan and the
Tagum area of Mindanao was evaluated through determination of mercury in hair samples.
9.2. I Background
In November 1994, the Philippines Environmental Monitoring Bureau (EMB) undertook preliminary analyses
of fish and shellfish from Honda Bay and concluded that several tissue concentrations fell within or above the
range recorded at Minamata, Japan. In March 1995, a Department of Health (DOH) survey of blood Hg-
concentrations in 42 subjects from the three barangays located in closest proximity to the PQMI operation
highlighted a 25%failure to meet the global threshold for 'normal' blood Hg levels of 20 ng/ml.
Media reports of the results of these preliminary biological and medical studies were, inevitably, interlinked
with the geochemical data of Benoit et a1 (1994), showing a major elevation of Hg (to 560 mgkg) on and
around the Sitio Honda Bay jetty which is constructed of about a million tons of Hg contaminated roaster
waste. Consequently, the situation portrayed by the media in August-September 1995 was one of unacceptable
human Hg exposure as a direct result of the contamination of Honda Bay and it's fishkhellfish reserves by
detrital Hg fluxes from Sitio Honda Bay, with subsequent methylation within the bay-floor sediment column.
This hypothesis formed the basis of a request by Palawan health officials for the granting of Disaster Area
status to central Palawan, and the immediate provision of central government funds to support one or more of
the following actions: - (i) detoxification of approximately 25% of the local population (based on the 25%
failure of subjects in the preliminary DOH survey to meet the 'normal' blood threshold of 20 ng/ml), (ii) provi-
sion of a laboratory facility at Puerto Princesa Provincial Hospital for the analysis of Hg in blood, (iii) removal
of the Sitio Honda Bay jetty and safe disposal of the contaminated tailings, (iv) resettlement of the approxi-
mately 200 population of Sitio Honda Bay, (v) dredging of sediments from contaminated sectors of Honda Bay.
By late 1995, the widespread publicity surrounding the Palawan mercury scare had imposed a significant
economic impact on the island, notably its fishing industry as a consequence of concern over product quality
amongst wholesale purchasers in Manila. Prior to the BGS/ITE survey, however, little quantitative data existed
to show the genuine extent of ecotoxicological risk to populations living close to the PQMI mine, on the Sitio
Honda Bay jetty, or those consuming fish from Honda Bay. Particular uncertainty may have arisen through the
misrepresentation of the geochemical data of Benoit et a1 (1994) in the media which, in failing to emphasise the
extremely localised nature of the study, inferred that anomalous Hg concentrations were characteristic of the
entire Honda Bay floor. In reality, the gradients reported by Benoit et al (1994) show concentrations declining
rapidly from 560 mgkg on the jetty, to 38 mgkg at 25 m distance, and 2.3-18.8mgkg at a distance of 200 m.
Data for control sites 7-10 km offshore indicate the prevalence of conditions within the global background
range (0.03 - 0.2 mgkg).
Uncertainties in the preliminary biological and ecotoxicological datasets collated by the EMB and DOH
primarily reflect the small sample populations involved (Williams et al., 1996a). Of the 12 people who yielded
blood Hg values exceeding the 20 ng/ml threshold, 50% were former miners or roasting plant operators. Data
for these individuals do not therefore infer any wider exposure of the population via the food chain. Within this
sub-group, the highest recorded value (25 ng/ml) can be regarded as unexceptional for individuals subject to
long-term occupational exposure. Although clinical symptoms of Hg poisoning have potentially been observed
in a limited number of Honda Bay miners, it is unlikely that these could have been caused by blood Hg levels
of this magnitude. Reference data from a comprehensive UNEPNHO-endorsed Monitoring and Assessment
Research Centre (MARC) study indicate that the lifetime exposure threshold required to induce pronounced
symptoms of clinical Hg poisoning is 80 ng/ml, with effects typically absent at levels of <200 ng/ml. Clinical
damage in miners could, however, have been caused by short-term acute exposure (no longer reflected in
blood) up to several decades previously.
30
mussel) were collected from two locations. The first was situated in shallow water approximately 10 m off the
southern margin of the Sitio Honda Bay jetty (Figure 2). The second was located close to the western shore of
Canon island, approximately 6 km off the Tagburos - Sitio Honda Bay coast. All samples were returned to the
haematology laboratory of Puerto Princesa Hospital for preparation and biomarker assessment within 8 hours
of collection. Samples were purged in clean water prior to sub-sampling. The soft tissues of mussels were air-
dried at 50°C prior to transport to the UK for final weight determination and analysis. The dry tissues were
partially digested in cold HN03 at ITE (Monks Wood) and forwarded to BGS for further reflux digestion and
total Hg analysis by CVAFS.
Previous work
It had been proposed that contamination by mining activities of the Honda Bay fish stocks may account for the
prevalence of elevated Hg levels in some individuals who had not worked at the mine or resided near the mine-
waste accumulation at Sitio Honda Bay. Previous studies had compared dry-weight Hg concentrations ranging
up to 1 1 mgkg with wet-weight values for fish and shell-fish at Minamata (0.4-30 mgkg and 1.3-14 mgkg
respectively) and concluded that there was evidence of serious contamination of the Honda Bay fish stocks.
However, recalculation of these values on a wet-weight basis reduces the concentrations to a more moderate
level (<0.0005 to 2.0 mgkg). Comparison of the wet weight Hg burdens in Honda Bay fish with threshold
values for marketed fish in the USA (0.5 mgkg, US-EPA), and with global average data for species of varying
ecologies (e.g. IRPTC, 1980; Table 1 1 indicates that the mean and, more significantly, the median levels pre-
vailing in the Honda Bay samples are not exceptional. Separation and subsequent statistical analysis of data for
individual specimens caught in the inner and outer sectors of Honda Bay yielded no significant differentiation.
Realistically, all sampled species are extremely motile; hence significant differences across a continuous area
of open water could not be expected.
A subsequent study of fish Hg burdens of 9 species with widely varying ecologies in Honda Bay conducted by
the University of the Philippines showed only two species to carry mean burdens in excess of the US-EPA
marketing threshold of 0.5 mgkg Hg. Highest concentrations (mean 0.924 mg/kg) were found to prevail in a
predatory species (talakitok), for which such values could be considered normal (Piotrowski and Inskip, 1981).
31
Table 10. Mercury burdens in Honda Bay fish (mgkg).
Table 11. Approximate average wet-weight mercury levels (mgkg) in muscle tissues of marine fish in major oceans
worldwide.
- 0.4
0.3
a *
* *
t.
