JOURNAl OF

GEOGNEHiGAl
EKPLORATION
ELSEVIER Journal of Geochemicd Exploration 52 ( 19Y5 ) 5-23

Environmental impact of metals derived from

mining activities: Processes, predictions, prevention

Mining activities affect relatively smdl areas but can have 3 lurgc local imp;lct on the environment.
Kclc;tsc of metals from mining sites occurs primarily through acid mine drainage and erosion of waste
tlur~~ps and tailings dcposils. The available melhods for predicting xitl mine drainage the fate ol
rclcmxl nwt;ds arc briclly rcvirwcd. Results of one cast study. ;I gcochcmical ~wdcl was usctl lo
predict copper concrnlrxlions in a river system affectal by acid mint drainage alld tailings inputs.
showcil good agrccnwit hclwfcn nwasured and prcdiclcd v;ilucs. For Iqc scale comnicrcial mining
operations, tools IO prcdic~ antI prcvcnt environmental impact arc avail;~hlc. I lowcvcr, mining opcr-
dons involving ;I large numhcr of small-seals activities xc diflicult to con(rol. Gold-mining activities
in f3radil. in which mercury is used to conccnkik gold Itavc already rcsukl in high conccnh-ations
of mercury in fish and may have long-lasting cffccts hr to thr nwchanisms of metal cycling in
tropical forcsI ccosyslcms.

1. Introduction: mining and environmental pathways of melals

Metals arc one of the foundations for the devrlopmenl of our present society. In addition,
many metals are csscntial for lift functions. Mining is only one of the pathways by which
metals enter the environment. The fate of metals from ore bodies deep in the earths crust
IO their final resting place on the surface of the earth. is shown in Fig. I. Mining itscll
affects relatively small areas. It is the tailings and waste rock deposits close to the mining
arca which are the source of the metals. When these deposits contain sulphides (pyrite) and
there is accessof oxygen, acid mine drainage (AMD) results. Depending on the nature of
the waste rock and tailings deposits, this AMD will contain elevated levels of metals. When
these leachates reach rivers, a wider dispersion of the metals both in solution and (after
adsorption) in particulate form is possible. Erosion of waste rock deposits or the direct

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dischqc of tailings in rivers results in the introduction of metals in p;trticulatc form into
arpnnic ocosystcn~s. Smelting of arc conccntratcs rcsultsin the rclcasc of metals to the
atmosphcrc and may. in lict, bc higher compared with the mining nctivitics thcmsclvcs
(Nriagu and Pucyna. 1988; Nriagu, 1990). Manulitcturin~ is the ncx~ step in the release of
rnotals to the environment.
Depending on the efficiency of the recycling of metals. mctnls initi:tlly rclcased by mining
nctivitics end up itficr ti numbsr of. years in the various compnrtmcnts of the surface layer
of the earth. When they hrtvc been rehxscd through the atmosphcrc or into waterways, they
end up as diffuse pollutimts in soils and sediments. Some of the mcutls is discarded with
wustes and ends up in w;Iste disposal sites.
Today, becauseof the efficiency of mining opcmtions, the loss of mcttils to the environ-
ment. based on complete pathways of ths metals. is low. Nevertheless, loceliscd impacts
c;Ln be highly visible and if containment hers not bcrn prxtised, ;LS occurred often in the
past (Moore and Luoma, 1990), dispersion can occur over hundreds of kilomctres. This
article will give a short overview of the basic processes involved in the release of metals
from mining activities and their fate after the release. Tools which are avaihtble to dcterminc
the potcntirrl impact of these releases ;Lre discussed. Two contrasting case studies will he
used to illustrutc the various proccsscs involved.
2. Processes at the mine site

2.1. Acid tninr drcritzctge (AMD)

Prediction of AMD is the key factor in predicting the release of dissolved metals from
active and past mining operations. Within an active mining operation. the AMD can be
generated from a number of sources including waste rock dumps. ore stock piles, tailings
deposits and the mine pit itself. The prerequisite for AMD is the generation of acid at a
faster rate than it can be neutralised by any alkaline materials in the waste; access of oxygen
and water: and a rate of precipitation higher than evaporation. The most common mineral
causing AMD is pyrite, but other metal sulphidcs will also contribute. The oxidation of
pyrite occurs in four steps ( Kleinman et al., I98 I ):

7FeS,+70,+2H,O=~Fe+4SOf-+4H (3)

J Fe+ + IO H20+0,=J Fe(OH),+S H+ (b)

2Fc+0,+2H=ZFe++Hz0 (c)

FeS,+ I-l FL+ +XH,O=lSFe+:!SOf +16H (d)

There are three stages in the process:

