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Analysis of Mining Sites in California and the Feasibility of Monitored Natural Attenuation
Abigail Hartman
ENVL 3531-001
Dr. Hallagan
05/01/20
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Abstract:
Ranging in location, climate and topography, four mining sites (A-D) located in
California will be thoroughly evaluated. Each mining site is used for the production of different
mineral ores, lead (Pb2+), copper (Cu2+), mercury (Hg2+) and chromium (Cr2+) and have a high
risk for acid mine drainage (AMD). The purpose of this paper is to consider the feasibility of
monitored natural attenuation (MNA) as a remedial strategy for each mining site, and to
calculate how effective the results would be. Monitored natural attenuation is a common
remediation practice used for that is inexpensive and used for low risk sites. This remedial
strategy is reliant on the soil chemistry and biology as a method to control the contaminants
mobility and bioavailability. The Environmental Protective Agency defines natural attenuation as
contaminants in soils and groundwater. Basic physical and chemical interactions between soil
particles and contaminants of concern (COC), such as exchange and solubility, will be an
important factor in determining the productivity of MNA over time. The thesis of this paper is
using data from the sequential extraction procedure (SEP) for MNA, major sinks for treated soils
will be recognized, and used to determine a method for removing different levels (mg/kg) of
contaminants (Pb2+, Cu2+, Hg2+, Cr2+). Conclusions will be determined focusing on SEP data and
site specific data, such as soil texture, exchange and organic matter content.
Introduction:
Throughout American history, California has remained one of the leading states for the
production of non-fuel minerals, having a valued income of around 3-4 billion US dollars per
year. In 1848, the Gold Rush was responsible for migrating 300,000 people into the state of
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California in the pursuit of wealth. This significant event had a devastating effect on the
environment and shaped California's landscape by degrading soil chemistry, fluvial systems,
vegetation productivity and the land's geomorphology. In 2019, California reported having 700
active mining sites, and nearly 20,000 abandoned sites. An estimated 3,000 of these abandoned
mines contain hazardous mine openings, commonly referred to as waste passes. The leftover
waste, commonly called tailings, are leachable residues varying in size depending on the type of
Modern mining practices release large quantities of trace metals that are able to bind
themselves to soil colloids using cation exchange capacity. Near mining sites, commonly found
metal contaminants in the soil are lead, zinc, copper, mercury, and chromium (Wilkins, 2008).
Abandoned and active mining sites pose a global issue due to the dispersal and mobility of
common trace metals, and their ability to reside in a specific area for up to a century. As heavy
metals and sulfuric acid begin to accumulate, erosion occurs, and AMD is produced. This type of
by product from mining causes a large ecological destruction in waterbodies and kills off any
living organisms in the area. Acid mine drainage is a main pollutant and occurs after being
exposed to water, air and metal sulfides oxidizing and generating acidity (Sparks, 2003). In large
quantities, these hazardous metals are detrimental to soil formation and natural systems, causing
toxic effects to humans, biota, and microorganisms. Plants are at high risk due to their ability to
absorb metal airborne pollution through their leaves, damaging cell membranes, and lessening
Sites that are left abandoned after mining different metal ores will commonly need to go
through MNA as a remedial strategy in order to control the mobility and solubility of these metal
contaminants. If these contaminants are removed from each site using MNA, soil formation will
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continue and be uninterrupted by contaminants. If sites are left alone and not treated using MNA,
metal contaminants will continue to be retained in the soils and overtime lead to AMD. Data
using the sequential extraction procedure will be beneficial in determining methodology for each
site. This is an analytical process that collects data on potential sinks for the metal contaminants
by leaching the metal out of the soil samples. Thesis of this paper is using data from the
sequential extraction procedure (SEP) for MNA, major sinks for untreated/treated soils will be
recognized and used to determine methods for removing different levels (mg/kg) of contaminants
B 0.319 0.95 0.80 0.70 0.70 9.80 9.60 9.60 9.60 0.43 2.00
C 0.398 2.20 2.15 2.10 2.10 17.50 17.50 17.50 17.50 0.24 4.00
D 0.487 1.60 1.50 1.50 1.50 35.00 35.00 36.00 37.00 0.20 4.00
Table 2. Sequential extraction procedure (SEP) breakdown for contaminants of concern (COC). The first pH
listed is for the original site conditions, and the second is for pH adjustment using lime as a soil amendment.