0.2
0.1
' a a
1:
Mackerel Malakapa Salmonete Sap Sap Taba Taba Tuko
Figure 25. Hg in fish from Honda Bay, Palawan compared with the USEPA marketing threshold value (dashed line = 0.5
mgkg).
Mussels. The average wet weight value (2.13 mgkg) and range (0.86 - 4.37 mgkg) established for samples of
Perna Viridis (green mussel) collected from within 10-20 m of the Sitio Honda Bay jetty is almost an order of
magnitude greater than that for Canon Island (mean 0.34 mgkg; Figure 26), located 7 km offshore. The Sitio
Honda Bay mean value falls within the lower quartile of the Minamata shellfish range (1.3 - 14.0 mg/kg),
indicating that mussels and analogous filter feeders from the immediate vicinity of the jetty may be unfit for
human consumption. The contamination of biota in this locality is entirely accordant with the high Hg concen-
trations observed in sediment from the same vicinity (see Benoit et al., 1994; or MGB survey data, September,
1995), and lateral concentration gradients for the two media are probably analogous. Accordingly, it is plausi-
ble that bivalve Hg tissue burdens decline to background within a few hundred metres of the Sitio Honda Bay
source. The maximum Hg concentration recorded in Perna viridis from Canon Island is within the international
background range for shellfish (< 3 mgkg dry weight), signifying that bivalves from the wider Honda Bay may
be suitable for human consumption.
32
E
1 0
m 0
1
H
asel
0
't i
l r
1
Figure 26. Hg in green mussel (Perna Viridis) from close to the Sitio Honda Bay jetty (Honda) and from Canon Island
(Canon).
Neutral-red biomarker assessment results A statistically significant difference (P<O.OOl) was observed
(based on a Student's t-test two sample analysis, assuming unequal variances) between the NRR times deter-
mined for mussels from the Sitio Honda Bay and Canon Island locations. The former had an average NRR-time
of 15 min (&3.0),while latter consistently displayed a retention of approximately 45 min (k4.0). These trends
are consistent with an increased level of toxicological stress and attendant cell dysfunction in the Sitio Honda
Bay sample population. While alternative causes of stress (e.g. between-site temperature, salinity or organic
pollutant variations) have not been specifically discounted, the close correlation between NRR times and Hg
tissue burdens at the two sample sites is most likely to be causal.
33
and transferred to 50 ml graduated test tubes. Ten mg of V205and 5 ml of HN03 was added to each tube, and
the samples were left under air-reflux overnight. The following morning all samples were heated to 140°C for 5
minutes, cooled and 2 ml of H2S04added. After a further heating period of 15 minutes, all solid material was
digested and the solutions were cooled and diluted to an appropriate volume. An aliquot of each solution was
used to determine total Hg content by CVAFS. Analysis of certified reference hair samples (0.36 and 12.3
mgkg Hg) indicated an average recovery of 92% (Williams et al., 1996a)
Hair Resuks
The results indicate that all Palawan residents are subject to high Hg exposure, relative to a control population
from Manila (Figure 27). Within the Palawan groups, only the Santa Lourdes group is statistically different,
possibly because this inland group is likely to consume less fish than the Sitio Honda Bay and Tagburos groups
and is also less exposed to Hg than the Santa Lourdes mine group. Fishermen of Tagburos and Sitio Honda Bay
(Figure 28) yielded a mean hair Hg concentration of 6.49 mgkg, compared to a mean of 2.73 g mgkg for non-
fishermen (of >16 yr. of age in the same localities). This trend has been observed frequently in coastal popula-
tions elsewhere (e.g. Italy, Paccagnella et al., 1973) and is typically equated with fish consumption.
The average hair Hg concentration recorded in the ex-miner group (3.3 mgkg) is slightly lower than re-
corded for the populations of Tagburos and Sitio Honda Bay as a whole, although the median values are almost
identical (Figure 27). All individuals within this group were aged >65 and two have been diagnosed as dis-
playing Hg poisoning symptoms. These individuals, however, yielded the lowest hair Hg burdens within the
group (<2 mgkg). Clinical damage in response to exposure at such levels is, on the basis of worldwide epide-
miological data, extremely unlikely. It is therefore probable that clinical damage was induced by a historical
exposure of a much greater magnitude (i.e. during employment at the PQMI mine). The emergence of Hg
poisoning symptoms in subjects with low hair or blood Hg burdens is common under such circumstances,
reflecting the long post-exposure latency period (approximately 10 years) which characterises several Hg-
responsive human conditions.
Hg in adult males (median 4.52 mgkg) is statistically higher than in adult females (median 2.67 mgkg)
(Figure 29), although these differences are unrelated to body weight and most likely reflect the higher occupa-
tional exposure of males in the fishing sector (Williams et al., 1996a). An evaluation of the Hg status of juve-
nile populations from Sitio Honda Bay and Tagburos showed that age and body mass had little effect on Hg
burdens. However, male children have slightly higher hair Hg than female children (Figure 29) do.
Comparative data on hair mercury concentrations in populations from artisanal gold mining sites in Brazil
and Colombia are presented in Table 12. The high Hg concentrations in hair of riverine populations from the
Tucurui reservoir and the Rio Negro reflect the high daily consumption (0.5 kg/day) of fish containing >2 mg
Hg g-’, which is approximately double that believed to be potentially harmful to human health (Lacerda and
Salomons, 1998).
Table 12. Mercury concentrations in hair samples from prospectors and riverine populations, for which fish is a major
dietary component, of gold mining and non-gold mining sites in Brazil and Colombia (adapted from Lacerda and Salomons,
1998)
34
12,
I
I 8 -
E
-B 7 -
P6-
.-
L
a 5-
I
4-
3-
2-
I
CON EX SL SLM TAG
Figure 27. Hg in hair samples, Palawan. (CON : Manila control group; EX : ex-miners; SHB : Sitio Honda Bay; SL :
Santa Lourdes; SLM : Santa Lourdes Hg mine; TAG : Tagburos).
Figure 28. Hg in hair samples from fishermen compared with non-fishermen >16 years of age (Housekeepers, Others,
Storekeepers) and children (<16 years of age) living in Tagburos and Sitio Honda Bay, Palawan.
18 -
16 -
14 -
ZJ12 -
2 10 -
L
I
S 6
4
CF CM F M
Figure 29. Hg in hair from female (CF) and male (CM) children (e16 years age) and adult females (F) and males (M),
Palawan.