Stage 1. Conditions at ;I pH ahovc 43, high sulphatc and low iron conccntr;ltions with
littlc or no acidity. Reaction ( a) proceeds both abiotically and by direct bacterial oxidation.
Reaction (b) is abiotical, and slows down with dccrcasing pll.
Stage II. The pll in shgc II is hctwccn 2.5 and 4.15; thcrc arc high sulphatc levels; acidity
;mtl total iron incrcascs. The Fc /Fc2 ratio is still low. During this stage step (a) proceeds
;Ihiotically and by direct bactcrkd oxidation. Step (h) is prcdomina~~lly dclcrmincd by the
ncli vi ty of 7: f:l,rrtt-0.~ic1trtt.v.
St;igc 111.This sl;igcoccurs al pl I v:~lucs hclow 2.5; high sulphatc and iron levels. The
r;ilioof I? /IQ is high. Reaction (c) is totally dctcrmincd by bactcriid oxidation.
Reaction (cl) is dctcrmincd by the rate of reaction (c).
The rate-dctcrmining s~cp in this whole scqucncc is the formation of Fc( Ill) (Singer and
Stumm, 1970). These three stages are the primary factors, directly involved in the acid
production process ( Fcrguson and Erickson. 19x8). All of the ahovc equations assume that
the mincrill oxidiscd is pyrite and the oxidant is oxygen. Other sulphidc minerals such as
pyrrhotitc and chalcocitc arc also amcnablc to oxidation and acid gcncration. Howcvcr,
rcscarch WI thcsc is limited. The intensity of ilcid generation by these primary factors is
dctcrmincd by chcmicnl p;mmictcrs such 3s pH, tcmpcraturc, oxygen concentrations in the
gas and water phase. chemical activity of iron-Ill. and surfucc ;Irca of the exposed mctul
sulphides. Biological paramctcrs involved include: biological activation encrpy. population
density of the bacteria, rlrtc of bacterial growth and supply of nutrients.
Secondary factors control the consumption or alteration of the products from the acid
generation reactions. Ncutralisation of AMD can occur when carbonate minerals (calcite,
dolomite or carbonates of Sr. Fc or mangancsc) are present. In the tailings deposits. SOIW
CaO is oftcn Icft from the metal extraction process and it can neutralise AMD. The combined
reaction of acid gcncration by pyrite oxidation and ncutralisation of the acid by culcium
carbonate has been dcscrihcd by Williams ( I%?) as:
X

This reaction shows that tuo moles of calcium carbonate are necessary to neutralise the
acid produced by one mole of pyrite. However, the total amount of carbonate is often not
available because the precipitation of iron hydroxide and calcium sulphate can form coatings
around the particles and prevent further neutralisation. Neutralisation by carbonates is ;1
relatively fast process and provides short-term buffering capacity. Acid is also consumed
through reactions with silicate minerals ( long-term buffering capacity ).
Tertiary factors producing and controlling AMD are the physical aspects of the waste
materials that intluence acid production. migration and consumption. The physical charac-
teristics of the mine waste and hydrological factors at the site determine the intensity of the
acid generation. Oxygen advection and diffusion are promoted by coarse-gmined waste,
which results in a high production of acid. Fine-gained material. on the other hand. limits
onygcn diffusion and although the finer-praincd particles have a high surface area (pro-
moting the reactions). the ouypen availability may be limiting. In fact. moditication ol
secondary and tertiary factors may bc looked on ;LS ways of arriving at geochcmical
cn4nccring approaches to prevent AMD.
Fhc dcvelopmcntof AMDkvith timcdcpcndson (hc amount and n;lturcofncid-consuming
minerals in the dump. The step-wise degradation in the pH, with periods of constant pH, is
shown in Fig. 3. This step-wise dcpradation in the pH and the kinetics involved must bc
taken into account in the intcrprctation of the various tests for AMD.
The initiation of AMD c;In bc fast: dumps may start Icnching AMD within one year. Even
under high rainfall conditions such as in the tropics. conditions may develop which citusc
AMD. Howcvcr, thcrc ;Irc also cx;m~plcs whcrc it hook years to dcvclop signikmt AMD.
Scvcrai test proccdurcs x-c nvail&lc for predicting AMI). Idcillly they consist of three steps
( I.apahko. 1003,; krguson NKI Erickson, IOXX; liohcrtson and Kirstcn, IWI):
- slatic tssls;
- kink tests; and
- Ill~~thCllliltilXl iiiotlclling.
Both static and kinetic gcochcmicid INS arc had 011 thl: nssumption th;tt gcochcmical
reactions are (he main factors that control AMD qu;dity. The static tests in use determine

b
fimc (days. years. ccnturics)
pyrite content or total \ulphur content to calculate the potential acidity. Titration procedures
are used to determine the acid-consuming ability. The net base ( net neutralisation) potential
is calculated from the results by subtracting the acid potential from the base potential. In
=CTenerrrl. a negative net value indicates ;L potential acid producer. The static tests. by their
nature. do not provide information on the time scules involved.
Geochemical kinetic tests involve weathering under laboratory conditions or under in-
situ conditions in order to contirm the potential to generate net acidity. and to determine the
rates of acid generation. sulphidr oxidation, neutralisation and metal depletion. Several tests
are available tvhich simulate some. or a combination. of the processes involved in AMD
( Robertson and Kirsten. 1989: Hutchinson and Ellison, 1002). Testing involves leaching
of representative samples and monitorin g water quality over ;I period of months or years
under laboratory or field conditions. Laboratory testing allows greutcst control ofthe factors
involved but extrupolation to the tield requires experience.
Although the basic chemical and biochemical processes involved in the production of
AMD and heavy metal behaviour are rather well known. application of this knowledge to
actual field conditions is still bcsct with uncertainties. The combination of hydrological.
biochemical. chcmicul and physical processes in actual watt dumps makes predictions
during and after mine lift still ;1 moving tar@.
AMD ml bc prevented by controlling the xwss of oxygen to the acid-generating
dcposits. A very efficient mcasurc. if local conditions allow. is to flood the waste deposits
a11d in this way prcvcnting the xxcss of oxygen. Other mcasurcs include covering with
allcrn;iling Iaycrs of malcri;il (clay. gravel. lopsoil 1 and ;I lin;il rcvcgctation programnic lo
prcvcnt erosion. Bactcricidcs have hccn invcstigatcd and arc ahlc to slow down microbial
proccsscs. Howcvcr. they do not last, bccausc they arc suhjcct to tlcgradation. Mcasuremcnts
taken after the end of mint lift arc cxpcnsivc . as is illustrated hy the well-tlocunicntcd cast
of the Rum Ju~~glc mint site in Australia ( I larrics ;md Ritchic, IOXX) by that of the Clark
Ikrk river syskm ( Axtmann and Luoma. 1901 ; Moore and Luol~~il, IWO). Measures which
C;III hc ~akcn, prcfcrably durin, 5 mint lift. dcpcnd on local circumstances such as availahlc
sp;icc. nature oflhc waslc materials. hydrology and sensitivity oflhc surroundings (carrying
capacity) lo impact.

