The University of British Columbia

Dept. of Mining Engineering

Earthworms as a Bioindicator of Mercury Pollution

in an Artisanal Gold Mining Community:
Cachoeira do Piri, Brazil
Jennifer J. Hinton
B.A.Sc. Geological Engineering

Marcello Veiga
Professor of Mining Engineering

Outline of Discussion
Mercury and
Artisanal
Gold Mining
Implications

Mercury
in the
Environment

Results

Mercury
in Cachoeira
do Piri

The
Earthworm
Protocol

Mercury and Artisanal Gold Mining

Worldwide:
13 million artisanal miners in 55 countries.
Mercury (Hg) Emissions:

to
Discharged
as tailings,
vapour, pure
Hg on this activity
80
100 million
people worldwide
depend
3000
4000 tonnes of Hg emitted in the Brazilian Amazon
for
their livelihood.
o

Continent

Number of Miners (million)

Asia/Pacific
Africa
Latin America
Developed countries
Total

6.7 - 7.2
3.0 - 3.7
1.4 - 1.6
0.4 - 0.7
11.5 - 13.2

Source: International Labour Organization (1999)

Gold is the main substance extracted:

~ 6 million people extracting 300 - 500 tonnes Au/year.

Exposure Pathways
1. Inhalation

Exposure Pathways
2. Ingestion

Fish may be contaminated several years

after mining activities have ceased

Mercury Transformations

[HgS, HgS2HgS2H-...]
Hgo

CH3SHgCH3

Hg(II)

(CH3 ) 2Hg

CH3Hg+

?
[HgCl2, HgOHCl
Hg(OH)2...]

CH3HgCl
CH3HgOH

Hg-humates, Hg-tannates,
Hg-fulvates

Mercury Transformations
70 to 90% of Hg is methylated
Thesis
Bacteria

CH3Hg+

Colloids

?
Metallic
Hg
Organic Acids

Bioaccumulation and
Biomagnification

Soluble
complexes

CH3Hg+

Bacteria
After Veiga et al. (1999)

Cachoeira do Piri, Brazil

Atlantic Ocean
BRAZIL

BELM
BR-316

Capanema

Cachoeira

Par State

Cachoeira do Piri, Brazil

An island of prosperity in a sea of poverty (Veiga, 1999)

Gold Rush: 1980 1990

-attracted 10,000 people (5000 miners)

- extracted around 4 tonnes

of gold

Cachoeira do Piri, Brazil

More than 4 tonnes of Hg emitted to the environment

Elevated Hg levels in biota (fish, pigs, cattle, humans)

Cachoeira do Piri, Brazil

Bela
Vista

Downstream
~2.5 km

Two Main Mining Areas

Important Fishing Areas
Cachoeira
do Piri

Wetland Zones

Soil/Sediment/Tailings Samples
(collected 1999-2000)

Rio
Macaco
Approx. 1 km

Cachoeira Mercury Distribution

189
202
513

756
445

227

Currutela
Creek
455

13
32

Tailings
155

140

4140

397

385
120
10500
320 2950 1805
1435

3730

455

1090

55 700
32
15
10

55
Barriquinha
Creek

1045
3920

295100

905
1230
10440
1210
3120
1910 135 Lake
Cachoeira

10
00
10
00
0

1720

Cachoeira

6
4

3120

Mercury Concentration (ppb)

Approx. 1 km

Soil/Sediment/Tailings
Samples
(collected 1999-2000)

Cachoeira Mercury Distribution (cont)

Tailings Revegetation in progress

Cachoeira Mercury Distribution (cont)

Effluent from active mining area entering Barriquinha Creek

Cachoeira Mercury Distribution

Cachoeira
Currutela
Creek

Lake
Cachoeira
10
00
10
00
0

Barriquinha
Creek

Mercury Concentration (ppb)

Approx. 1 km

Cachoeira Mercury in Fish

FISH
Exposure
Group

Times above
Safe Limit

Cachoeira
Adult Male
Adult Female
Child (1-4 yrs)
Bela Vista
Adult Male
Adult Female
Child (1-4 yrs)

2
4
14
6
17
56

Hg (ppb)

% > 500 ppb

Carnivorous
Trara

925 ppb

68%

Jej

1274 ppb

100%

Me Rosa

667 ppb

63%

Mandi*

108 ppb

0%

Acar

347 ppb

21%

Piaba

215 ppb

0%

Herbivorous

* Mandi omnivorous

A Comparative Methodology

How to identify/prioritize hot spots?

How do materials influence bioavailability?

Can bioavailability be reduced?

Simple, Low-Cost Methodology Using Earthworms:

Accumulate Heavy Metals from soil and other media

Ingest large quantities of soil and are in full contact with the substrate they
consume

Participate in many food chains

Constitute up to 92% of Invertebrate Biomass in soils

Eisenia foetida species recognized for toxicity testing by several international

organizations (Including: European Economic Community, U.S. EPA, ASTM, etc.)