35
Hair-blood relationships
The relationship between hair and blood Hg concentrations, and hence the reliability with which data inter-
comparisons for the two media can be attempted, has been examined extensively through statistical analysis of
global epidemiological datasets (Piotrowski and Inskip, 1981). A reproducible empirical constant for hair is
250 x the simultaneous blood Hg concentration (e.g. Kershaw et al., 1980). Mean blood Hg values inferred
from hair data for the five sample groups ranged from 8.8 - 17.6 ng/ml, with a maximum individual value of
74.1 ng/ml. Such blood Hg concentrations values are typical of populations consuming fish at a daily fre-
quency.
36
Blood concentrations in inhabitants of mining settlements in the SE Amazon region of Brazil are in the
range 90-149 ng/ml methyl mercury which corresponds to 72-99% of the total Hg in the blood (Lacerda and
Salomons, 1998). Lacerda and Salomons (1998) note that most toxicological studies indicate that concentra-
tions are almost always 4 0 n g / d in unexposed individuals, with symptoms typically developing in the range
20-50 ng/ml. With sensitive equipment it is possible to detect ‘shake’ at exposures of 20 ng/ml but the 50 n g / d
would be the level at which to become concerned (pers. comm. 1997, Guy’s and St Thomas’ toxicologists).
This is equivalent to 12.5 mgkg in hair, which is in excess of the WHO ‘acceptable’ threshold level (7 mgkg).
The data obtained in the present study do not fully substantiate the claims made in the Philippine media
during August and September 1995 regarding the occurrence of a major mercury-poisoning episode in Pala-
wan. Total mercury body burdens are not considered to reflect geological or mining influences as statistical
analysis of data for five Palawan sub-groups failed to significantly discriminate between those living on a
mine-waste substrate and other populations. However, it should be noted that these conclusions are based
largely on a single field sampling programme and longer-term monitoring is recommended to gain a more
comprehensive understanding of the sources, environmental behaviour and toxicity of Hg on the island of
Palawan and elsewhere.
Amelioration strategies
Detoxification procedures (typically involving the use of a sulphydryl receptor) are suited to the treatment of
occupational rather than dietary exposure, and is unlikely to provide a long-term mechanism for reducing the
impact of dietary Hg exposure in the coastal communities of Palawan. No record has been encountered of cases
where clinical detoxification has not been proposed, or applied, for the treatment of individuals/populations
exposed via fish consumption. A more common amelioration strategy under such circumstances involves pro-
gressive modification of the diet (notably methods of fish preparation) through community education. Pro-
grammes of this type have been successfully deployed among native American Indian populations in Canada
and the USA.
9.3. I Background
Apokon, near Tagum, is the principal centre for processing gold ore from the major mining areas, including
Diwalwal. Although C P is now the dominant gold extraction method, amalgamation continues to be used,
especially through the direct addition of mercury to ball and rod mills. Tailings from the amalgamation process
are then treated by cyanidation so cyanometallic complexes could have an important role in mercury mobilisa-
tion. Enhanced Hg levels (up to 2.30 mgkg wet weight) have been reported for fish flesh from the Agusan
River and tributary systems draining Diwalwal and Mainit, and from the estuarine outflow of the Agusan at
Butuan Bay (Torres, 1992). In Davao del Norte, air Hg concentrations of 42 - 1664 pg m-3were recorded in
four different gold commercialisation shops, with 65% of samples exceeding the WHO (1976) industrial
exposure limit of 50 pg m-3(Torres, 1992). However, only 6% of 230 potentially exposed workers sampled by
Torres (1994) showed elevated blood levels, and all had urine Hg below 50 pg 1-’.
An initial survey in 1996 by the Philippines Department of Health (DOH) of blood Hg levels in Apokon
residents revealed that the maximum was 20 ng/ml (Williams, 1997). Clear clinical indication of Hg poisoning
was reported and detoxification of residents with >10 ng/ml was proposed and instigated. Media coverage
prompted public and political pressure for compensation of the Apokon residents and for the closure of the
gold processing operations. The response of the DOH to the blood Hg data was unusual because values of up to
20 ng/ml are fairly common in fish-eating communities such as Apokon. It is possible, therefore that the
Apokon residents Hg burden derived principally from fish and was not related to Hg used in the gold process-
ing operations. Interviews with 50 residents from Apokon revealed that the majority consumed fish at least 7
times a week. The 10 ng/ml action level used by the DOH for detoxification could be considered clinically
unsound and arguably unethical; clinical symptoms are virtually impossible to detect at 10 ng/ml and sophisti-
cated instrumentation is required to detect nerve response suppression at 20 ng/ml. An increased risk of mild
non-specific neurological damage may result from life-long exposure beyond a blood Hg threshold of 80 ng/l
(Williams et al., 1996a) or above 200 ngA for shorter exposure. A short-term exposure threshold of 50 n g / d
may be more realistic for the general population whereas 100 ngA may be more appropriate for pregnant
women.
37
9.3.2 Hair sampling
In order to re-assess the toxicological impact, if any, of mercury from the gold processing plants on human Hg
status in the Apokon area, a survey of Hg in the hair of 48 subjects was carried out by the BGS and the MGB in
April 1997. Samples were taken from (1) eight Kimpro workers involved in the CIP processing of tailings
previously treated with mercury; (2) two ballmill operators using mercury; (3) a blow-torch operator involved
in burning amalgam; (4)17 people living within 50 m of the Kimpro, Godenez and Bulbscor processing plants;
and (5) 19 residents from Bar Hall, Omandac, Edgehill and Dabaweno communities located 100-200 m from
the main processing plants.
e
12 - 1
2c18 ° ~
Figure 30. Hg (mgkg) in hair results for Apokon human impact assessment (50m : people living within 50m of CIP
processing plants; BM : ball mill operators using mercury; BT : blow torch operator; CIP : workers at CIP processing plant;
0 : other people not included in previous groups).
38
ner, 1991; CODIGEM & DINAPA, pers. comm.). Part of this mercury (estimated to be about 100 kg per year)
directly contaminates streams and rivers leading to a gradual increase in Hg concentrations in the aquatic
environment. Methyl mercury is more readily taken up by biota and less slowly released than inorganic mer-
cury. Thus bioconcentration factors for methyl mercury are 30 to 900 times greater than for inorganic mercury
(WHO, 1981). Bioconcentration is likely to be further enhanced at the high ambient temperatures prevailing in
hot tropical regions, such as the Ponce Enriquez area. Methylation of inorganic Hg in organic rich stream
sediments would magnify the environmental hazard because methyl mercury is readily absorbed by aquatic
organisms. The potential risk to the economically important shrimp farms located downstream from the Ponce
Enriquez mining district is thus of particular concern.