Residual
Soluble Bound Bound to Bound Total
SEP Exchange- Bound to (Phosphate
COC (DI to Oxides/ to Levels
pH able Carbonates and
Water) SOM Hydroxides Sulfides (mg/kg)
Silicate)
5.8 49 65 41 125 237 101 329 947
Pb 7.0 12 15 52 137 277 119 335 947
6.1 27 25 31 19 77 47 161 397
Cu 7.0 20 23 34 21 89 44 149 397
7.3 0.5 0.2 6 0.2 4 1 7.3 21
Hg 7.0 0.3 0.1 6 0.1 4 1 9.5 21
6.3 7 4 21 35 76 30 68 219
Cr 7.0 5 4 25 55 68 45 17 219
Table 3. This table shows the redox potential, OM% and CEC ratings for different depths at each site.
Note: The erosion factor K measures the rate of soil to rill and sheet erosion, and the higher the
value, the more susceptible the soil is to rill and sheet erosion by water. The T factor is an estimate
of the maximum average annual rate of soil erosion due to wind and/or water.
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Site A is located at a Galena cave in Wilsonia California and is used for the extraction of
lead (Pb2+). Lead II does not biodegrade, decay or dissipate, allowing this element to have the
ability to be strongly retained in soil (Sparks, 2003). Galena is a metallic lead sulfide (PbS)
mineral and is the most common ore mined on Earth. Mining from a Galena cave is one of the
only commercially viable way of extracting lead, but during this metal mining process, harmful
sulfuric acid is excreted. Galena mineral ores contain metal sulfides, and when water binds with
these sulfur bearing materials in the presence of oxygen, acid mine drainage is created. This site
has a high chance of experiencing acid mine drainage, due to the high chance of surface runoff
and large amount of pollutants in the soil (Kushwaha, 2018). Site A is located in the Central part
of the state, in Tulare County, and has a dry sub-humid mesothermal climate with warm, dry
summers, and cool, moist winters (Web Soil Survey, 2020). The mean annual precipitation is
around 16 inches and the mean annual air temperature is around 62°F.
The major soil series for site A is the Las Posas series, located on mountainous upland
regions, ranging anywhere from 200 to 3,000 feet in elevation. The major soil order located in
site A is alfisols, and the taxonomic classification is fine, kaolinitic, thermic Typic Rhodoxeralfs
(Web Soil Survey, 2020). The soil texture is a fine loam mixture, likely to experience high
surface runoff and slow permeability. This site experiences high amounts of waste material and
erosion per year (Table 3), based on the K factor, 0.37, and the T factor, 3 tons per acre per year.
Alfisols are moderately weathered soils that are commonly found in glaciated areas and show
extensive development. are well-drained soils, have a medium to high base saturation, and a
distinct argillic/kandic sub-horizon (Bt) (Sparks, 2003). In site A, the mineral properties of
kaolinite are likely to create a kandic sub-horizon with a low charge, typically due to a low CEC,
2-15 cmolc kg-1. Based on Table 3, the percentage of organic matter decreases below 10 cm, and
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the clay content and CEC beings to increase. Site A has a pH of 5.8, and contains the highest
amount of pollutants, 947 mg/kg of Pb2+. The pH of soil in these sites will greatly impact the pH
dependent properties, such as soil organic matter (SOM). Soil organic matter usually has a
negative charge, due to the presence of carboxyl and phenolic groups (Sparks, 2003). These site
properties are pH dependent and with a neutral pH (7), solubility and exchangeability of Pb2+
decreases.
Site B is located at a clearwater mine in Hi Vista California and is used for the extraction
of copper (Cu2+). Pilings from copper mining waste are highly erodible and make the land
susceptible to experiencing acid mine drainage. When mining for Cu2+ highly acidic discharge is
released containing copper-iron-sulfides, thus becoming a major culprit of acid mine drainage
(Wilkins, 2008). The location of site B is in the Angeles National Forest area, in Los Angeles
County, along the San Gabriel and Sierra Pelona Mountains. The climate is semiarid
mesothermal with dry warm summers and somewhat moist cool winters (Web Soil Survey,
2020). The mean annual precipitation of site B is around 10 inches and the mean annual air
temperature is around 62°F. The major soil series for site B is the Trigas series, located on
dissected fan terrace regions, ranging anywhere from 200 to 2,000 feet in elevation (Web Soil
Survey, 2020).