3. Ikhviour of nl~lillS in stremis atid rivers

The kachatc from mining comptsxcs and WUIC rock deposits may drain into nearby
aquatic ccosys~cms. Once in ILL streams the heavy metals can bc transported considerable
distances downstream ( Axtmann and Luoma, I99 I 1. There arc scvcral physical and chcm-
ical processa operating in a stream which can give rise, directly or indirectly, to attenuation
of pollutants. The four main physical pn~csscs arc udvcction. dilution, dispersion and
scdimcntation. Chemical procrsscs include solution reactions, prccipitlrtion, coprccipitation
and adsorption onto strcambcd sediments or suspcndrd particles. Ncutralisation of AMD
C;IUSLSan incrclrsc in pH. The rise in pH C~USCS an adsorption of the dissolved metals on
the various solid phases in the water column. The solid phases interacting with dissolved
 IO

Dissolved copper vg/l

25/

constituents in natural waters corisist of a Variety of components including clay mincrds.

carhonatcs. quartz. fcldspilr and orgnnic solids. These components arc usually coat4 with
hydrous manganese and iron oxides, and hy organic substances. These coiitings regulate to
;I liirge extent the adsorption process ( Salonwns ancl Fiirstner. 19X-l: Hart and Hints. IO04 ).
The most important paramctcr which dcscrihcs the adsorption hchaviour to a lirst approx-
imation is the ptl. Typically, the adsorption ofmct;ds incrcascs from near zero to near I()()%
as pH incrcascs through ;I critical rang 1-Z units wide. This IIIWIIS that ;I rclativcly small
shift in pH in surface water C;IIISCS :I sharp incroasc or rlccrcasc in the conccntriltion ol ;I
dissolvctl mtAill. This hshaviour is a11 ~xan~plc of non-lincw rcsponsc ol heavy nwtals to
~nvironnwnt;II chilngcs ( Salo~n~ns. IO03 ). The onset ol the adsorption is characteristic li)r
each mctd. In natural waters more than OIW heavy metal is prcwnt ilncl compctitivc adsorp-
tion nl:ly titlic ~~;Icc. Major cittions SUCK ;IS Mg or Gil also conlpctc Ihr idsorptiOn sites
with the nictds.
Other dissolved major constituents such as dissolved organic matter. and anions such ;IS
chloride, sulphatc, etc.. may torm dissolved cwnplcxes with the metals and keep them in
solution.
Knowlctlgc ol the mock ol occurrcncc of heavy metals (c.6. their distribution in ionic
forms. their associ;ition with li&llldS :lnrl ilclsorption on suspCnclucl llliltkr) is not simply of
acudcmic intcrcst. hccilusr ~hc ionic form of the mctill is gcncrally the most toxic. If this
toxic form tissoci;ltcs itself with either the suspcndcd mattcror dissolved ligmds. the toxicity
of the surface water or groundwater dccrcascs (Kelly, 198X). Since most of the organic
matter in ;1 water body is usually dissolved organic carbon ( DOC), it may be expectcd that
soluble mrtal-organic complexes can be formed. and this may tend to increase the dissolved
frilction of the metal. DOC dcrivcd from degradation of plant and animal tissues has
functional groups that can form chellrtcs with metals. Humic and fulvic acids can form quite
stable complexes (Tipping and Hurky. 1092). Usually. the DOC levels in rivers vary in
the range I-10 mg/l, while solid ~lnd dsorbcd organic carbon lcvcls varies in the range
0. I-I mg/l. Copper, due to its chcmicd propcrtics. is a metal which is strongly associntcd
with organic matter in surf;lcc waters (Fig. 3). With an incrcasc in DOC concentrations,
the total dissolved copper concentration increases at the expense of copper in suspended
matter (particulate). The increase in dissolved copper is due to the formation of dissolved
organic-copper complexes. Although the total dissolved copper concentrations increase.
the concentrations of the toxic inorganic copper ion decrease. Fig. 3 shows that an increase
in total dissolved copper due to complexation does not necessarily imply an increase in
toxicity.
Dissolved concentrations of metals in surface waters are controlled by a large number of
chemical variables. However. it should not be forgotten that dilution processes also have to
be taken into account when two streams meet. Dilution affects master variables such as pH,
alkalinity and major cation composition. and hence the dissolved concentrations. TempoA
and spatial changes in these parameters. in addition to variable metal inputs. are responsible
for changes in metal concentrations in surface waters on a day-to-day basis.