Conflicting reports were received during the case study survey regarding the use of water from the Rio Siete
for irrigation of the banana plantations and for pumping into the shrimp ponds. Although only a very limited
amount of data is available, there are indications that fish from the estuary of the Rio Siete have Hg concentra-
tions in the range 0.31-0.36 mgkg (wet weight) whereas the few samples of shrimps examined from shrimp
farms adjacent to the Rio Siete contained lower Hg concentrations (0.01-0.04 mgkg, wet weight; unpublished
data). These Hg concentrations in fish do not exceed the human health safety threshold value for marketed fish
in the USA (0.5 mgkg; USEPA) and may fall close to the average concentrations for marine fish in the Pacific
(0.16-0.30 mgkg in tuna and mackerel; 0.07-0.09 mgkg for other non-predatory fish; IRPTC, 1980, quoted in
Williams et al., 1996a). Additional sampling and analysis of both fish and shrimps has been carried out as part
of the World bank funded PRODEMINCA (Sub-components 3.1,3.2) project, but the results have not yet been
reported.
9.5 Cyanide
Although the use of cyanide leaching does carry some environmental risk and also tends to raise somewhat
emotive opposition because cyanides are such well-known poisons, in fact its use is more environmentally
benign than that of mercury. This is because although cyanides are highly toxic, they have a very limited sur-
vival time in natural waters where they are very quickly oxidised to harmless compounds such as bicarbonates,
nitrates and nitrogen gas. Thus a cyanide spill may have an immediate and dramatic toxic effect on river life,
but the toxin will be completely removed by natural processes within a matter of a few days. At Diwalwal,
Ponce Enriquez and Nambija there is evidence from elevated concentrations of Na and C1 in water that gold
cyanidation processes are impacting surface drainage. This is not surprising as most of the cyanidation plants
are located close to rivers (see Figure 12). However, the presence of Na and C1 in river waters need not neces-
sarily indicate that cyanide concentrations are also elevated. Cyanide was not measured during the case studies
reported here.
10. I Introduction
The third major objective of the project was to evaluate alternative gold recovery methods that are particularly
applicable to the artisanal sector and promote their use within the case study areas. This objective was ad-
dressed by carrying out a comprehensive literature review which led to the recommendation that gravity sepa-
ration should be evaluated and promoted as an efficient alternative to mercury amalgamation for the
concentration of fine gold within the small-scale gold mining sector. A simple BGS-designed gravity separator
was constructed and tested under laboratory conditions using Au-bearing material (ore) collected from three
sites in the Philippines. Following design modifications, the gravity separator was tested under field conditions
and donated to the Philippines MGB as a model for the development and construction of full-scale production
equipment. The overall aim of the use of improved gold recovery methods was to help reduce mercury pollu-
tion hazards and their negative impacts on both the environment and human health. The widespread dissemina-
tion of such technologies is beyond the remit of the current TDR project, but is the central objective of a BGS
project which started in April 1998 (R7120: ‘Recovering the lost gold of the developing world’).
39
10.2 Review of gold recovery methods
Table 13. Particle-size range and typical efficiencies of gravity and chemical gold recovery methods
40
Mine
Crusher
I Cyanidation
1
Final tailings
Figure 31. Flow chart for gold beneficiation processes employed by artisanal mining sector in the Philippines and Ecua-
dor. Stages at which Hg is lost to the environment are indicated by the shaded boxes.
10.2.3 Cyanidation
Cyanidation is the process whereby gold is recovered using a cyanide solution. Gold is dissolved using the
cyanide solution and the resulting complex, Au(CN)2, can be removed from solution by various methods
(Deschenes, 1986):
i) The “Merill-Crowe” process, is used to remove the gold from the cyanide by cementation with powdered
zinc.
ii) Activated carbon absorption (otherwise known as C-I-P, carbon-in-pulp) is used for the processing of ores
with a high slimes content which are difficult to treat by the Merrill-Crowe process. Typical gold recovery
efficiencies for cyanidation range from 95 to 99% (Marsden h Fuerstenau, 1993). Cyanidation is more effec-
tive for finer grained gold as it relies on dissolution and is particularly effective for the recovery of gold finer
than 200 pm. Free coarse gold is often recovered prior to cyanidation to avoid the cost of grinding and of the
extra reagents required.
41
Table 14. Relative* cost and potential environmental impact of gold recovery methods
Recovery method Relative* cost Relative* potential en-
vironmental impact
Sluice box 1 1
Jig 3 1
Shaking table 2 1
Spiral 3 1
Rotating cone 2 1
Bowl 4 1
Drum 4 1
Magnetic separation 4 1
Electrostatic separation 4 1
Hydrocycloning 2 1
Froth flotation 3-4 3
Amalgamation (mercury) 2 4
Cyanidation 3-4 3
42
Trommel Screen
500pm Sluice (Au
1 c500pm
Coarse Au;
> 500pm
Tailings <500pm
Sluice (Au
200 -500pm)
Screen 200pm
Fine Au;
fl
Tailings <200pm;
Au c40pm
Figure 32. Flow chart for recommended small-scale sluice box processing
Appropriate configuration
It is recommended that the tilt of the sluice box should increase with increasing particle-size. Typically (in the
Yukon, Canada) for material finer than 1 mm a tilt of 7 to 12" is used. The tilt angle is increased to 12 - 14"for
material coarser than lmm.
43
Processing coarse and fine separately
Operating conditions appropriate for the recovery of coarse-grained gold are different to those for fine-grained
gold. Typically, material containing coarse and fine-grained gold will be processed on the same sluice. This
will invariably lead to a loss of gold. Ideally coarse gold should be recovered on a steep sluice using high feed
and wash rates, whereas fine gold should be recovered on a shallower sluice using lower feed and wash rates. It
is recommended that ore is screened prior to sluicing and the resulting coarse and fine streams are diverted
down different sluices. This will improve overall gold recovery.
10.4. I Introduction
The aim of this work was to construct a simple device, using technology appropriate for less developed coun-
tries, for the recovery of fine-grained gold (e100 pm) from alluvial deposits or crushed bed rock ore. This
device would be, to a large extent, an alternative to the environmentally damaging use of mercury for gold
recovery.
Previous work indicated that the most appropriate method of recovering fine-grained gold is through the use of
a shaking table type gravity separator (Mitchell et al, 1997). Shaking tables are one of the most common forms
of gravity separators in use. They consist of a flat ‘deck’ with parallel riffles that ‘trap’ gold during operation.