The major soil order located in site B is Entisols, and the taxonomic classification is
Loamy, mixed, superactive, nonacid, thermic, shallow Typic Xerorthents (Web Soil Survey,
2020). The soil texture in site B is fine sandy loam mix, likely to experience high rates of surface
run off and moderately rapid permeability. Based on Table 3, this site is the most susceptible to
rill and sheet erosion by water, K factor is 0.43, and has a T factor of 2 tons of soil erosion per
acre per year due to wind and water. Entisols are soils that are recently formed and commonly
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found in extremely steep and rocky environments. The soil development of Entisols are heavily
limited by climate and time, and a various of other site-specific factors, such as soil moisture,
particle size, litterfall and aerobic decomposition rate (Sparks, 2003). In area with more
precipitation, iron oxides get coated and lots of the exchange sites are blocked. Entisols in site A
are likely to experience fast rates of aerobic decomposition and consist of an ochric epipedon.
Ochric epipedons include eluvial horizons of thin organic layers, and have base saturations less
than 50 percent (USDA, 2014). Based on Table 3 for site B, the percentage of organic matter
decreases below 10cm and the CEC is low and consistent throughout. This site has the lowest
amount of organic matter and a high percentage of sand, likely to experience excessive drainage
(Web Soil Survey, 2020). Site B has a pH of 6.1, and contains a large amount of pollutants, 397
mg/kg of Cu2+.
Site C is located in a gypsy mine in Los Banos California and is used for the extraction of
mercury (Hg2+). Mercury is a persistent soil contaminant that greatly affects soil respiration,
structure and reduces microbial activity (Sparks, 2003). This element is likely to form in a
sulfide ore, called cinnabar found in gypsum crystals. A sulfur bearing ore is used to extract Hg,
and when combined with oxygen and other hazardous waste materials, acid mine drainage is
likely to occur at this site (Sparks, 2003). Site C has a sub-humid climate with dry, warm
summers and moist, cool winters (Web Soil Survey, 2020). The mean annual precipitation is 15
The major soil series for site C is the Laveaga series, located commonly on hillslopes of
mountains, ranging from 1,100 to 3,300 ft in elevation. This soil series is weathered from
andesitic flows and agglomerates, resulting in deep, well-drained soils (Web Soil Survey, 2020).
The major soil order located in site is mollisols, and the taxonomic classification if fine, mixed,
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mesic Typic Argixerolls (Web Soil Survey, 2020). The soil texture is sandy clay loam, likely to
experience slow permeability and medium to rapid surface runoff. Site C experiences high
amounts of erosion annually (Table 3), based on the K factor, 0.24, and T factor, 4 tons per acre
per year. This site experiences high annual rainfall leading to high amounts of soil erosion from
water and wind. Mollisols are dark soils that commonly have high CEC, a mollic epipedon and a
high base saturation throughout. Mollisols are commonly rich in organic matter and have mollic
epipedons that are derived from the addition of organic materials (USDA, 2014). The mollisols
in site C have an argillic horizon, consisting of clay accumulations with moderate to high charge
and exchange. Based on Table 3, this site has the highest percentage of organic matter and
moderately high CEC that both stay consistent with depth. With high amounts of SOM, this site
is likely to experience low amounts of dissolved organic matter. Mercury is a bio accumulative
pollutant and the rate of sorption is likely to decrease with a pH above 5 (Sparks, 2003). Site C
has a pH of 7.3, and contains the lowest amount of contaminants, 21 mg/kg of Hg2+.
Site D is located at a rough crossing mine in Old Adobe California and is used for the
extraction of chromium (Cr2+). Using both underground and surface mining techniques, this
metallic elements mining process relies on the reduced form of Cr2+, Cr3+. The reduced form,
Cr3+, is the only ore that is commercially viable to extract (Sparks, 2003). Soil pH and the
percentage of organic matter play a huge role in the potential reduction of Cr2+ into Cr3+ (Web
Soil Survey, 2020). Chromium is a sensitive element that depending on the specific site
conditions, can change from one form to another, likely to increase in toxicity (Sparks, 2003).
The climate is sub-humid mesothermal with dry, warm summers and moist, cold winters (Web
Soil Survey, 2020). The mean annual precipitation is around 16 to 24 inches and the mean annual
air temperature is about 61°F. The depth to lithic contact in this area is around 20 to 40 inches
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(Web Soil Survey, 2020). During the dry period in this location, it is common for soil to crack
vertically to lithic material. With high annual precipitation, cracking occurs less frequently and
there is significant movement in the subsoil, likely to cause issues with roadways, infrastructure
and buildings.
The major soil series for this site is the Cibo series, located along foothills and
mountainous upland regions, ranging from 50 to 4,600 feet in elevation. The major soil order in
site D is vertisols, and the taxonomic classification is clayey loam mix, montmorillonitic, thermic
Typic Chromoxererts (Web Soil Survey, 2020). The soil texture of site D is a clayey loam mix
(Cibo clay), likely to experience slow permeability and medium to very rapid surface runoff in
the moist seasons (Web Soil Survey, 2020). Vertisols are known as productive soils based on a
high percentage of clay content, exchange and isomorphic substitution. Vertisols are soils with
high shrink-swell clays (montmorillonite in this area) that crack to depths of 1 meter or more.
