Sohn International Symposium ADVANCED PROCESSING OF METALS AND MATERIALS

VOLUME 5 - NEW, IMPROVED AND EXISTING TECHNOLOGIES:

IRON AND STEEL and RECYCLING AND WASTE TREATMENT
Edited by F. Kongoli and R.G. Reddy TMS (The Minerals, Metals & Materials Society), 2006

ANAEROBIC BIOREMEDIATION OF METALLURGICAL WASTES

USING ORGANIC/WATER EMULSIONS

Robert W. Bartlett

2505 Loch Way, El Dorado Hills, CA 95762-5623

Keywords: Solid Waste, Bioremediation, Organic/Water Emulsions

Abstract

Hazardous metal contaminants in liquid and solid wastes and from ground spills are important
environmental problems in many metallurgical production operations. Acid rock drainage, from
mines and huge quantities of permeable mine waste, is probably the most ubiquitous example.
Fixing mine waste contaminants in situ has been practiced, using sulfate reducing bacteria (SRB)
and organic reagents as electron donors to create anaerobic conditions and precipitate metal
sulfides. Aqueous solutions of sugar and alcohol have been percolated into mine wastes with
good results. However, maintaining anaerobic conditions permanently is unlikely, as these
solutions are eventually washed out of solid waste and contaminated ground by inflow of either
groundwater or meteoric water, allowing re-oxidation from entering air. Emulsions of
inexpensive, non-aqueous organic microdroplets dispersed in water provide earth wettablility
equal to aqueous solutions and easy percolation into both the ground and mine waste.
Subsequent breakdown of the O/W emulsion provides permanent retention of the organic phase,
attached to earth particles, that secures lasting anaerobic conditions, precipitates metals as
sulfides and prevents re-oxidation of these sulfides. This process and its optimization are
described, including experiments with sand-filled columns representing a vertical section
through solid waste. Results of organic and metal retention in solid waste are provided from
analyses of acid mine water drainage before and after waste treatment.

Introduction

Solid and liquid wastes containing hazardous metals are a ubiquitous industrial problem. The
present research focused on permeable solid waste and began with mine waste. Large quantities
of spent ore heaps, previously leached to recover metals, and larger amounts of overburden mine
waste exist at many locations. The residual metals in the broken rock are often present as sulfide
minerals that are easily oxidized and leached causing acid rock drainage. Because of infiltrating
rainfall, this problem continues indefinitely. Consequently, successful mine closure requires
prevention of acid rock drainage. Capping the mine waste with a thick, compacted clay layer to
prevent water infiltration is frequently practiced. A properly engineered clay cap can be
impervious, but it is subject to fracturing and leakage of rainfall if the underlying solids settle,
making it an unreliable method.

Another mine closure method is injection of an organic substance into the contaminated rock to
establish anaerobic conditions and prevent further sulfide mineral oxidation. Bacteria are
usually present that will reduce sulfate and re-precipitate soluble heavy metals and arsenic as
sulfides. The organic substance is an electron donor in this biochemical process. Aqueous
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organic solutions easily infiltrate mine waste. Solutions of carbohydrates, usually molasses and
alcohol, have been used. This method is deemed to be less expensive than clay capping.
However, over time and sufficient rainfall these organic solutions will drain out of the waste,
making this method impermanent.

Petroleum refinery products are less expensive than carbohydrates, but they are non-aqueous
liquids and by themselves cannot wet and penetrate into earth materials, or into the other solid
wastes that are typically encountered. However, hydrocarbon liquid microdroplets, if uniformly
dispersed within solid waste, would likely be permanently retained. A method for accomplishing
this would allow permanent anaerobic conditions to be established within solid wastes, so that
bioremediation processes requiring anaerobic conditions could occur without ceasing. Fixing
heavy metal contaminants in situ as sulfide precipitates using sulfate reducing bacteria is just one
example of this bioremediation approach. Contaminants in solutions entering the solid waste, as
well as the contaminant solution originally contained within the waste, could be treated.

Furthermore, this approach could be used for anaerobic treatment of metal contaminated liquid
wastes, by passing them through a process vessel, containing a permeable bed of hydrocarbon
coated particles. Reducing hazardous Cr+6 to Cr+3 is one example of this approach...