During operation the deck is vibrated longitudinally, with an ‘end-knock’ induced at the end of the table where
the concentrate will form. The feed is introduced as a slurry, along with wash water, from the upslope side. The
‘end-knock’ encourages heavy minerals to migrate along the riffles to the end of the deck and light minerals are
washed over the riffles to the downslope side of the deck. Shaking tables are effective in the processing of
material in the size range 3 mm to 50 pm and are capable of recovering up to 90 wt.% of gold present in that
size range.
In the absence of shaking tables, sluice boxes are the most commonly used means of recovering gold from
alluvial gravels and crushed ores in less developed countries. Efficiently operated sluices can achieve gold
recoveries of up to 80 wt.%, whereas the makeshift sluices operated by small-scale miners recover less than 50
wt.%. These low gold recoveries are in part related to the particle-size of the gold. Gold finer than 200 pm will
invariably be lost to the tailings. Other factors leading to poor recoveries include inappropriate sluice box
design and operation, high feed and wash water rates and long time intervals between riffle clean-out to remove
accumulated heavy minerals.
The shaking table constructed as part of this work was designed to be used in Stage 3 of the recommended gold
recovery scheme (Figure 32). A set of samples collected from the Philippines were first characterised and then
used as test materials for the shaking tables.
44
10.4.2 Sample collection for beneficiation tests
A pre-requisite for beneficiation tests was a supply of feed material (hand crushed or milled ore, alluvium),
representative of that currently processed by artisanal miners in the Philippines. On account of the widely
variable granulometry of gold in both primary and alluvial deposits, samples for experimental beneficiation
studies were obtained from a range of settings within two independent gold provinces of the Philippines. These
comprised the small-scale processing operations at Acupan and Kias Creek centred on Baguio (Luzon) and the
Gango mining area near Cagayan de Oro, Mindanao. On account of the nugget effects which characteristically
bias gold assay data for small ore or alluvium samples, a minimum of 20 kg of crushed or milled material was
collected from each site.
Kias Creek
Small-scale workings along Kias Creek, approximately 1 km from the northern end of the Philex mine access
road, are focused along a N-S trending structure within which silicic fault breccia carries up to 100 g/t Au.
Samples were collected from two adjacent millinghecovery plants. The first operated an identical system to
that encountered at Acupan, although overspill tailings were reportedly discarded rather than sold. The second
did not utilise a sluicing system. Instead, the coarse (>150 pm) milled output was panned and amalgamated,
while the fine fraction was fed to an agitation tank containing a sodium cyanide solution. Both milled ore
(BG5) and tailings overspill (BG6) samples were collected from the first of these operations. Due to the nature
of the process described, milled ore only was available from the second (BG7).
Gango
At Gango, near Cagayan de Oro, Mindanao, Au mineralisation occurs in narrow veins in phyllites close to the
contact with serpentinised peridotite. Mining of placer deposits was initiated in 1960 and gold production in
1990 was estimated at 153 g/day, with 18 rod-mills operative for the processing of ore. Until the late 1980s,
gold was amalgamated by the direct addition of Hg during milling, after which the residues were discarded.
More recently, small-scale CIP cyanidation plants have been developed locally, and are utilised on a co-
operative basis. Because the low-recoveries attained by amalgamation, tailings previously treated in this man-
ner (and hence containing Hg-residue) are now being widely reprocessed by CIP operators. Samples (approxi-
mately 15 kg each) of hand- crushed material with an estimated grade of 40 gh were obtained from two
independent adits.
45
10.4.3 Characterisation of gold bearing samples
The mineralogy, gold grade and gold size distribution of the test samples is summarised in Table 15 and Figure
33.
Table 15. Gold assay & mineralogy of gold-bearing samples ‘as received’, Philippines
Note. g/t = grams per tonne. **** = dominant (>50 wt.%), *** = major (20-50 wt.%), ** = minor (7-20 wt.%) and * = trace (c7 wt.%).
Figure 33. Gold grain size (pm) distribution in sluice box feed.
46
Tailingscollector Concentrat
collector
Drive mechanismCam-
-
, 7I Riffies --
Reciprocal motion
I
. 1
4 ~
Water in
pt
l Aain i I0
o[ t
I I
A
7
Or 1
0
10.4.5 Results
The mineral processing trials conducted using the gold-bearing samples from the Philippines confirmed the
effectiveness of shaking tables for recovery of gold, down to a particle-size of approximately 50 pm. Both of
the samples used for the large-scale trials contain a significant proportion of gold finer than 50 pm. Sample BG
5 is coarser than BG 1 with a higher proportion of gold between 125 and 500 pm (Figure 33). This accounts for
the dramatic difference in the processing results. The concentrate produced from BG 1 has a relatively low
gold assay and also only represents a tenth of the gold in the sample. This is probably due to its fine grain size;
the small gold grains were probably entrained within the tailings and swept over the riffles. In contrast, the
concentrate produced from BG 5 has a much higher gold recovery, albeit at a lower gold assay, due mainly to
its coarser particle-size (Table 16).
Table 16. Laboratory results: Gravimetric concentration of gold from ground rock using shaking tables
Au (g/t) original Yield (%) Au (dt)concentrate Gold recovery (wt.%)
AcupanWBGl 97 2.8 1867 57
AcupanBBG1 97 2.5 2305 62
Kias CreekWBG5 12 5.0 360 85
In artisanal gold beneficiation operations, sluice box concentrations are upgraded by panning. This process was
simulated in the laboratory tests by using a ‘Superpanner’ to upgrade concentrates from the shaking tables.
Processing of BG1 using both the Wilfley and BGS-designed shaking tables produced markedly different
results. The Wilfley table concentrate has a gold assay of 25%, but this only represents 10% of the gold present
in the sample; whereas the BGS-designed table concentrate has a gold assay of only 10%, which represents
20% of the gold present in the sample (Table 17). The BGS-designed table has therefore removed a higher
proportion of gold from the original samples, albeit at a lower gold content, but this indicates that it is more
effective than the Wilfley table.
47
Table 17. Laboratory results: Gravimetric concentration of gold from ground rock (using shaking tables with concentrates
upgraded using a ‘Superpanner’)
Another means of comparing the performance of the two shaking tables is to ignore the results of the final
upgrading by Superpanner. The performance of the BGS-designed shaking table is then seen to be comparable
to, if not slightly better than, the Wilfley shaking table (see Table 16, results for Acupan BG1). The gold assays
and recoveries prior to final upgrading by ‘Superpanner’ can be seen in Table 16.