Invertebrate Protocols
ASTM 1676-95 Standard Guide for conducting laboratory soil toxicity tests for
the Earthworm Eisenia foetida
US EPA 600R94024 Methods for measuring the Toxicity and Bioaccumulation of
Sediment-Associated Contaminants with Freshwater Invertebrates
ASTM 1383-93A Standard Guide for Conducting Sediment Toxicity Tests with
Freshwater Invertebrates
Lockheed Martin Environmental Restoration Program: Development and
Validation of Bioaccumulation Models for Earthworms
Goats and Edwards (1988) Prediction of Field Toxicity of Chemicals to
Earthworms by Laboratory Methods
Hazardous Materials Assessment Team (HMAT) 14-Day Soil Test using
Earthworms

Earthworm Methodology
28d Exposure

#1
#2
#3
#4

Jars

} {

20 Worms
60g Soil/sand
20 g. cellulose

Depuration

+ 80 ml

Distilled Water
Organic Acids

Worms removed, cleaned, weighed

and starved for 24 hrs.

Acid
Digestion

Worms cleaned, weighed and

tissues dissolved in 0.7M HNO3

CVAA

Digested tissues
analyzed

Experimental Program
Earthworm Protocol
B-1

Solutions
Moisture
content assessment

B-2

Organic-rich
and tailings
6 Seriessoil
of Tests

B-3

Humic acid (3) and tailings

Soils / Sediments / Tailings

A-1 Exposure time / depuration

{
A-2

7 Series
of Testsdesign
time
/ experimental

1. Verify
Evaluate
Evaluate
efficacy
of and HgA-3
A-2 the
/ Hgefficacy
dose vs.of
uptake
1. the
Organic
acids
Bioaccumulation
the methodology.
the methodology.
3
different
soils
mixed
w.
tailings
B-4
2. Hg Bioaccumulation in Cachoeira
acidthe
habitability
Compare
effectiveness of
2. Determine influence of
A-42. Humic
3. variables.
Reducing
Hg Bioaccumulation
in Cachoeira
different
soils in inhibiting Hg
specific
Humic
and
tannic
acid
B-5
tailing and lateritic soil
bioavailability.
uptake in humic, tannic acid
A-5 Hg
3. Assess the bioavailability
3. Assess the influence of
seds and tails
of Cachoeira
of Hg-organic
complexes.
B-6 Soils,
organic
Hg to Hg in
MeHg
in acids
wormsonexposed
A-6
Tannic acid tailing / lateritic
bioavailability.
humic,
fulvic and tannic acid

B-7

1.

soil / tails-lat mix

Solution Tests Effect of Organic Acids

Solubility directly linked to
bioaccumulation
Metallic Hg Solubility:
0.56 ng g-1 in water
After 24 hr stirring
(1-6 g of metallic Hg excess removed):
1150-8150 g L-1 in tannic acid
3780 g L-1 in humic acid

Solution Tests Effect of Organic Acids

Test Description

Hg in Tissues*
ppb

Hg Substrate
ppb

2693 (sd 244)

828

2655 (sd 1041)

828

2499 (sd 875)

828

5680 (sd 1625)

828

Series A-3

4359 (sd 1463)

1424

Control worms

178 (sd 15)

Series A-1

Series A-2

* Average of replicates shown

Solution Tests - Methylation and Organic Acids

Worms

Substrate

MeHg
(ppb)

% of Total
Hg

MeHg
(ppb)

% of Total
Hg

HA + Hg

5.22

0.005

0.033

2 x 10-7

HA + Hg

6.19

0.005

0.018

1 x 10-7

TA + Hg

7.42

0.009

0.008

5 x 10-8

TA + Hg

4.22

0.005

0.009

5 x 10-8

TA + Hg

32.2

0.012

0.013

4 x 10-3

FA + Hg

3.14

0.020

0.007

2 x 10-5

FA + Hg

3.11

0.010

0.006

2 x 10-5

Average

4.88

0.009

0.014

7 x 10-6

Description

TA = tannic acid; HA = humic acid; FA = fulvic acid

Methylation Potential of Earthworms

- SRB

++ SRB

CONTROLS WORMS
(with Hg)

+ SRB

WORMS
(no Hg)

++ SRB

+ SRB

+ SRB

WORMS

WORMS

++ SRB

SRB
(TA, no Hg) (HA, no Hg) (culture bin) Innoculant
WORMS

- No SRBs
+ SRBs probable
++ SRBs present

The potential for intestinal methylation of Hg

(or direct bioaccumulation of Hg-organic complexes)
warrants further study!!