Organic/Water Emulsions and Their Significant Properties

Emulsions of non-aqueous organic microdroplets dispersed in water as the matrix phase have
fluid and rock wetting properties essentially identical with water. They can be infiltrated into
any bed of solid particles that will accept water, including, but not limited to mine waste.

Once in the solid waste, the emulsion must disengage (break) to leave the organic microdroplets
adhering to solid waste particles, but emulsion breaking should not occur before adequate
penetration of the emulsion infiltrating into the waste. Breakage is governed by the emulsifier
(surfactant) chemistry stabilizing the emulsion and by the surface chemistry of the solid particles.
In addition to timely breakage, the organic phase must have acceptably low water solubility, so
that organic rock drainage will not be a problem. Heavy petroleum refinery products are less
water soluble than lighter fractions.

Asphalt, the residue of complete petroleum distillation, is essentially water insoluble, and very
adherent to most solids. Asphalt has a low economic value, among petroleum refinery products,
making it an inexpensive material for an anaerobic bioremediation treatment. Asphalt/water
emulsions are extensively used in highway construction and repair, and readily available. They
are manufactured by feeding liquid asphalt and water, with an emulsifier, into a high shear
reactor, usually a colloid mill. Several commercial grades are manufactured using anionic,
cationic and nonionic emulsifiers, with different setting rates. The rapidity of reacting with
mineral solids is indicated by the setting rate. Commercial emulsions usually contain about sixty
percent asphalt and one percent emulsifier, with the balance water.

The purposes of this research were twofold. First, was to identify a diluted, commercial grade
asphalt/water emulsion that (1) would infiltrate mine waste to a suitable depth, but (2) not allow
subsequent rainwater leaching to drain a significant amount of the asphalt from the mine waste.
Second, was to determine if the asphalt is sufficiently reactive to achieve anaerobic conditions
and remove soluble arsenic and heavy metals from mine water. Asphaltenes are less reactive
electron donors in biochemical processes than are lighter petroleum refinery products. However,
mine waste isnt going anywhere, and rainwater infiltration is usually slow. Hence, reaction time
becomes less critical than it is for many biochemical processes.
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 Infiltration of Asphalt/Water Emulsions in Sand-Filled Columns

Vertical columns, 7.6 cm (3 inch) diameter x 5 m (16 feet) high, were filled with -30 mesh
washed sand to replicate the finer particle fractions in mine waste and the coarser fractions of a
typical mill tailing. The nominal sand grain size was 0.5 mm. Hydraulic conductivity, measured
after water flooding and prior to emulsion addition, was 0.46 mm/sec. Prior to infiltration,
commercial asphalt/water emulsions were diluted with water to 20% asphalt, or less.

Both anionic and cationic emulsions were used. Cationic emulsions break too quickly and
penetrated only a few centimeters, when introduced into the sand, before sealing off the sand and
stopping further infiltration. Sand (silica) and most minerals have anionic surfaces that are
strongly attracted to a cationic emulsifier. Consequently, further experiments with cationic
emulsions were terminated. Satisfactory results were obtained using a slow setting, anionic
asphalt/water emulsion, grade SS-1 h (ASTM D977 and ASSHT M208). Examples of some
experimental results with the SS-1 h emulsion follow.

1500 ml of 20% emulsion were added to the wet, drained sand column at an average superficial
velocity of 0.003 mm/sec, which corresponds to an application rate typical of an impact sprinkler
or drip irrigation system used in ore heap leaching. The column was open to drainage at all
times. Clear drain water was collected steadily, indicating transit of liquid through the column in
nearly plug flow. The final amount of drainage was 1350 ml.

Large emulsion additions were made to a sand column, amounting to an inserted carbon weight
that was 1.5% of the sand weight. After a 21 day column rest period, 4.5 liters of water were
passed through it. This rinsing is equivalent to 40 cm of rain, which is more than the total
amount of rain falling during two years in most of the Western USA. Laboratory analysis
showed the asphalt loss caused by the rinsing to be less than 0.5% of the amount of asphalt in the
sand column.