The combined concentrate produced using the BGS-designed shaking table and ‘Superpanner’ resulted in a
product with a slightly higher gold assay and recovery than that produced by the Wilfley shaking table (Table
17). However, despite these small differences the results are effectively identical. This indicates that for gravity
separation the BGS-designed shaking table is as effective as the Wilfley shaking table.
Processing of the tailings samples (BG2 & BG6), using the ‘Superpanner’, yielded similar results to those
produced by processing of the corresponding feed samples (BGl and BG5 respectively) using the Wilfley
table. The proportion of gold recovered from BG6 is approximately four times that recovered from BG2. This
is probably due, as with the difference between BG5 and BGl, to the coarser grain size of the gold present in
the samples from Kias Creek. However, the relatively high proportion (68 wt.%) of gold recovered from BG6
demonstrates that simple methods of gravity separation can be used to extract fine-grained gold from tailings,
provided it is coarser than 50 pm (Table 18).
The results of the investigation have shown that a relatively high proportion of gold can be recovered using
simple gravity methods. However, the gold content of the products has generally been low, less than 1%. This
is a function of the amount of material available for processing, as after each processing stage the amount of
material available for subsequent processing stages decreases. In these studies, a Superpanner was used to
make higher concentrations with around 10% gold and this might be possible using the table if sufficient mate-
rial were available. Processing larger amounts of material would enable further processing stages to be carried
out and production of higher-grade gold concentrates. For example at a mine, the concentrates produced during
a whole day could be reprocessed. There is still a need to establish whether the table could be used to clean the
concentrate to a purity suitable for sale as if not another method for this final stage is still required.
The findings of the investigation have reinforced the value of characterisation prior to mineral processing.
Mineralogy, particle-size and texture all have an influence on the performance of mineral processing trials. For
example, the proportion of gold finer than 50 pm in an ore has a significant effect on the proportion of gold
recoverable using simple gravity methods. Therefore, a determination of the particle-size distribution of gold
could be used to indicate the likely success of using gravity methods for the recovery of gold from a given ore.
48
10.5. I Existing practices
Ore from small mines is carried in sacks to the ‘processing plant’ where the ore is crushed in a ball mill POW-
ered by a diesel engine. After wet milling for a long period (2-3 hours), the slurry is emptied into a ‘washing’
tank (3m by 2m and 50 cm deep), where the slurry is agitated by a miner with a wooden paddle to separate the
mud from the heavier minerals. After washing for about an hour the muddy water and ‘washed’ milled ore are
passed over a shallow sluice, with no riffles, covered with blanket cloth. A heavy, gold bearing, concentrate
collects on the cloth and this is removed periodically by washing the cloths in a large basin. The tailings were
collected for further processing. At Kias the miners no longer use mercury but are now experimenting with
cyanide extraction, both by heap leach and CIF’ separation in an oil drum. The tailings from cyanidation were
disposed of by dumping them in the creek. At Acupan, the main procedures were the same as at Kias, except
that the tailings are sold to Benquet Mining Company.
Laboratory Tests
The field concentrates were further processed with the Superpanner. The concentrate from ore material con-
tained gold with a wide range of grain sizes, with several around 0.5 mm, many around 0.1-0.2 mm, much very
fine gold around 50pm and some down to 20pm. The concentrates were not as rich as those from Kias but
contained far more than was expected from the field examination. The concentrate from tailings contained a
few ‘coarse’ grains around 0.2 mm but most was less than 60pm with many around 30pm (Plate 12). The trials
at Acupan though not as successful as at Kias had actually been far better than was realised at the time. This is
possibly because in the field it was difficult to see the gold due to Fe-oxide coatings on the coarser grains and
the finer grains being hidden in the fine muddy material.
49
10.5.4 Miners reaction to the shaking table trials
The miners at Kias were very impressed by the trials as they had seen fine gold recovered from the tailings
from their current operation. Although they no longer use mercury to try to recover this gold, they were aware
that cyanidation also has associated problems and hazards and could see that a simple gravity method that only
used water was preferable. This was both from a pollution point of view and also because they did not need to
buy relatively expensive reagents. They studied the table in detail and made sketches of it, and asked if it could
be made larger to increase the throughput, which it can. They suggested some modifications to the design and
in particular thought that it could be powered by a belt drive from the ball mill shaft so that it could be run
continuously for long periods without a need for hand winding. Once we had started the trial, several other
miners from nearby mines brought samples of their tailings for testing and similar good results were obtained.
The miners would be very keen to have a table in regular use if it could be produced at a price they could
afford.
The miners at Acupan had been involved in the problems of setting-up the shaking table and were unfortu-
nately unable to appreciate the effectiveness of the table, that was only revealed by laboratory examination of
the field concentrates. They were interested to try it further, particularly due to the reports of successful trials
at Kias the previous day. They were unsure whether this might violate their concession agreement that defi-
nitely precluded the use of chemical extraction.
The MGB staff who were involved in the trials were impressed by the simple construction but effective op-
eration of the table. It was unfortunate that we were unable to demonstrate it to a greater number of staff in
Manila due to the water shortage. The shaking table was donated to MGB and they plan to carry out further
trials and particularly in the mining areas further from Manila where mercury amalgamation is widely used. For
time and logistical reasons, it was not possible to test the table in these areas during a short visit.
10.6 Conclusions
1. Laboratory characterisation of gold bearing ores and tailings from the Philippines established the grade and
grain size distribution of gold within the samples. This showed that they contained dominantly fine-grained
gold with one of the main samples studied having 60% <63pm. References in the literature suggested that
shaking tables are only effective on grain sizes down to about 50pm.
2. Laboratory separation test using a commercially produced laboratory-scale Wilfley table recovered only
20% of the gold from the finest-grained sample but nearly 80% from one that was slightly coarser.
3. A simple, hand-powered, shaking table was designed and constructed of cheap and simple materials that
are available in developing countries. It was particularly aimed at the recovery of fine-grained gold. Labo-
ratory trials showed that this table was as good as and probably slightly more effective for the separation of
fine-grained gold than the commercial Wilfley table.
4. The simple shaking table was taken to the Philippines for field trials. Field trials demonstrated that it is
remarkably good at recovering fine-grained gold when properly set-up and recovered a significant quantity
of gold from miners tailings where the grain size was only around 30pm. The trials also showed how im-
portant and sometimes difficult it can be to adjust the table to the correct settings.
5. The small-scale miners were impressed by the performance of the table and were keen to test it further and
possibly produce a larger version for regular use as an alternative to cyanidation.
