Danielle Watt

Remediation of Heavy Metals Contaminated Soils by Stabilization using Clay minerals

ENVL 3531

Professor Jessica Favorito

April 25 2018

Introduction
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Worldwide, reported sources of heavy metal pollution into the environment from

anthropogenic activities such as industrial, agricultural, pharmaceutical, mining, and atmospheric

sources such as smelting, pose a risk for human as well as environmental health. These heavy

metals end up in soils where they do not biodegrade, but instead persist in nature, where they

generally leach into groundwater or can be accumulated into plants and enter the food chain.

There are three main methods that have gained attention in the past for remediating heavy

metals, the first is soil washing. Soil washing involves excavation of the contaminated soil,

adding a chemical to extract the heavy metal from the soil where it then will be sent to

somewhere to be disposed of, then putting the soil back in place. Soil washing can be very

expensive and also add to the waste issue. The second is phytoremediation, which uses plants to

reduce the concentrations and/or toxic effects of heavy metals, which can take years and also

pose other problems such as biowaste together with possibility of entering food chain. Lastly,

stabilization, or immobilization techniques, can decrease leaching of heavy metals and also be

very cost-effective. This is achieved by adsorption, precipitation, and complexation reactions,

which result in the redistribution of heavy metals from the solution phase to the solid phase,

reducing their bioavailability and transport in the environment (Xu Yi, p.194). In order to

achieve this goal, you can use several different amendments such as lime, limestone, clay

minerals, zeolites, phosphates and organic composts, although some, such as organic materials,

have been known to produce secondary pollutants (Id.). Clay minerals have a lot of potential

because of their low cost, high abundance as well as performance. In this review, the potential of

three different clay minerals, sepiolite, vermiculite, and montmorillonite, to immobilize heavy

metals in soils is summarized.

Discussion:

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Clay minerals have had several important roles such as the development of human

civilization, acting as a natural scavenger for pollutants through the uptake of cations and anions

by ion exchange or adsorption (Xu Yi, p.194) and the use for environmental protection in the use

of disposal and storage of hazardous chemicals. Clay minerals are hydrous aluminosilicates,

which make up the the colloid fraction of soils, sediments, rocks, and water (Id). They can

remove pollutants from aqueous solutions because of a high CEC as well as high specific surface

area associated with the small particle sizes (Malandrino, Adsorption of Heavy Metals). Clays

can also help to restore and enhance plant grown, especially when there is a large CEC known in

a clay (Zhang, p.461). Since clays are phyllosilicates, have a small grain size, <2 micrometer,

and isomorphic substitution from the electric charge of the layers, they can easily interact with

heavy metals by adsorption, ion exchange reactions, and the formation of inner-sphere

complexes (Id.)

Sepiolite

Sepiolite is a porous fibrous hydrated magnesium silicate (Xi Yi, p.194). Its structure

contain blocks of two tetrahedral silica sheets, sandwiched between an octahedral sheet of

magnesium oxide/hydroxide (Id.). Many previous studies before have shown the potential of

absorbing heavy metals, especially Cd, Zn, Cu and Pb (Id.). Sepiolite has shown many

advantages such as in the remediation of Cd polluted acid paddy soils, with sepiolite having a

high performance, universal application, low cost as well as simplicity of use (Id.). Sepiolite was

shown to reduce the Cd content of brown rice to 0.18 mg kg -1, which was below the maximum

levels of contaminants allowed in foods in China as well as World Health Organization (WHO)

(Id.). Also, sepiolite helped to increase of pH of the acid paddy soils as well decrease the

bioavailability of Cd in the soils (Id.). The change in pH was the biggest factor for the cause of

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stabilization and plant uptake of Cd. Sepiolite was also shown to decrease the heavy metal

content of other vegetables such as spinach, lettuce, and radishes (Id, p. 197). In addition,

sepiolite was also combined with other amendments such as limestone and phosphate fertilizer

which was shown to have remarkable effects on immobilizing heavy metals (Id.). Sepiolite has

many great advantages when using it to immobilize heavy metals, but it also shown to issues in

its use. The first relates to its natural composition in that it differs from the theoretical formula

and varies in terms of its chemical/mineral composition (Id.). A sample taken from Hebei

Province China had a make up 41.7% CaO, 16.8% MgO, 7.4% Al2O3, and 32.5% SiO2 with its

main minerals being calcite, sepiolite, and SiO2. While a sample taken from the Oreo deposit in

Zaragoza, Spain consisted of 87% sepiolite, 7% dolomite, 4% quartz and 2% illite (Id.). These

differences in the composition can have possible different outcomes when remediating. The

second issue with this clay mineral is that doses of sepiolite used in immobilization remediation

vary. Studies have shown a variation when using sepiolite such as a minimum dosage of 0.2%

and then a maximum of 10% (Id.). Determining an appropriate dosage is still unknown when

using sepiolite.