Erosion from active and inactive mining areas or direct discharge of tailings or waste
rock introduces metals in particulate forms to aquatic environments. These particulates will
bc partly weathered and contain metal forms or discrete minerals which arc stable only
under the geochcmical conditions of the mine site. In addition. the eroded mutcrial may still
contain sulphides. The resulting concentrations of metals in the aquatic environment, are
not determined by adsorption reactions but rather by relcasc from the particulates and
(depending on circumstances) suhscqucnt adsorption. In the cilsc of mctalsulphidcs, a shift
takes place from equilibrium concentrations of dissolved metals which arc indcpendcnt 01
the concentrations in the eroded material: determined by the low soluhility product 01
sulphidcs. to concentrations which are dctcrmincd by adsorption reactions (Fig. 4A).
Bccilusc dissolution is ;I solid state reaction. kin&s play iu1 important role. In addition,
only iI fraction of the particulate mctills will dissolve (Fig. 4B). Part of the minerals will
bc locked up in a silicitte matrix and protected against environmental changes. For modclling
A B
Concentration
in solution
I

Adsorbed phase

phase

Concentration in
solid
Fig. 3. (A) Theccmcl;ltion ofthe concentrations of metals in solution when discrctc minerals arc prcscnt( soiuhility
pnduc~ controlled) and when mcrals arc adsorbed with the concentrations in the solid phase. ( B) Rclcasc of
mctsls from sulphidic prticlcs in crdcd WSIL r(nvk or tailings marcrid.
 Concentratton uq/q
10000
Speciation of copper

mExchangeable
acarbonates
&Zasfly reducible
Ok Tedt @Moderately
reducible
&Nides/orgamc
aResidual

upper Fly
->63pm I 20-63 pm
(75 lJg&l Cu)
I Z-20 vrn I CZprn

purposes it is important to make ;I distinction between the gcochcmicnlly reactive and

inrtctive fractions (Salonions and Eagle, 1990). II modelfing predictions have to hc made
for an active mine over the mine life, it is ncccss;lry lo obtain rcprcscntativc samples of the
ore body rendc:trry out tests to determine the reactive rnctnl riactiot~
It is well known that adsorhcd trrrce metals ;u+cconcentrated in the finciy gckd pru-ticks
(Snlomons and Fiirstncr. 1084 ). The high surface NW and the n;lturc ol the fine grained
p;irticles ( 12.g.organic IlMttCr) IuJ to inany sites for adsorption 0fmct;lls rckrscd in solution
or derived from dissolving discrete rnct;tl miner;11parklcs. An cx;unplc: of the distribution
of metills (in this USC copper) or ;I river influenced by metal mining activity is shown in
Fig. 5.
Copper is mainly present in the liactions < 63 pm; which in-etransported in suspension.
Several constituents of the sedimentary particles ;lre involved in the adsorption and fixation
ofthc heavy metals. In connection with problems ;!rising liotn the disposal o1contau~inatcd
dredge matcri;4, sequential extraction procedures have been dcvclopcd. which include the
successive lonching of metals from sediments (Tessicr et ill., 1979,, Fiirstner. 1993) . The*;c
.
methods heve been applied extensively (and modified) for scdimcnts and soils. Based on
rhcsc operationally &fined sequential extraction procedures, the mcttlls present in soils and
sediments can be classified in various catc@cs (spcciation; see ;riso Table 1).
The distribution of metals over various phases depends on the origin of the sediment or
soil, but in gener4 copper is ti metnl which is associated with organic matter more thornany
other.. The relative amount present in the residual fraction, the fmction remaining after all
extractions have been carried out, dependson the degreeofcontamination. In pristine rivers
more metals wilt report to the inert fraction than in polluted rivers (Gibbs. 1973: Salomons
and Fijrstncr. 1980). In pollured rivers and soils, more metals arc present in the chemically
accessible forms. These kinds of sp&htion schemes thus give ;1 first impression of the
reactivity of the metals on the sediments as wctI3s qualitative informntion on their re&vity
under changing conditions. However. it is not yet possible to derive qutintitative inform&)n
which can be used for mathematical modetling.
 I?

Table I
RclaGvr mobility ad availabiliry offr~c~ mrM\

hlrral species and association hlohility

E.whanprable carionz, High. Changes in the major cationic compwion (e.g.

rstuarinr environment J fwy cauw il rdc9he due 10 ion
exchange
hlrM compound\ associatd with iron and manganew hlcdium. Chongcs in rcdox conditwn~ (reducing
hydroxidex conditions I may cauw II release but if hulphidc i\
present inwlublr metal wlphidec are tivmrd
Mailurn. AtIer decomposition otthe orpanic mawr
Strongly &pendant on rnvironmenkd condilions.
Under oxygen-rich conditions. oxidation ofsulphidr\
occurs