6 . A simple shaking table can be very effective for the recovery of fine-grained gold down to a grain-size of
around 20pm and hence could play an important role in providing an alternative to the use of mercury in
the extraction of gold from bulk samples. The heavy mineral concentrates produced contain several weight
percent gold and still require further processing to remove the remaining impurities. This might be possible
with the table but this has not yet been demonstrated. Carefully controlled amalgamation followed by
roasting to release the gold and condensation of the mercury vapour using a retort might still be required.
10.7 Recommendations
1. The use of a shaking table can increase the amount of fine-grained gold recovered during processing of ore.
Figure 35 illustrates the recommended sequence of process stages, incorporating a shaking table, for the re-
covery of fine gold.
50
2. It is assumed that most artisanal gold miners have little knowledge of the particle size distribution of the
gold present in their ore. Therefore, the most practical method of establishing the effectiveness of the
shaking table for the recovery of gold from a particular ore, would be to perform trials.
3. It is also unlikely that the use of mercury amalgamation for the final concentration of gold from gravity
concentrates will be easily replaced. However, its use could be restricted to this stage only. The use of
mercury in tromol mills, sluice beds and other process equipment could be significantly reduced or elimi-
nated by demonstrating the effectiveness of simple gravity techniques.
Ore extraction
v
Gold concentrate Coarse-grained gold
(coarser than 500 recovery
microns) (sluice box stage)
‘Short-circuit’
(ore finer than 500
9
microns)
Final concentration of Tailings
(containing gold
4 0 0 microns)
Gold concentrate
(finer than 500 Fine-grainedgold recovery I
microns) (shaking table stage)
Cyanidation
Tailings
(if significant proportion of
gold <30 microns)
Figure 35. Recommended sequence of process stages, incorporating a shaking table, for the enhanced recovery of fine-
grained gold.
51
I I. LEGISLATION AND ENVIRONMENTAL STANDARDS
Some of the strategies and policies for the small-scale (artisanalandor informal) mining sectors have been evaluated in Mining and
EnvironmentalResearch Network (MERN) Working Papers (Holloway, 1996; Echavania, 1996; Hanai, 1996;Warhurst and Thomas,
1998).
52
damage to the environment and human health. Prior to drafting appropriate legislation it was necessary to (a)
establish practical targets for environmental mercury levels, (b) provide economically viable alternatives to
mercury amalgamation procedures used by the small-scale mining sector and (c) design an appropriate moni-
toring protocol to assist in enforcing environmental controls. In the event, the new Philippines mining laws
were pushed through much faster than had been envisaged, effectively precluding BGS’ involvement in this
aspect of the project programme. Insufficient information has been compiled through the current project to
establish maximum permissible environmental levels (based on impact assessmentldose response data).
One specific problem with regard to environmental standards incorporated in legislation is the lack of suit-
able Certified Reference Materials (CRMs) certified for their content of specific chemical forms (species) of
elements like mercury and arsenic. The lack of CRMs for speciation analysis hampers quality control, although
CRMs for methyl mercury in biological matrices and sediments are reported to be available.
Legislative approaches have serious limitations, especially as a mechanism for controlling the small-scale,
artisanal mining sector. The use of legislation to control working conditions among artisanal miners is com-
mendable in theory but somewhat unrealistic within the context of most artisanal gold mining operations
(Cleary and Thornton, 1994). Legislation for the artisanal sector is in many respects futile as such activities
usually operate beyond the law. For example, at Diwalwal in the Philippines, up to 100,OOO people work a
world class gold deposit which is officially held by four major international companies. In the absence of the
political will to enforce the law, legislative controls will be ineffective. Having a legislative framework does
not necessarily mean that it will be adhered to.
Drivers to bring about change and adoption of safer practices must be economic rather than regulatory. Arti-
sanal miners must be provided with more cost-effective methods of gold beneficiation from which they can
gain tangible economic benefits. These benefits must have immediate impact, as the pre-eminent concern of
people involved in the artisanal mining sector is to earn a living. Human health and financial security over the
long-term is a much lesser concern, as is the impact of their activities on the environment.
In order to bring about the adoption of cleaner technologies and the stakeholder approach to enforcement,
there is a need for educational, training and awareness-raising programmes (e.g. Eve et. al., 1996; Camara et.
al., 1997; Veiga et. al., 1995a, 1995b). Development agencies, and especially NGOs, have a critical role to play
in supporting this approach (Scott, 1998). The implementation of cleaner technologies and the ‘stakeholder’
approach have been the important foci of NGO led projects in Bolivia (Manejo Zntegrado del Medio Ambiente
en la Pequeria Mineria; Appleton, 1998b), Ecuador (Proyecto Mineria sin Contaminacion) and Zimbabwe
(Shamva Mining Centre: run by Intermediate Technology and the Small-scale Miners Association of Zim-
babwe). The projects in Bolivia and Ecuador are advised by PROJEKT-CONSULT GMBHand partly financed by
COTESU(Swiss Government Technical Co-operation)
53
12. DISSEMINATION WORKSHOPS
The project results were promoted at two dissemination workshops held in Quito, Ecuador and La Paz, Bolivia,
and also at the First Asia Pacific Symposium on Environmental Geochemistry held in Hong Kong.
The Quito workshop sessions were attended by up to 73 participants from the state, parastatal, mining and
environmental protection organisations, the university/polytechnic sector, and a wide range of NGO environ-
mental action group. Participants found the workshop both useful and educational and especially highlighted
the wider application of geochemical data for planning, agriculture and other environmental studies. Requests
were received for DFID KAR project reports - these were distributed through the British Geological Mission
in Quito.
The La Paz (Bolivia) workshop provided a forum for discussions between professionals and academics in-
volved in mining, mineral exploration and environmental monitoring as well as representatives of the main
environmental NGO’s in Bolivia. The workshop sessions were attended by up to 95 participants. Participants
were highly complimentary about the workshop, particularly with regard to its practical application of geo-
chemistry to mining potential, environmental contamination and humadanimal health-related problems.
Magnitude of contamination
Monitoring studies highlighted the marked impact of artisanal gold mining on the flux of mercury into the
aquatic environment. In the vicinity of the Diwalwal artisanal gold mining area on the island of Mindanao, in
the Philippines, this impact is particularly notable because of the localised prevalence of ‘dissolved’ Hg at
concentrations hitherto undocumented in artisanal gold mining localities world-wide. The magnitude and
extent of contamination by mercury, derived from both mine tailings and mineral processing activities, and
potentially harmful elements (such as arsenic, copper and lead) derived from sulphide mineralisation is highly
variable, but is generally a predictable function of geological, environmental, social and technological factors.
