SOIL POLLUTION AND REMEDIATION

V. SOIL POLLUTION AND REMEDIATION

a) b) c)

Soil components Saline Soil pollution and treatment Pollution by heavy metals

d)

Pollution by hydrocarbons

S OIL

Soil is made up of air, water, minerals and organic material and is one of the most important natural resources on earth. Most life on earth depends on soil as a direct or indirect source of food. Plants and animals source their nutrients from the soil and it is home to many different forms of life.

How is soil made?

Soil is formed in two general ways: When weather conditions cause rock to break down. When soil is carried from one place to another.

Air: Moving air, such as the wind blows sand against rock to wear it down.
Water: The force of running water can wear away rock. Rain and snow also help to break down rock into smaller particles. Plants: it helps the soil as they grow and when they die. As dead plants decay, it adds an organic material to the soil, which makes it more fertile. Animals: The body waste of many animals helps to keep the soil fertile, as well as the remains of dead animals as they decay.

Humus: Organic part of the soil. It helps to retein water so its filtration comes slowly. It is charge (-) so it maintain ions such as K+, Ca+, NH3+. The gases exchange takes place (O2, N2, CO2) and it is the mineral nutrients deposit. The leaching process takes place (organic matter exchange from one horizon to another horizon) by the rain.

Accumulation of matter washed from horizon A such as Ca, N, K, Ni, Na, Mf, Fe, Al, Si by the leaching process (there is a larger concentration of non organic matter).

Mother rock (horizon D), when the erosion of the soil is present is the unique layer that remains intact (sand, rocks).

 Support of life Provides the mineral resources Land to the earth ecosystems

decrease of natural resources land contamination Change of use of land.

Soil components

Mineral Components

Mineral particles are inorganic materials derived from rocks and minerals. They are extremely variable in size and composition.

RESERVE M INERAL RESOURCES

Soil

Renewable

No Renewable
Oil Minerals Metals

Crops Forests Grasslands

World reserves of metals Metal Al Cu Fe

Reserve (Tg) 21 000 340 65 400

T IEMPO QUE PERDURARN LAS RESERVAS DE MINERALES .

Demanda del material es constante

=
Ts = Tiempo transcurrido hasta el agotamiento

F = Masa de reserva del mineral A = Demanda Actual

Demanda del material no es constante

(1 + ) 1 =
i = Incremento anual de la demanda como fraccin n = Nmero de aos para consumir la reserva

En el 2001 la produccin anual de Fe fue de 1 060 Tg. Suponiendo que la demanda del 2001 permanece constante, Cunto tiempo durara las reservas?. La produccin mundial aumento 1.6% de 1996 a 1997. Si esta tasa de incremento permanece constante, Cunto duraran las reservas mundiales?.

Types of primary and secondary minerals

Primary minerals are formed at high temperature and pressure, under reducing conditions without free oxygen. These minerals are mainly present in soils as sand and silt particles. They are not crystallized and deposed from molten lava.

Secondary minerals are formed at low temperature and pressure through oxidation. They are the weathering product of primary minerals, either through alteration of their structure or through reprecipitation. Secondary minerals are usually present in soil as clay particles.

Most common elements in soils

The elements that are found in soils in the highest quantities are O, Si, Al, Fe, C, Ca, K, Na, and Mg. These are also major elements found in the Earths crust and in sediments. Oxygen is the most prevalent element in the Earths crust and in soils.

Size of soil particles The mineral particles present in soils vary enormously in size from boulders and stones down to sand grains and minute clay particles that cannot be seen by an optical microscope. An arbitrary division is made by size-grading soil into material: a) that passes trough a sieve with 2-mm diameter holes - the fine earth (consisting of sand, silt, and clay particles).

b) that is retained on the sieve (> 2 mm) the coarse fragments (gravel, cobbles, and stones). Coarse fragments (diameter > 2 mm) are defined as rock fragments and do not include fragments of pads or concretions.

Soil texture Refers to the relative proportions of sand, silt, and clay in a soil. It is often the first and most important property to be determined when describing a soil, since many conclusions can be drawn from this information (water intake or infiltration, water storage in the soil, soil aeration, soil fertility, trafficability, etc.). A number of different classification systems have been devised to divide soil particles according to their size. The figure below shows the limits of different size classes in three systems of soil particle size classification.