Montmorillonite has the ability to adsorb water in its interlayer and become hydrated, leading to
ground swelling (Sparks, 2003). Based on Table 3 for site D, the organic matter is consistent,
and the CEC rating is very high throughout. This site is likely to experience slow drainage rates,
Site D has a pH of 6.3 and contains 219 mg/kg of Cr3+ in its oxyanion form.
Methods:
When beginning to examine sites A-D for MNA, each site needs to be preliminarily
screened for specific properties, such as soil texture, CEC, pH and redox potential (Eh). Texture
by feel methods, such as the ribbon and ball test, can be performed to determine soil texture and
estimate the percentage of clay content. The CEC for sites A-D can best be determined using an
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ammonium chloride (NH4Cl) extraction requiring no pH buffer. This extraction method involves
adding reagents and centrifuging soils to remove soluble salts, extract exchangeable cations and
extract ammonium for analysis. The soil pH of each site can be easily determined by placing a
pH meter into a damp section of the soil. It would be beneficial to take multiple pH readings
around each site, giving us ranges in pH for each location. The pH measures the activity of the
protons (hydrogen ions) while the redox potential measures the activity of electrons. Redox
potential is a measure of a chemical species tendency to lose or gain electrons (Sparks, 2003). To
measure the redox potential in soils (Eh), electrodes are used to detect the oxidizing and reducing
agent of the system. These reactions can then be broken down into half reactions for a more
accurate measurement. The redox potential of soil strongly affects the ionic forms of many atoms
and molecules and these ionic forms determine solubility and or reactivity.
Screening for these site properties will be beneficial for MNA results because each
contaminant has specific natural attenuation pathways and contraindicators. When collecting
samples to determine the feasibility of MNA, it is important to close off the area to prevent any
using a score card to determine data needs, attenuation mechanisms and to develop a conceptual
MNA work plan. During this case study SEP is the method used to analyze for metal fractions in
soils. Sequential extraction procedure is performed to characterize metal sinks and provide
qualitive assessments of metal attenuation mechanisms. This data is useful because it provides
means of assessing long-term stability of natural attenuation and aids in determining mass of
Graph 1: This graph shows the major sinks from SEP data for lead, before and after lime application.
400
350
300
250
200
150 Lead Sinks pH 5.8
100 Lead Sinks pH 7.0
50
0
Bound to SOM Bound to Bound to Oxides/ Bound to Sulfides Residual
Carbonates Hydroxides (Phosphate and
Silicate)
For site A, the increased pH adjustment greatly reduced the amount of exchange and
solubility for Pb (Table 2). The major sinks for Pb are carbonates, oxides/hydroxides, and the
residual fraction. Lead has sorption to iron hydroxides, organic matter, noncrystalline
sulfides, sulfates and phosphates (Brady, 2003). Looking at data from Graph 1, Pb bonds more
effectively to SOM, carbonates, oxides/hydroxides, and sulfides with a pH of 7. Sites with a low
pH and high metal solubility can be cheaply treated with simply adjusting the pH and increasing
the redox potential. To increase the redox potential above 0.298 (Table 3), organic matter can be
added to the soil providing microbes with a major electron and food source (Sparks, 2003).
Monitored natural attenuation will be effective at this site with the application of lime, organic
matter and iron oxides into the soil, but because of the large amount of COC, this site will need
Graph 2: This graph shows the major sinks from SEP data for copper, before and after lime application.
140
120
100
80 Copper Sink pH 6.1
60
40 Copper Sink pH 7.0
20
0
Bound to SOM Bound to Bound to Bound to Residual
Carbonates Oxides/ Sulfides (Phosphate and
Hydroxides Silicate)
For site B, the increased pH adjustment slightly reduced the amount of exchange and
solubility for Cu (Table 2). The major sinks for Cu are oxides/hydroxides, sulfides and the
organic matter and silicate clays; sparingly soluble to carbonates, hydroxide and sulfides (Brady,
2003). Looking at SEP data from Graph 2, Cu with a neutral pH of 7, bonds more efficiently to
SOM, carbonates, and oxides/hydroxides. Dealing with MNA for site B, it might be beneficial to
add organic material, or iron oxides to the soil to increase the soils redox potential above 0.319
(Table 3). By increasing the redox potential of this site, we will be allowing more electrons to be
transferred between chemical species. With a higher redox potential in the soil, contaminants
will be removed more efficiently from MNA. This site experiences the highest rate of erosion, so
for MNA to be successful this site needs to be watched for over three years, with frequent
Graph 3: This graph shows the major sinks from SEP data for mercury, before and after lime application.