A qualitative interpretation of the mobility and biological availability for the various
fractions is given in Table I.
Hydrological circumstances (e.g. discharge) affect particulate metal concentrations in
river systems. Metal concentrations are low during periods of high discharge. whereas
during low discharge the concentrations may increase by :I factor of 5. Especially for mcfals
which show high increases over base-line levels, the inllucnce of dischnrgc is very strong
(Snlomons and Rirstner. IOX3).
This phcnomcnon is prohahly cnused hy the following effects:
proportional dilution as the discharge incrcascs. assuming :I constant lend of metals into
the river sys~cm;
Dilution as the increased erosion during high discharge (surface run-off) causing ;I
mixing ofcont~uninatcd fluvial par&dates with uncontamiaatcclerotlcd soil particles:
Difference in grain sizecomposition. At low discharge the suspended matter is relatively
liner. The coarser particles are settled on the river bed. Because metals are mainly
associated with the finer particles. the dilution c:tuscd by the less contalninated coarse
particles is absent.
However, the reverse occurs when the river flood plain and other ilreas vulnerable to
erosion are already contaminated. A high discharge with erosion will c;u~seincreased levels
in the river; as a result the contaminants becomemore widely dispersed in the environment
( Bradley. 1084; Bradley and Cox. I986a. b).
Physical mixing of sediments from different origins and with different metal loads causes
changes in metal concentrations in sediments downstream. Natural trileers for sediment
transport can assist in understanding these physical processes ( Salomons and Mook. 1987 ).
In the Fly river system in Papua New Guinea the difference in minerltlogy between the
middle Fly river and the Strickld was used to explain the decreasein metal concentrations
in the lower Fly ( Salomons and Eagle. IWO).

Models arc uv:Glahle which describe adsorption processes in river systems and calculate
the speciation of metals in surf~e waters ( Honeyman and Santschi, 108X). The complex
 I-l

hydrology, sediment transport and biogeochemistry of rivers has to bc coupled Lvith motlcls
describing thr behaviour of metals. The few models actually applied to river systems have
only been for snlall streams and creeks. In a numhcr of cases the fate of mrtals from AMD
has been modrllcd (Chapman ct al., 1983; Chapman et al., 19X8). However, prc-mint
prediction or predictions basal on mint plans arc limited. In one cast a geochcmical model
with simple sediment transport and hydrology routines (Saio1no11s and Eagle, IWO) was
used to predict tht: fate of copper containing tailings and waste rock in ;I major river system.
When larpc dnta scrics arc avail;&lc, statistical motlsls based on the partition cocfficicnt
( K,,) concept can hc uscd to dcrivc rclutionships which tlcscrihc the past hchaviour of the
system. In this way the bchaviour of the past of the river system is consitlcrcd as hcing ;I
chemical oxpcrimcnt from which the necessary prcdictivc constants can hc dcrivcd. Limitcd
cxtrapolntion is possihlc on the assumption that the propcrtics of the tailings and waste rock
do not change and that hydrological conditions also remain the WIIIC. An cxamplc of the
results of such ;I motlcl, for ;L location in the Fly river system, is shown in Fig. 6.
Kcsults obtaincd with all coupled models arc only as rclinble as the weakest link in the
model. If any data on hydrology, scdimcnt lransport, mint plan and prcdictcd propcrtics ol
tailings. waste rock and AMD arc doubtful, then the predictions for metal conccntrntions
will ills0 hitvc large error bars. Even relatively simple modsls such as those which predict
the pll of polishing ponds or rivers receiving AMD art: complex. bccnusc the time &pen&
rncy ofproccsscs such ;IS oxidation rates of Fc( II) and, ifprcscnt, Mn( II). and subsequent
precipitation as hydroxides have to be linked with the hydrology (Mcynink ct al., 1904).
Dcspitc the fact that the results from models for AMD or the fittc of heavy metals and their
biological impact should be used with caution. such models and thrir related monitoring
schrmcs must be part of an environmental management programmc ( Higgins, 1988).

4. Case studies

Bougrtinvillc Copper opcratcd a large open pit mint on Bougainvillc Island. Papua New
Guinea. The mint was locotsd at Panguna, 7(X) m above sea Icvcl in the cutchmcnt arca of
the Kawcrong/Jaha/P~un~una river system. Tailings were discharged to the river system.
The river flows into Empress Augusta Bay OII the west C()iIStof the island. The arc body is
iI low-g& porphyry copper &posit I~:II illso contains SOIIIL' gold and silver. The cnviron-
mcntd impact OII the systc111 id measures IO rcmcdiatc nL,.
*4vc impacts have hccn well
doc~111c111cd (Jcllicy et al.. 198X; Archer et al., 19X8).
Sources of acidity for the river SYS~CIII itrc the AMD from fhc wnstc ~UIII~S and acid
gcncrad in rhc uns:~turiWd patI of the tailings deposits in (11~river flood plain (Fig. 7).
The freely drained sections of the river banks with widths ol IO0 lo 300 m of the channel
ilrt amcnahlc to ilCCLSS01 oxygen.
Drainage from the waste dumps Hows into the Kawcrong river. Low flows iIre largely
due to groundwatcr Ilow from rhc dumps. whereas peak Ilows inch& ;I signilicant amount
of run-off from the nitturd cntchment and dump Ia~s. This run-off Irom the dump fuccs
has little contact with the wastt! rock mutrrial itself. Leuchatr from the w:tsk dumps is the
major input of acidity and soluhlc copper. Rclcasc of dissolved copper was cstimcltd at
1500 [pa (Jeffrey ct al.. 1988). Howcvcr. not all the kd produced from the WWIL dumps
enters the river system. Three types of neulralisation reactions in the waste rock and tailings
deposits were recogniscd:
Fast exchange reactions in which H exchanges with base cations (mainly Ca+ ), This
ncutralisation reaction has a limited impact due IO the low cation exchange capacity
(CEC) of the tailings.
Short-term neutralisation capacity. Neutralisation ofacidic cations by carbonateminerals
which occurs in the tailings IS a result of lime addedto the ore in the concentrator.
Long-term ncutralisation capacity. Neutralisation through the dissolution of silicate min-
erals. This neutralisalion capacity was measured through titration of tailings with Fe3 +.
Al3 + and Cd + solutions over periods of four IO live weeks. Average acid consumption
 2 Log Cu concentration (mg/l) i ~__ _
1

