Arsenic Background, Associated Elements and Factors Controll

Arsenic Background, Associated Elements and Factors Controlling Mobility
Richard K. Glanzman
CH2M HILL
100 Inverness Terrace East, Englewood, CO 80112-5304
T: 303-771-0900, F: 303-754-0196, E: rglanzma@CH2M.com
This presentation includes representative arsenic multimedia background concentrations, mineralogy and controls
on arsenic mobility with case histories illustrating these controls. There is a rich history of background arsenic
concentrations in most media that are readily sampled in the environment. These background values are strongly
related to their origin but the physiochemical conditions where they originate are generally poorly described in
tabulations from the literature. Background arsenic concentrations can be used to determine distribution,
attenuation and bioaccumulation coefficients but the site-specific conditions within which the background
concentrations were determined and for which one is interested need to be carefully evaluated before their use.
Arsenic naturally occurs as a major element in hundreds of minerals and is associated as a minor or trace element
in hundreds of additional minerals. Fortunately, most of these involve sulfide and sulphosalt minerals or iron
oxydroxide/oxide phases. This considerably simplifies the geochemical conditions one requires to estimate
arsenic mobility and arsenic concentrations. From the above mineralogical relationships it is obvious that pH and
closed-cell oxidation reduction potential measurements are required field measurements. Unfortunately, most
regulatory data requirements collect laboratory instead of field pH values and dissolved oxygen instead of ORP
values.
Ongoing geochemical research on arsenic has lead to the quantification of arsenic adsorption onto iron
oxyhydroxide/oxide phases under natural conditions involving multiple competing ions. The specific rank of
arsenic speciation with respect to commonly associated dissolved metals and other common ions has been
developed along with the total adsorption capacity of iron oxyhydroxide/oxide phases. The kinetics of most of
these reactions is generally very rapid, commonly less than a few seconds to a few hours, therefore unlike
manganese, kinetics is not usually an issue. Current research defines the actual adsorption mechanisms and range
of irreversible sorption characteristics under oxidizing conditions but not the range of probable arsenic release
under reducing conditions. Reducing conditions needs to be considered in the TCLP protocol for landfill disposal
of arsenic adsorbed to iron oxyhydroxide.
Arsenic Background and
Associated Elements
Controlling Mobility
in Groundwater
Richard K. Glanzman
Arsenic in Igneous Rocks (mg/kg)
Average 1.5, Range 0.2-13.8, Adriano, 1986

Means 1 to 4
Overall Range 0.06 to 113
Sediments/Sedimentary
Rocks/Metamorphic Rocks (mg/kg)
Mean SD Range
Fresh Water Sediment 1.1 B,1998
Ocean Sediments 33.7 46.7 <0.4-455 B&J, 1973
Shale 14.5 13.8 0.3-500 “
Slate 18.1 16.5 0.1-143 “
“
Sandstone 4.1 4.7 0.6-120
“
Quartzite 5.5 2.4 2.2-7.6 “
“
Limestone/Dolomite 2.6 3.0 0.1-20
“
Schist 1.1 1.8 0.0-18.5 “
“
Gneiss 1.5 1.3 0.5-4.1
“
Phosphorites 41 12.5 3.4-100 “
“
Iron Formations 45 1.0-2,900
“
Soils (mg/kg)
World Normal Soils Mean 7.2 Range <0.1-97 S&B, 1984; A, 1986; ASTM, 1995
Median 6.0 Range 0.1-40 H, 2000
Geometric Mean 5.2 Range <0.1-97 B, 1998
Bog/Peat Soils Mean 13.4 Range 2-36 B&J, 1973
Standard Deviation 9.4
Near Arseniferous Deposits Mean 126 Range 2-8,000 B&J, 1973
Standard Deviation 167
Water (µg/L)
Mean SD Range
Rain & Snow 1.44 2.17 0.01-13.9 B&J, 1973
Streams, Rivers, Lakes 3.08 5.42 <0.002-0.59 W, 1988
Streams 0.02-264 W, 1988
Lakes 0.38-1,000 W, 1988
Oceans 2.57 1.98 0.006-11.2 B&J, 1973
Groundwater 17.9 13.9 0.01-800 “
“
Travertine Springs 304 233 30-500
“
Springs, Volvanics 22,200 34,800 120-37,500 “
“
Hot Springs 2,090 2,650 0.2-40,000
“
Mine Waters 3.0-400,000 “
Arsenic Minerals
N %
Native Arsenic (As) 1
Arsenides (X As) 39 14
Sulfides (X AsS) 64 23
Arsenites (X AsO3Y) 26 9
Arsenates (X AsO4Y) 147 53
Arsenides (X As)
X N %
Ni 9 21
Cu 6 14
Fe 5 12
Pd 5 12
Sb 4 10
Co 4 10
Se 3 7
Pb 2 5
Ru 2 5
Ag, Bi - 1 each
Sulfides (X AsS)
X N %
Sb 22 21
Pb 20 18
Cu 14 13
Tl 9 8
Ag 8 8
Fe 6 6
REE (Ru) 6 6
Hg 4 4
Co 2 2
Ni 2 2
Na, Te, Zn, Sn, Se, Bi - 1 each

Arsenic in Common Sulfides
Pyrite 5%
Galena 1%
Sphalerite 1%
Marcasite 0.78%
Chalcopyrite 0.166%
Pyrrhotite 0.015%
Arsenites (X AsO3Y)
X N %
Mn 9 17
Pb 9 17
Fe 6 11
Pb 6 11
Ca 5 9
Cl 5 9
Mg 4 8
Zn 4 8
Si 4 8
Cu 3 6
Sb, Na, K, F - 1 each

Y = (OH)
Arsenates (X AsO4Y)
X N %
Ca 53 16
Fe 42 13
Zn 34 10
Cu 29 9
Mn 26 8
Pb 26 8
Mg 22 7
UO2 13 4
Cl 10 3
SO4 9 3
PO4 9 3
Co 6 2
Sb, Bi, F 5 2
Ni, Ba, Sr 4 1
Si, Mo, REE 3 1
Ti, Y, B, Cd, V 1 0
Y=both (H2O) and (OH)

Arsenic Mineralogy
Arsenides Ni>Cu>Fe = PD>Sb = Co>Se>Pb
Sulfides Sb>Pb>Cu > Tl>Ag>Fe = REE>Hg
Arsenites (OH) = Mn = Pb>Fe>Ca = Cl>Mg = Cu=Zn=Si
Arsenates (H2O)>(OH)>Ca>Fe>Zn>Cu>
Mn=Pb>Mg>UO2>Cl>SO4=PO4>Co>Sb=Bi=F
Zykaite
Fe4+3(AsO4)3(SO4)(OH) 15H2O
Milltown Reservoir
As
Milltown Tailings
Relative Competitive Adsorption
Ferric-Oxyhydroxide, pH 6.5, Atmospheric Conditions

PO4>AsO4>SeO3>SiO2>MoO4>>
SO4>SeO4>>
Cl
Iron vs Arsenic
Sediments in Crumpton Creek
As-Water
Fe-S-Water
Dis
so
lve
di
ron
As-S-Water
Ba-As-S-Water
Lead ThioArsensite
PbAsS(SH)(OH)

Arsenic Background, Associated Elements and Factors Controll

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Arsenic Background, Associated Elements and Factors Controlling Mobility

Average 1.5, Range 0.2-13.8, Adriano, 1986

Na, Te, Zn, Sn, Se, Bi - 1 each

Sb, Na, K, F - 1 each

Y=both (H2O) and (OH)

Ferric-Oxyhydroxide, pH 6.5, Atmospheric Conditions

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