10
8
6
4 Mercury Sink pH 7.3
2 Mercury Sink pH 7.0
0
Bound to SOM Bound to Bound to Oxides/ Bound to Sulfides Residual
Carbonates Hydroxides (Phosphate and
Silicate)
For site C, the decreased pH adjustment reduced the amount of exchange and solubility
for Hg (Table 2). The major sinks for Hg are SOM, oxides/hydroxides, and the residual fraction.
Mercury gives formation to sparingly soluble sulfides and has sorption to organic matter (Brady,
2003). Looking at the data for SEP (Graph 3), by decreasing the pH to 7, solubility and the
amount of Hg bonded to carbonates decreased, and the residual fraction increased. The amount
of Hg2+ that bonded to SOM, oxides/hydroxides, and sulfides did not change after lowering the
pH. Mercury will have a higher solubility and exchange at a higher pH, making the application
of lime unnecessary at this site. Overtime MNA will remove these metal contaminants in the soil
because of the high CEC, high OM percentage, and high redox potential. With a high redox
potential, the species in this soil tend to gain electrons from new species (Brady, 2003). In
are able to transform this toxic trace metal into a highly bioaccumulated contaminant, called
methylmercury (MeHg) (Brady, 2003). This site has the lowest amount of pollutants but due to
the toxicity and health hazards of Hg and MeHg, this area would be declared a high risk site. It
might be beneficial to stabilize this soil with organic matter so there is more food for the
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microbes, ultimately preventing the methylation of Hg in this soil. By keeping the pH above 7.0,
remedial objectives for natural attenuation will be met in this soil and MNA will be successful.
Graph 4: This graph shows the major sinks from SEP data for Chromium, before and after lime application.
70
60
50
40
30 Chromium Sink pH 6.3
20 Chromium Sink pH 7.0
10
0
Bound to SOM Bound to Bound to Bound to Residual
Carbonates Oxides/ Sulfides (Phosphate and
Hydroxides Silicate)
In site D, the increased pH adjustment decreased the solubility of Cr and CEC remained
the same. The major sinks for Cr are carbonates, oxides/hydroxides, sulfides and the residual
fraction. The presence of chromium in these insoluble sinks indicate that this trace metal will not
be easily resolubilized. Chromium has sorption to Fe/Al/Mn oxides, organic matter, and
hydroxides (Brady, 2003). Sequential extraction procedure data (Graph 4) shows that at a neutral
pH of 7.0, Cr bonded more efficiently to SOM, carbonates, and sulfides. This data shows us that
with a more acidic pH, Cr is more soluble, bonds stronger to oxides/hydroxides, and the residual
fraction. This site has a very high CEC, and high redox potential leading to the tendency for
species to gain new electrons. This site will be successful when dealing with MNA and will not
need the application of lime to increase the pH because Cr is more soluble at a lower pH. By
adding amendments to this sites soil, such as organic matter and Fe/Al oxides, MNA will be
successful overtime and the high amounts of trace metals will be removed from the system.
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Conclusion:
The purpose of this paper is to consider the feasibility of monitored natural attenuation
(MNA) as a remedial strategy for each mining site, and to calculate how effective the results
would be. Modern mining practices pose huge threats to the environment due to the release large
quantities of trace metals that are able to bond to different sinks in the soil using exchange
capacity. Abandoned and active mining sites pose a global issue due to the dispersal and mobility
of these trace metals and in large quantities, are detrimental to natural systems. The thesis of this
paper is using data from the sequential extraction procedure (SEP) for MNA, major sinks for
treated soils will be recognized, and used to determine a method for removing different levels
(mg/kg) of contaminants (Pb2+, Cu2+, Hg2+, Cr2+). Site evidence and SEP data (Table 2) showed
that all the sites evaluated in this case study will be able to undergo MNA and the removal of
Annotated Bibliography:
Brady, W.D., E.J. Matthew, G.R. Paul, and B.V. Patrick. 2003. A Site-Specific Approach for the
NRCS. Web Soil Survey. 2020. United States Department of Agriculture, Natural Resources
Sparks, D.L. 2003. Environmental soil chemistry. Academic Press, San Diego.
USDA. 2014. Keys to soil taxonomy. United States Department of Agriculture, Natural
Wilkin, R.T. 2008. Contaminant Attenuation Processes at Mine Sites. Mine Water and the