These experiments show that diluted asphalt emulsion SS-1 h will provide excellent infiltration
into mine waste, with 99+ retention of the injected asphalt within 5m (16 feet) of penetration.
This asphalt penetrated zone is a biocap that potentially substitutes for constructing a compacted
clay cap. As rainwater enters the mine waste, oxygen will be stripped as it percolates through
the biocap, provided the retained asphalt is sufficiently reactive. This will be discussed in the
next section.

The time for rainwater to pass through the top five meters of mine waste depends on the amount
of rainwater and the hydraulic conductivity of the mine waste. For the 30 mesh sand used in
these experiments, continuous raining for more than two months would be required for
infiltrating rainwater to pass through five meters of it.

Heavy Metal and Arsenic Removal Using an Asphalt Emulsion

Approximately one liter batch tests were used to follow the removal of soluble arsenic and
selected heavy metals from solutions within simulated mine wastes. Each batch container was
filled with pea gravel and mixed with 100 ml of asphalt emulsion SS-1 h. While mine waste was
simulated with pea gravel, actual acid rock drainage obtained from Newmont Mining
Companys Rain Mine waste dump, near Carlin, Nevada, was used. This mine water had a pH
of 2.69 and contained large amounts of Group I and II metal sulfates, as well as arsenic and
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heavy metal sulfates. The sulfate concentration was 26 g/L. A biosludge inoculate containing a
natural consortia of sulfate reducing bacteria was grown. A starting liquor was prepared
consisting of 100 ml of biosludge and 10 ml of (NH4)3PO4 in each 2000 ml of Rain Mine acid
rock drainage. This liquor was filled to the brim of each batch container, previously filled with
pea gravel and emulsion, and sealed during the test period.

Upon completion of each batch experiment, the container was opened. Solution was removed,
filtered and analyzed by a certified laboratory using EPA methods, primarily ICP/MS. The
reduction in arsenic and metal concentration indicated that anaerobic conditions were established
in the sealed containers. Once the containers were opened, solutions were exposed to air. Hence,
solutions were not analyzed for oxygen.

The experimental results in Table 1 show a substantial removal of arsenic and heavy metals from
each of the solutions, using asphalt as the only source to obtain anaerobic conditions and
precipitate the soluble species as sulfides.

Table 1. Analysis of Arsenic and Metals in Solution, After Batch Treatment

(Percentages Remaining are Shown in Brackets)

Treatment Species Concentration (micrograms per liter)

Period (days) Fe(T) As Cu Zn .

01 370,000 4,200 14,000 9,000

7 4,200 (1.14%) 15 (0.36%) 2,300 (16.4%) 4,900 (54.5%)

7 4,300 (1.17%) 14 (0.33%) 2,300 (16.4%) 4,900 (54.5%)

28 3,400 (0.92%) 13 (0.31%) 920 (6.6%) 3,000 (33.3%)

120 1,600 (0.43%) 8 (0.19%) 520 (3.7%) 2,200 (24.5%)

EPA Method: 200.7 206.2 200.7 200.7

1. Analysis of acid rock drainage obtained from the Rain Mine waste dump

Conclusions

Infiltrating commercial asphalt/water emulsions into mine waste shows promise as an effective
method of permanently preventing acid mine drainage from mine waste. The dispersed asphalt
microdroplets adhere to particles in the waste. They render it anaerobic and fix metal
contaminants in situ as sulfide precipitates. This method may be less expensive and more
reliable than the present mine closure practice of constructing a thick compacted clay cap over
mine waste. Slow setting, anionic emulsions, diluted with water were most effective. Using
asphalt/water emulsion grade SS-1 h, infiltration in sand, representing mine waste, was not
impeded. Furthermore, 99+ percent of the asphalt was retained in the top five meters of the sand.
In the presence of sulfate reducing bacteria, the asphalt is sufficiently reactive to provide
anaerobic conditions and substantially lower the concentration of soluble arsenic and heavy
metals in mine waste. This approach may be extended to other permeable solid wastes requiring
bioremediation. Metal bearing waste liquids requiring anaerobic bioremediation may be treated
by passing them through a permeable bed of asphalt coated media, contained within a suitable
process vessel.
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