Vermiculite

Vermiculites have a very high CEC, and this is because of substitutions of Mg2+ and Fe2+

in place of Al3+ in the octahedral sheets, and also, substitutions of Al3+ in place of Si4+ in the

tetrahedral sheets (Malandrino, Adsorption of Heavy Metals). Vermiculite also swells less than

smectites because of the higher charge in the tetrahedral sheets, together with higher elasticity

and plasticity than kaolinite and mica (Id.). They are also perfect for adsorbing heavy metals by

two different mechanisms. First, cation exchange at the planar sites, which results from

interactions between metal ions and negative permanent charge (outer-sphere complexes) and

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second, formation of inner-sphere complexes through Si-O- and Al -O- groups at the clays

particle edges (Id.). In a study using lettuce and spinach and using vermiculite to decrease

phytoaccumulation of of metals (Cu, Ni, Pb, and Zn), vermiculite shown to be strong influential.

(Malandrino, Accumulation of Heavy Metals). Adding vermiculite also shown to raise soil pH

by two units, from 4.17 to 5.99. The addition of vermiculite greatly decreased the translocation

of toxic metals to the plants, except for Mn, which is due Mn being essential for plants and is

also present as an exchangeable ion in the interlayer of vermiculite (Id.). Vermiculite shown to

be a good candidate as amendment for chemical stabilization because it significantly reduced the

uptake of metal pollutants by lettuce and spinach (Id.).

Montmorillonite

Montmorillonite is a subclass of smectite, a shrink-swell clay based mineral, and is a 2:1

mineral. Water and other polar molecules can enter between the unit layers and cause the

structure to expand, this is due to its weak interlayer bonding. There is greater isomorphic

substitution in the octahedral layer than in the tetrahedral layer (substitution of Al3+ ions for

Mg2+ in octahedral layer). In a study on remediating Copper polluted red soils with clay

minerals, montmorillonite showed good adsorption for Cu2+. Maximum adsorption of Cu2+ was

at 1501 and 3741 mg/kg (Zhang, p.463). Montmorillonite also showed a high desorption rate,

which was used to characterize the degree of Cu2+ binding to the clay, the higher the desorption,

the more loose the binding (Id., p.464). When Cu concentrations reached 50 and 100 mg/L,

adoption rates for montmorillonite were 1826.4 and 3359.5 mg/kg (Id.). The adsorption of Cu by

montmorillonite was shown to be both irreversible and reversible, mainly in ion exchange (Id.).

This polluted site was very acidic (pH of 3.99), after 30 and 60 days of montmorillonite, soil pH

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had increased with an increasing montmorillonite dose (Id.). The clay mineral had an increase of

about 0.37-1.12 in pH.

Conclusion:

The clay minerals of sepiolite, vermiculite, and montmorillonite shown to be a good

candidates for stabilization of heavy metals in soil remediation. Sepiolite was shown to be very

effective in the use of immobilization of heavy metals. Sepiolite also had a few disadvantages, in

that dosage is still unclear and makeup of the mineral can be different depending on location.

Vermiculite was also a good candidate for stabilization of heavy metals because of high CEC

and isomorphic substitution in the tetra and octahedral sheets. Vermiculite also had the highest

increase of pH out of sepiolite and montmorillonite. A greater dose of montmorillonite shown

significant results in the immobilization of metals, also, montmorillonite was shown to be both

irreversible and reversible due to ion exchange in the adsorption of Cu. All three clay minerals

were able to decrease phytoaccumulation, immobilize metals in the soil, as well as increase soil

pH. This paper shows the success that clay minerals such as sepiloite, vermiculite, and

montmorillonite can have in the immobilization of heavy metals in soil.

References

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Malandrino, M. (January 2011). Accumulation of Heavy Metals from Contaminated Soil to

Plants and Evaluation of Soil Remediation by Vermiculite. Retrieved on 24 April 2018
from: https://www-sciencedirect-com.ezproxy.stockton.edu/science/article/pii/S004565
3510011719.
Malandrino, M. (15 July 2006). Adsorption of Heavy Metals on Vermiculite: Influence of pH and
Organic Ligands. Retrieved on 24 April 2018 from:
https://www-sciencedirect-
com.ezproxy.stockton.edu/science/article/pii/S0021979706001
901.
Xu Yi, Liang Xuefeng. (23 January 2017). Remediation of Heavy Metal-Polluted Agricultural
Soils Using Clay Minerals: A Review. Retrieved on 24 April 2018 from:
https://www-sciencedirect-
com.ezproxy.stockton.edu/science/article/pii/S1002016017603102?_rdoc=1&_fmt=high
&_origin=gateway&_docanchor=&md5=b8429449ccfc9c30159a5f9aeaa92ffb&ccp=y.
Zhang Gangya. (13 June 2010). Remediation of copper polluted red soils with clay minerals.
Retrieved on 24 April 2018 from:https://www-sciencedirect-com.ezproxy.stockton.edu/
science/article/pii/S1001074210604317.