For example, this project has identified how mangrove systems can act as natural filters for particulate con-
taminants and prevent mercury contaminated sediments from reaching the marine system of Honda Bay, Pala-
Wan.
54
study, for example, such data demonstrated quite clearly that contamination is strictly localised in the near-
shore zone.
Single pollution episodes involving non-persistent contaminants are difficult to detect and quantify in the
absence of continuous monitoring data. This is a very common problem with respect to cyanide, for example,
and nitrate residues have been used in the USA to infer contamination of the aquatic environment. Periodic
releases of contaminants in solution or as suspended matter may be detectable only for a relatively short period
until the contaminant flux passes through the drainage system. Bottom or interfacial sediments are often the
best sample media for non-biological sampling. However, biomarkers, such as those used in the Palawan case
study, are generally more effective because stress induced by short-term exposure is detectable long after the
ambient contaminant level has declined. This is particularly true where species death is involved. From dose-
response data it is possible to tentatively infer exposure magnitude and/or time.
Mineralogical and chemical characterisation of mine and mineral processing waste piles, tailings ponds, and
acid mine drainage is a valuable method for assessing the potential hazards associated with these contaminant
sources. The Palawan case study demonstrated that very high mercury concentrations (in the range 31 to 339
mgkg) found in the Sitio Honda Bay waste substrate are held predominantly in non-sulphide alteration prod-
ucts of probable low bioavailability. The contribution to total human exposure among the Sitio Honda Bay
population (through hand to mouth ingestion and particulate or volatile phase respiration) is therefore likely to
be modest.
55
dictable function of diet. Theses data do not provide clear evidence of abnormal food chain contamination by
mercury andor human exposure via additional pathways, such as hand-to-mouth ingestion of contaminated
soil.
Hair Hg data indicate that ballmill operators and workers at the cyanidation plants processing Hg contami-
nated tailings at eastern Mindanao’s principal gold beneficiation centre, Apokon, may be subject to enhanced
occupational Hg exposure. However, even these workers have Hg hair concentrations which fall within the
range found in fishing communities where there is no exposure to Hg derived from gold processing sources.
Hair Hg data indicate that the wider population of the Apokon area has not been impacted significantly by Hg
contamination related to gold beneficiation.
With regard to human exposure, detailed epidemiological information, and body burden data would be criti-
cal precursors to a full impact assessment. Such studies are now required in the Ponce Enriquez, Nambija and
Diwalwal areas.
56
of the process. Numerous NGOs (such as Intermediate Technology) have tried this approach which in gen-
eral appears to have been unsuccessful. In Ecuador, for example, small-scale gold processors frequently
have retorts but they are never used.
3. Increasing the use of cyanidation in an environmentally acceptable way would reduce the need for amal-
gamation. This would require better control on the location of cyanidation plants and management proce-
dures.
4. Perhaps the greatest potential for reducing environmental impact would be through the adoption of an
effective system of co-operative production. This should lead to better management of mineral processing
plants with reduced environmental impact while still leaving the means of production in the hands of the
poorer sector of the population. In theory it should permit a more effective and economical production
system to be adopted through upsizing production systems and providing access to capital for larger in-
vestments (e.g. shaking tables and efficiently run cyanidation plants). An alternative outcome in areas with
major gold deposits currently being worked by artisanal miners but suitable for large scale exploitation
(e.g. Mindanao) would be to let the mining rights to a major company, evict the artisanal miners and for the
Government to use tax revenues for the benefit of the rural economy.
Finally, coal-oil agglomeration is a novel process that might merit further evaluation. It is reported to have
many advantages compared with conventional amalgamation and cyanidation procedures such as lower opera-
tional and capital costs and less environmental impact. (Marciano et al., 1994; Zhao et al, 1997).
I4.TAKE-UP
The TDR project provided data of direct interest and concern to the Philippines Government and were used to
inform the policy formulation process. In both Palawan and Mindanao the results of the project have materi-
ally affected how and where people live. More important, the project has been instrumental in providing a
balanced input to emotive issues - namely the supposed poisoning of populations on Palawan and Mindanao.
There is a vast array of press cuttings available that highlight the environmental problems associated with
mercury use in the Philippines. The work in the Philippines has been acknowledged as one of BGS's major
successes in the field of environmental geochemistry.
IS. ACKNOWLEDGEMENTS
Logistic support and field guidance in the Philippines was provided by staff of the Philippines Department of
Environment and Natural Resources (Mines and Geosciences Bureau), particularly Tony Apostol, Resty Go-
mez, Juliet Miguel, and Carlos Miranda. In Mindanao, the mine and processing-plant owners and operators for
permission to examine the mining operations and carry out the sampling, and the local people who acted as
guides to some of the more obscure areas. In Palawan, University of the Philippines researchers Ms. Grace
Doming0 and Mr Mike Reyes participated enthusiastically in all aspects of the Palawan field programme and
the additional logistic support was provided by staff of the Puerto Princesa Hospital,. Discussions with Dr G.S.
Jacinto (University of the Philippines) and Dr A. Socrates (Provincial Health Officer, Palawan) were invalu-
able throughout both the design and execution of the case study.
In Ecuador, the collaboration, advice and logistic support provided by Ing. Hug0 Orbea of CODIGEM
(Corporacidn de Desarrollo e Investigacidn Geoldgico-Minero Metalu'rgica), Ing. Milton Carrasco of
DINAPA (Departamento Nacional de Proteccidn Ambiental), Ing. Roque Maldonado of DINAMI (Direccidn
Nacional de Mineria), Swedish Mission consultants, Reider Hoffner, Goran Fredrikson and Bo Erikson
(PRODEMINCA Subcomponents 3.1 and 3.2) and Dr John Aspden and all other members of the resident
Mision Britanica team in Quito is gratefully acknowledged. The assistance and cooperation of Guido Villegran
(CODIGEM driver) during the Ponce Enriquez field campaign is gratefully acknowledged.
Barbara Vickers (BGS) was responsible for the CV-AFS Hg determinations, and Mark Cave and Linda Ault
(BGS) for the ICP-AES analyses. Clive Mitchell, Mike Styles and Ellie Evans (BGS) carried out all the gold
mineral processing laboratory and field investigations. Jason Weekes of the Institute of Terrestrial Ecology
(ITE)carried out the ecotoxicological studies in Palawan.
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APPENDIX I :PROJECTTECHNICAL REPORTS
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