C LASIFICACIN DE T EXTURAS

Los resultados de una distribucin del tamao de las partculas revela que una muestra se compone con 30 % de arena, 40 % de lodo y 30 % de arcilla. Determnese a que textura pertenece este suelo

Barro Arcilloso

D ISTRIBUCIN POR EL
TAMAO
Arena
120 110 100 90

Lodo y Arcilla Analisis del Hidrometro

200

Analisis de la Criba
10 16 30 40 60 100

Curva de distribucin del tamao de la partcula en el suelo. Cribado > 0.075 mm

Porcentaje mas Fino

80 70 60 50 40 30 20 10 0 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0

Diametro de la particula (mm)

C RIBAS E STNDAR
# Criba 4 6 8 10 12 16 18 Abertura (mm) 4.75 3.35 2.36 2 1.68 1.18 1 # Criba 20 30 40 50 60 70 80 Abertura (mm) 0.85 0.6 0.425 0.3 0.25 0.21 0.18 # Criba 100 140 170 200 270 Abertura (mm) 0.15 0.106 0.088 0.075 0.053

A NLISIS H IDROMTRICO
0.075 mm < Todas las Partculas son esfricas Ley de Stokes

( )2 = 18

vs = Velocidad de sedimentacin (m s-1) s = Densidad de la partcula (Kg m-3) = Densidad del Fluido (Kg m-3) d = Dimetro de la Partcula (m) = Viscosidad Dinmica (Pa s) g = Gravedad

Water and air constantly compete for pore space in soils. Most of the time soil pores are not full of water, but occasionally (after heavy storms or in swamps and bogs) some soils may be saturated with water and little or no air is present in pores.

How do we know how much water is available in a soil?

For every soil there is a different distribution of pores of various sizes. Also, soils have different salt contents and particles. All of these factors will determine the energy at which the water is held in the soil and are reflected in the water retention curve.

Soil Air
Soil pores, the voids between minerals, organic matter, and living organisms, are filled with air or water. There is a dynamic equilibrium between water and air content within a soil. When water enters the soil, it displaces air from some of the pores.

Composition of soil air

The composition of soil air is different from that of the atmosphere because it cannot readily mix with air above the soil.

The metabolic activity of plant roots, microbes and soil fauna all affect the composition of soil air.
For example, the concentration of carbon dioxide (CO2) in soil (between 0.3 and 3%) is often several hundred times higher than the 0.03% found in the atmosphere. In extreme cases oxygen can be as low as 5-10%, compared to 20% in the atmosphere. Soil air has a higher moisture content than the atmosphere, with relative humidity approaching 100% under optimum conditions. (humidity is not as variable in soil as it is in the atmosphere).

Organic Components
Soil organic matter (SOM) can be of plant, animal, or microbial origin and may be relatively fresh or highly decomposed and transformed. One of many definitions of soil organic matter states that it is a complex and rather resistant mixture of brown or dark brown amorphous and colloidal organic compounds that result from microbial decomposition and synthesis and has chemical and physical properties of great significance to soils and plants. Many species of fungi and bacteria soil particles decompose soil organic matter. The fungi and bacteria that can break down the woody tissues and cellulose of intact leaves, stems and dead roots of plants perform the function of decomposition of organic matter that often builds humus and returns nutrient back to the soil.

Soils may vary greatly in their organic matter contents. For example, a typical prairie grassland soil may contain 5-6% SOM (by weight) in surface horizons, sandy desert soil may have <1% of SOM, while Organic soils (by definition) contain >30% SOM (by weight).

A simple test that allows qualitative comparison of soil organic matter content

Organic matter is an important soil component because it:

Holds soil particles together and stabilizes the soil, thus reducing the risk of erosion
Aids crop growth by improving the soil's ability to store and transmit air and water Stores and supplies many nutrients needed for the growth of plants and soil organisms Prevents or minimizes soil compaction Retains carbon from the atmosphere Reduces the negative environmental effects of pesticides, heavy metals, and many other pollutants.