Soils Tests Effect of Organic Acids

Hg Solubility - Shake Flasks:
Tailing (10500 ppb)

Tannic Acid
Humic Acid
Distilled Water

210 g/L
110 g/L
12 g/L

Hg Bioavailability Earthworm Experiments*:

Substrate

Tannic Acid

Tailing (10500 ppb)

Lateritic Soil (150 ppb)

5590
3180

Humic Acid
2930
3399

Water
1373
121

*Average of replicates shown

Concentrations shown are Hg in worm tissues in ppb ( g/kg)

Soils Tests Effect of Organic Acids

Hg Bioavailability in association with Tannic Acid (TA):
Tailing (3180 ppb), Lateritic Soil (135 ppb), and Tail/Lat Mixture (1933 ppb)

Tailing + TA > Lateritic Soil + TA > Tailing:Lat Soil + TA

Increasing bioaccumulation

Hg Bioavailability in association with Humic Acid *:

1.
Substrate2.

Organic acids and Hg Bioaccumulation

Humic Acid
Hg Bioaccumulation
in Cachoeira
0.25 g/L 0.125
g/L 0.05 g/L

Distilled
Water

3. Reducing Hg Bioaccumulation in Cachoeira

Tailing (1180 ppb)
129
97
98

48

*Average of replicates shown

Concentrations shown are Hg in worm tissues in ppb ( g/kg)

Bioaccumulation in Cachoeira
Test DescriptionHg in Worm Tissues*
ppb

Hg in Soil
ppb

Tailings

710
190
1373

2925
315
10500

Lateritic Soil

120
1630
1370
120

150
270
1180
90

Organic-rich Soil

380
330
430

3730
205
20

Clayey Sediment

37
250

70
440

*Average of replicates shown

Distilled water applied to Jars

Bela
Vista

Bioaccumulation in
Cachoeira

70
(37)

440
(250)

Downstream
~2.5 km

20
(430)
90
(120)

Important Fishing Areas

205
(330)

Hg (ppb) in Soil
Hg (ppb) in Worms
Cachoeira do Piri

3730 2925
(380) (710)

1180
(1370)
Rio
Macaco

Wetland Zones
Mining Areas

Dense Vegetation
10500
(1373)

Moderate Vegetation

270
(1630)

70 (37)

315
150 (190)
(120)

20 (430)
270 (1630)
N

315 (190)

clay
organic soil
lateritic soil
tailings

Options for Mitigation

Wetland Remediation? May exacerbate problem
Permeable or Impermeable walls? Costly; maintenance/monitoring
Phytoremediation/Phytoextraction? Promising but not yet proven

Information-Based Measures
- Communication of health risks

Appropriate Technical Measures

- Use of local materials to cap hot spots
- Clean lateritic soils or clayey sediments

Reduction of Hg Bioaccumulation
Hg Bioavailability Earthworm Experiments*:
Tailing

Org-rich soil
+ tails

Lateritic Soil Clayey Sediment

+ tails
+ tails

Hg in Tissues*
(ppb)

1370

1247

918

840

Rel. Influence
on Hg uptake

++

++

++ Relatively strong, positive influence on Hg Bioaccumulation

+ Positive influence on Hg Bioaccumulation
Negative influence on Hg Bioaccumulation

*Average of replicates shown

Conclusions:
Hg-organic acid complexation definitely important pathway for
Hg bioavailability:

Solutions: Concentrations in Worm Tissues of 2499 - 6296

ppb following exposure to Hg in tannic acid.

Tailings: 200-540% more uptake in association with humic

and tannic acids than with distilled water.

Lateritic Soil: 100-2810% more uptake in association with

humic and tannic acids than distilled water.

Intestinal Methylation? Methylmercury bioccumulation orders of

magnitude higher in worms than substrate. Also presence of
SRBs.

Significant in terms of current understanding of

biogeochemical cycling of Hg in darkwater systems!

Conclusions:
Hg pollution in Cachoeira presents hazards to area residents:

Soils, Sediments and Tailings:

Hg concentrations range from 5 ppb to 10500 ppb (ave. 695
ppb)

Tailings-associated Hg: Mobilizing from mining areas into

organic-acid rich watercourses.

Fish Consumption:
Residents of Cachoeira 2 to 14 times safe ingestion levels
Residents of Bela Vista 6 to 56 times safe ingestion levels

How can Hg pollution in artisanal mining communities

be mitigated?

Conclusions:
Appropriate responses to effectively mitigate impacts from artisanal
mining activities are critically needed:

Earthworm Methodology:
Low cost, simple method to assess hazards and mitigation
measures

Capping using Local Materials:

Clayey sediments highly effective; Lateritic soils also effective
(except in the presence of organic acids)

Non-technical Measures also needed:

- Educational campaigns
- Consumption advisories

Integrated approaches are the most effective!

Recommendations:

Replicate earthworm experiments statistical confidence in

results.
Assess the methylation potential of earthworms.

Explore mechanisms influencing Hg uptake from lateritic soils in

conjunction with organic acids.

Conduct Risk Assessment in Cachoeira and Bela Vista.

Develop remediation technologies appropriate to artisanal mining

communities.

Develop educational programs and consumption advisories.

Artisanal Mining is an essential economic activity

concrete solutions must be developed!

Many Thanks:

NSERC Operating Grant #217089

Colleagues and Faculty in the Mining Department

My Family and Friends

Research Committee:

Dr. Marcello Veiga Mining Engineering

Dr. Ken Hall Civil Engineering

Dr. Malcolm Scoble Mining Engineering

Dr. Kevin Telmer University of Victoria