was 100 mEq k;2 _ . with ;I tinal pH of approx. 4. In addition. leaching trials were used
in which fresh tailings were leached with waste dump Icachate. For the tailings deposits
the results showed that the acid generated in the surface. 0.5 m (unsaturated part) could
be neutralised if it passed through an additional 0.5 to I m of tailings. These results show
that only the tailings deposits close to the channels arc of signiticancc for acid input into
the river systcrn.
The neutralisation capacity of the system. as present in the tiiilings and supplied by the
rivers Jab;1and fiu~~i~r;I. wils enough to k~p the pH of the river systcnl ;[t values above 7.
Precipitation of copper compounds from the AMI) was followed by adsorption on the
tailings particks resulting in fairly low copper conccntrutions in the river system. The input
of and thus ncutralisation by the CaO in the tailings will stop after the end-of-mint-lift.
with iI subscqucnt dccrcascin pH of the river system. A pt.1drop is aIs0 cxpcctcd if tailings
;Irc transported by pipe lint directly IO the constnl arc;I. This wils ON of the options for
tailings disposal which was considcrcd to protect the river systcni. To dctcrminc the cnvi-
r()nmLntitI impact of vinious options for tailings disposal. ;I river mani~g~n~cntmodrl was
used IO predict copper concentrations and pH kvcls. The m;ljor components of such a model
arc:
I. acid and tract metal rclcasr: from the waste rock dumps and tailings deposits;
3
_. alkalinity inputs from conccnttator tailings and natural rivers;
3. sorption of trace metals and/or precipitation reactions of trace metals;
4. tract metal compkxation due to organic and inorganic ligands:
5. temporal varirrlions in flow.
The results of some of these scenarios which reprcsrnts tin end-of-mine-life situation
with no tailings (and alkalinity input) or the direct transport of tailings to the coastal arca
(bypassing the river system) xc shown in Fig. 8. In both sccnnrios. the ncutralisation by
(30 is gone but there is still input of AMD and dissolved copper. The results show thitt
copper concrntrations remain high until the Jaba enters the systems and cx~ses the pH to
increase. Malachite prccipitatcs and part of the coppsr also adsorbs on the tailings put-ticks.
Dilution by the Pangura further downstream couscs ;L disappcaranccof malachite 11sII stabk
phase and all copper in the particulate form is adsorbed. Predicted copper concentrations
are around 0.5 mg/l. Thus. only the first part of the river system is still affrctrd strongly by
the mint.
 17

2 4 6 8 10121416162022242628303234

-2
AMD
2 4 6 6 10 12 14 16 16 20 22 24 26 26 30 32 34
Fig. 9. Mcusurcd pH and copper levels in the river system sew-al months afkr clowrc of the mine ( Van dcr
Linden .1997J.

The closure of the Bougainvillc mine due to political unrest provided tin excellent and
unique opportunity to test these model predictions. Several months after the closure. samples
were taken and analysed for copper and pH (Van der Linden, 1992). The pH drop does
indeed take pllrcc (Fig. 9). but before the Jaba enters it already beings to rise again. This
uncxpectcd/unprcdictcd rise is probably due to the erosion of tailings deposits with some
residual GO. The copper concentrations for the main river system show the expected drop,
but concentrations are lower than predicted. Visual observations from the air showed green
banding on the tailings deposits probably due to the formation of malachite. The differences
in predicted and obscrvcd coppcr values may be due to the initial guestimatcs for copper
concentrations in the AMD. In the model, it was assumed, based on the best available
evidence at that time, that the concentrations would be around 300 mg/l. However, actual
concentrations after closure of the mine were lower. This difference and the differences in
pH are probably responsible for the lower values observed for dissolved copper. Neverthe-
less, the agreement between predicted and actually observed values remains quite good.