SOM includes primary components that are inherited from plant and animal residues entering the soil. Primary components are sometimes referred to as non-humic substances. These compounds are relatively easily decomposed by microorganisms and they persist in soil for a brief time (e.g. several months or years). They make about 20-30% of total SOM.
These include: carbohydrates amino acids lipids

Secondary components also include humic substances, which are rather different from most primary components.
Humic substances are products of biochemical decomposition. They are complex substances of high molecular weight, which are resistant to further decomposition. Consequently they tend to accumulate in the soil. Most are dark and are hence responsible for the dark soil color that is commonly associated with soils of high organic matter content. Humic substances make up 60-80% of total SOM.

There are three general groups of humic substances: (1) fulvic acids (2) humic acids (3) humin.

Soil Management
Soils are integral components of agro-, forest, and grassland ecosystems. They also influence watershed and coastal ecosystems, as well as urban ecosystems. Every management practice (timber harvest, fertilizer application, installation of irrigation or drainage system, application of biosolids) that we apply affects the soil and all soil organisms and higher plants growing in or on the soil.

Soil Degradation

During the past 50 years various land-use practices have degraded about 5 billion ha (about 43%) of Earths vegetated land. This land degradation results in reduced productive potential. The loss of arable land has been caused by a number of factors, many or most of which are tied to human development. The primary causes are deforestation, overexploitation for fuelwood, overgrazing, agricultural activities and industrialization.

The major forms of soil degradation can be divided into the following four groups: erosion, physical, chemical, and biological degradation.

R EPORT OF A CONTAMINATED
SOIL

REMEDIATION OBJECTIVES

Saline Soil pollution and treatment

Releases of salt to land often occur in association with activities such as oil and gas production, salt/sand processing and storage facilities at highway maintenance yards, rendering plants, runoff from snow removal dumps and the transportation of saline material for industrial use. These salts can be very mobile and may easily move with water over the surface or down through soil.

When salt concentrations in the soil are high, the movement of water from the soil to the root is slowed down. When the salt concentrations in the soil are higher than inside the root cells, the soil will draw water from the root, and the plant will wilt and die.

The damaging effects of salt on plants are caused not only by osmotic forces, but also by toxic levels of sodium and chloride. Fruit crops and woody ornamentals are especially sensitive to high levels of these elements. Also, the high pH value (a measure of the acid/alkaline balance) caused by excess sodium may result in micronutrient deficiencies.

The most efficient and cost effective method of avoiding adverse effects and the attendant remediation costs associated with salt releases is spill prevention. When spills do occur, a fast, effective response based on a comprehensive understanding of impacts, salt movement, and assessment and remediation procedures can avoid or mitigate adverse effects on the environment.

Pollution by heavy metals

Mining, manufacturing, and the use of synthetic products (e.g. pesticides, paints, batteries, industrial waste, and land application of industrial or domestic sludge) can result in heavy metal contamination of urban and agricultural soils. Heavy metals also occur naturally, but rarely at toxic levels. Potentially contaminated soils may occur at old landfill sites (particularly those that accepted industrial wastes), old orchards that used insecticides containing arsenic as an active ingredient, fields that had past applications of waste water or municipal sludge, areas in or around mining waste piles and tailings, industrial areas where chemicals may have been dumped on the ground, or in areas downwind from industrial sites.

Excess heavy metal accumulation in soils is toxic to humans and other animals. Exposure to heavy metals is normally chronic (exposure over a longer period of time), due to food chain transfer. Acute (immediate) poisoning from heavy metals is rare through ingestion or dermal contact, but is possible. Chronic problems associated with long-term heavy metal exposures are:
Lead mental lapse. Cadmium affects kidney, liver, and GI tract. Arsenic skin poisoning, affects kidneys and central nervous system. The most common cationic metals are mercury, cadmium, lead, nickel, copper, zinc, chromium, and manganese. The most common anionic compounds are arsenic, molybdenum, selenium, and boron.

T REATMENT M ETHODS

Traditional Remediation of Contaminated Soil

Once metals are introduced and contaminate the environment, they will remain. Metals do not degrade like carbon-based (organic) molecules. The only exceptions are mercury and selenium, which can be transformed and volatilized by microorganisms. However, in general it is very difficult to eliminate metals from the environment.