4.2. Gdrl mining in Brrrzil

Large scale mining for gold in Brazil involves hundreds of thousands of individual miners.
It is an example of how uncontrolled mining can have an important impact on the environ-
ment. Presently the gold mining activity in the Amazon involves circa I.2 million people,
covering an area of circa 170.000 km and with an estimated gold production ranging from
40 to 100 tons per year between 1983 and 1988 ( Lacerda and Salomons, 1992). In 1989,
due to the increasing intensity of the activity as a reflection of the countrys economic
difficulties. a production of circa 200 tons of gold was obtained. ( DNPM, 1983; Souza and
Lins. 1989: Laccrda et al.. 1989; Ferreira and Appcl, 1990. 1991 ). Mercury is used for the
separation of the fine gold particles through amalgamation after a gravimetric preconcen-
nation step to remove the heavy fraction from the river sediments. soils or grounded rock.
depending on the mining site (CETEM, 1989; Souza and Lins. 1989: Garrido et al., lY89:
DNPM. 1983).
The various procedures to recover the gold can be grouped in two basic categories used
in differentgold mining regions. The first involves the recuperation of gold from soils and
rock. with the gold content ranging from 4.0 to 20.0 g per ton. It consists of digging out
large amounts of Au-rich material. generally soils containing quartz veins. and then passing
it through grinding mills and centrifuges to produce a Au-rich gravimetic concentrate. The
concentrate is then moved to small amalgamation ponds. of a few metres square each or to
amalgamation drums, where it is mixed with liquid mercury and then separated in round
pans. The amalgam-Hg mixture obtained is separated by pressing it through leather or cloth
into the highly viscous amalgam ( AuzHg and Au,Hg) and liquid mercury. 11is common to
roast the amalgam in pans in the open air (temperatures of 350 to 600C). thus releasing
nearly all the Hg content of the amalgam directly to the atmosphere. The impure gold. still
with about I% mercury. is sold nearby. Therefore, wherever gold is sold, re-burning is a
most common practice. The practise of roasting at the mining site and re-burning can cause
direct human health risks. Mercury in the form of vapour is resorbed by the lungs in a ratio
of 75 to 80% when it enters the body by respiration. It gets into the kidneys via the
bloodstream and with a half life of approx. two months it is excreted as a Hg-protein
compound. If mercury vapour is inhaled over long periods, chronic mercurial poisoning
occurs (Hentschcl and Priestor. 1992; Marins ct al., 1991; Malm et al., 1990).
Any residue of the concentrate is rcturncd to the amalgamation pond and is rcworkcd
until exhaustion of the gold in the area. After the gold in an area is exhausted. the tailings
left have spots of high Hg concentrations in amalgamation ponds (CETEM, 1989; Andradc
et al.. 1988; Laccrda et al., I99 Ii1, b; Ramos and Costa. 199 I ) .
The second typical process is catricd on in most Amazonian rivers. Gold is extra&d
from bottom sediments by dredging. After removal of large stones, the material is passed
through carpctcd rifllcs which retain heavier particles. This operation takes 20 to 30 hours:
then the dredging stops and the heavy fraction is collcctcd in barrels for amalgamation. The
amalgam is then scparatcd in the same way as dcscribcd ahovc.
According to estimates by Ferreira and Appel ( 1990). of 337 tonnes of Hg imported in
1989. 62% (210 t) was not rccupcrated. Thercfore, they assume that this quantity was lost
mostly to the environment. To these losses gold mining is supposed to contribute with circa
80% ( I68 tonnes). while the chlor-alkali industry contributes 8% and other industrial
activities less than 5%.
The amounts of Hg released into the environment to produce I .O kg of gold in mining
sites in the Amazon are quite variable and depends on the site, the gold containing material
and the gold concentration, as well as the extraction process used (Farid et al., 1991 ).
Observations made by Mallas and Benedict0 ( 1986) in mining sites in Para State, NE
Amazon, where gold is extracted from the soil, yielded values ranging from 2.0 to 4.0 kg
of Hg for I .O kg of Au produced. Pfeiffer and Lacerda ( 1988) have estimated Hg losses to
the environment in a mining site in the Madeira River, Rondonia State, NW Amazon. They
estimated that the major proportion of Hg loss takes place during the burning of the AU-
Hg amalgam, reaching 50% to 60% of the total Hg loss; an extra 5% is vaporised during
the various extraction steps. From 40% to 50% is lost as metallic Hg to rivers during the
amalgamation process. and from 5% to 10% during the recuperation of the mercury used
in the process. In a large survey of 800 mining sites in central Brazil. the National Department
for Mineral Production ( DNPM ) found valuesof circa I.7 kg of Hg for each kg of Au
produced ( Hacon. 1991). Notwithstanding the variability of the reported data, all authors
agree that Hg emissions to the atmosphere are much greater than those to rivers and soils,
and account for 65% to 83% of the total releases.
The effects upon the environment of the release of such large amounts of Hp. will be a
function not only of the total discharge. but mostly of Hg dispersal mechanisms and patterns;
its speciation in the different environments: and the specific ecological conditions of the
complex Amazonian ecosystems.
The evaporated mercury by roasting of the Au : Hp amalgam in gold mining sites released
into the atmosphere is returned to land surfaces and waters with wet and dry deposition and
accumulates in soils and sediments ( Pfeiffer and Lacerda. 1988: Lacerda et al.. 1989; Marins
et al.. 1991 ). This process results in a much broader distribution of mercury than when it is
released into rivers as metallic Hg. reaching remote areas. In these remote areas where there
is no direct inout of Hp from minin,. 7 There is a steady accumulation of Hg in lakes and
reservoir sediments in equilibrium with its atmospheric deposition rates over these arus.
Therefore. sediment cores from remote lakes and reservoirs may provide an excellent way
to determine the history and extent of mercury contamination in gold mining areas.
The distribution of Hg in lake sediment cores was studied in the Pantanal area. which
receives atmospheric inputs of Hg from important gold minin, 17sites located along its
northern border, but not from direct mining cfllucnts. Mercury concentrations wcrc higher
in the surface lake sediments and ranged from 61 to X0 I_L~.kg . dccroasing steadily with
depth to nsarly constant values bctwcon I2 to 30 pg. kg . which arc similar to background
values rcportcd for the arca ( Laccrda ct al.. I991 ). The location of the lakes was approx.
SO km from the main site whcrc refining of ths amalgnm took place. This value gives an
indication of the wide dispersion of mercury through the atmosphcrc.
Contamination of aquatic organisms. in particular of fish. by Hg rclcascd in the environ-
msnt by gold mining activity has been reported in various Amazonian rivers. The highest
tlg concentrations were found in traditional mining sites loca~cd in large amazonian rivers
such as the Madeira River, the larger tributary of the Amazon River. where Hg conccntra-
tions up to 2.7 pg . g - in carnivorous tish were reported and in the Itacaiunas-Par;lobcbas
river system. in the Carajris Mining District in Northern Parti State. where Hg concentrations
in eight fish species ranged from 0.0 I to 2. I9 pg. g _ . Thcsc high concentrations rcllcct
~hc large Ilg load IO the environment due IO gold mining activities. However. they are also
a result of the major environmental conditions of most Amazonian aquatic ecosystems
which favour high rates of Hg methylation. These conditions include, high bacterial activity,
the slightly acidic conditions of most water bodies, fast turnover and high concentrations
of organic matter, and therefore accumulation in high trophic level lish species (Lindqvist
et al.. 1984). At various sites, Hg concentrations in tish are nearly five times the maximum
pcrmissiblo ones for human consumption. Other important organisms for Amazonian food
chains like freshwater snails and aquatic macrophytes also have elevated Hg concentrations
again indicating a widespread contamination of the region ( Laccrda and Salomons, 1992).
A total of IOOO-2lOO tons of mercury has accumulated in the Amazon ecosystem. This
amount will increase, because large undctectcd gold rcscrvcs still exist.
3)

orest rivers
and forest soils:

mercury

There is information available on the cycling of inorganic substances in temperate systems

to infer and predict their long-term impacts. tropic4 ecosystems differin too many ways to
apply this knowlcdgc without critical evaluation. The cycling of inorg;mic substances in the
Ama/.on li,rcst is very efficient (Fig. IO). Biological interactions at the root-soil lcvcl
( miccorhiza) and at the ntnlosphcrc-canopy (epiphylac and high biom;lss ;tnd diversity of
cpiphytcs) arc extrcmcly cfticicnt for the uptake ofnutricnts from atmospheric precipitation.
In tcmpcratc forests this pathways of nutrients is ncgligihlc. In tcmpcratc ccosystcms the
IilrgCr nutrient rcscrvoir is the soil, WhClTiIS in tropicill li)rcst it is the plant biomass itself.
Even when these nutrients ;Irc cvcntually rcturncd to the soil ;ts plant litter. klst dcco~~lpo-

sition rates mcdiatcd by root-iissoci:Wd flu@ rccyclc then\ very f;Ist ;Ivoiding Iilrgc IOSSCS
to the suh-soil itnd out ofthc ccljsystcm.
The m;tjor p;Ithwily Ior mercury in the Anlii/.<)n ccosystcm is Irom the ntmosphcro.
Mercury v;lpour is readily itbsorbcd by plant Icavcs lrom the atmosphcrc. it is likely Ihilt it
will li)llow the s;InIc pathways ;IS nutrients do. This is ;I m;ljor dilfcrcncc from the f;ltc 01
mercury in tompcratc ccosystcms. dominated by in which imtnobilisiltioll in soils iltld in
other slowly cycling cnvironmcntal comp;u?mcnts. In most tcmpcratc ccosystcms. when
sources of a given contaminant ;lrc controlled, one can expsct that through time it will
svcntually itccumul;ltc in long-term sinks. and that the concentrations in cycling compart-
mcnts will constantly dccrctisc. unless the cilp;lcity of the sink is cxcccdcd or cxtcrnal
changes occur.
Through elficient recycling in Amazon ecosystems. mrrcury and other contaminants is
simply move from one biologicnl compartment to another. increasing the probability ol
mcthylation and accumulation in high trophic lcvcls animals. Accumulation of pollutants
in the biomass (tropical system) instead ol in sinks such w soils (tcmpcratc systems)
makes it much more dilficult to mtinage the system once the pollutants have entered it.

5. Conclusions

For mct;ll mining the mnin issue is control of AMD during and after mint lift and erosion
control of w;ts~c rock and tnilings dcposits. Tools arc prcscntly :IviIilitblc which illlow
assessment of the potential for AMD and methods for controlling AMD. However. their
implemrntcltion depends on local conditions and economics. Revegetation has been carried
out successfully in temperate climates and information is becoming available on how to
handle revepetation under the more adverse conditions of the tropics. Modellinp of the fate
of metals discharged by mining activities in streams and rivers has shown some promise
and models con be used as management tools to evaluate the potential impact of ;L mine
plan. During mine life a continuous assessment of current and future impacts sould be
carried out, taking into account the carrying capacity of the surrounding environment. Such
a strategy can anticipate and prevent undesirable impacts and will be more economical than
taking action after the event.
Past evidence has shown that uncontrolled mining can have a large and lasting impact
on the environment and this situation still exists when controls arc difficult to implement.
as is the case when a large number of individual miners are involved.

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SIIUU. V.P. and Lins. F.A.F.. IYSV. Recupsracao do ours pw am~l~;lm;l~;1~~
e ~~~ewx~. Ser. Trcnol. hlineral.
Crtrm-CNPq. 44: l-27.
To\ier. A.. Cumphcll. P.G.C. and Blwm. hl.. I97Y Srqurntial eitrac!aon prtxaiure for the \peciation cd partic-
ulate metals. Anal. Chrm.. 5 I : X4-bXS I.
TIpping. E. and Hurlry. M.A.. 1092. A unifying mcdtl of catitw h~nchn~ h! hums wh~tancr~. Gccwhim Co\-
mtxhim. Actn. 56: 2627-364 I
\'JII der Linden. 1.. I YO?. Pcrwnal coIIlIIIurlic;itI(~ri~.
U~ll~;nns. E.G.. 19X?. Factor\ wnrrolling the gcncr;~tion ofacid mint Jr;un.~;c. Rcpc~fl10 the I:mtcd Sratcs Bureau
of Mince.