Traditional treatments for metal contamination in soils are expensive and cost prohibitive when large areas of soil are contaminated. Treatments can be done in situ (on-site), or ex situ (removed and treated off-site). Both are extremely expensive.

Soil remediation Methods

Some treatments that are available include: 1. High temperature treatments . 2. Solidifying agents . 3. Washing process .

High temperature treatments (Ex-situ)

The following management practices will not remove the heavy metal contaminants, but will help to immobilize them in the soil and reduce the potential for adverse effects from the metals Note that the kind of metal (cation or anion) must be considered:

1. Increasing the soil pH to 6.5 or higher. Cationic metals are more soluble at lower pH levels, so increasing the pH makes them less available to plants and therefore less likely to be incorporated in their tissues and ingested by humans. Raising pH has the opposite effect on anionic elements.

2. Draining wet soils.

Drainage improves soil aeration and will allow metals to oxidize, making them less soluble. Therefore when aerated, these metals are less available. The opposite is true for chromium, which is more available in oxidized forms. Active organic matter is effective in reducing the availability of chromium.
3. Applying phosphate. Heavy phosphate applications reduce the availability of cationic metals, but have the opposite effect on anionic compounds like arsenic. Care should be taken with phosphorus applications because high levels of phosphorus in the soil can result in water pollution.

4. Carefully selecting plants for use on metal-contaminated soils (Phytoremediation). Plants translocate larger quantities of metals to their leaves than to their fruits or seeds. The greatest risk of food chain contamination is in leafy vegetables like lettuce or spinach. Another hazard is forage eaten by livestock.

Table 1. Most frequently used additives in process of phytostabilization of heavy metals and action mechanisms.

5. The electro kinetic method. By feeding an electric current through soil one induces movement of charges, which is generated by migration of ions and colloids in water present in pores and by reductive reactions on the surface of electrodes. The direction and velocity of the movement depends on the charge (size and polarity) of the ions and the velocity of the movement of the flow generated by electro-osmosis.

6. Composting or Bioremediation. based on microorganisms activity, which are commonly used for the reclamation of soils polluted by organic compounds. However, recently there have also been many investigations into applying microorganisms for detoxication and cleaning soil polluted by inorganic substances (e.g. heavy metals).

Pollution by hydrocarbons

Potential hydrocarbon-contaminated sites

Filling stations, distribution depots Oil production, refineries and associated Garages/automotive industry Haulage yards Scrap metal industry Airports, aerospace industry Waste processing & disposal Gasworks Metalworking industry Paints/inks/coatings industry Anybody who uses solvents! Agricultural facilities Including domestic oil storage

Weight Percent

40

30

35

25 20

15 10 5 0

Relative distribution of components

C2-C4 C4-C6 C6-C8 C8-C10 C10-C12 C12-C14 C14-C16 C16-C18 C18-C20 C20-C22 C22-C24 C24-C26 C26-C28 C28-C30 C30-C32 C32-C34 C34-C36 >C36
Carbon Num ber

Crude

Diesel

Gasoline

How oil components might be distributed

Petrol Spill

soil surface Residual Hydrocarbons (~1% HC by weight) in Soil Pores (soil contamination)
Before Oil Flow Through Soil

vadose zone

Volatilised (~50mg HC/kg soil) Constituents (vapour plume) Mobile & Residual Hydrocarbons (~9% by weight) (free-product) capillary fringe

During Oil Flow Through Soil

After Oil Flow Through Soil

water table saturated zone Dissolved Constituents (plume) (~130 mg HC/L water)

groundwater flow

Remediation Methods
Bioventing (In-situ): It is based on soil vapor extraction using a pressure difference generated by pumping air from the outside. It applies in unsaturated soils contaminated with hydrocarbons. The gases must be treated, usually by passing them through retaining filters containing substances suitable for each gas, for example, activated carbon. This technique is low cost and minimum impact. Does not apply to the recovery of non-aqueous liquid phase (FLNA), a situation that takes place when the hydrocarbon percolation came to impact the groundwater.

Soil Vapor Extraction (In-situ): The volatiles are removed in the soil vapor phase by obtaining a pressure gradient / concentrations by application of vacuum is applied through wells extraction. It applies to VOC's and some volatile fuels but is not adequate for oils, heavy hydrocarbons and PCBs. Not effective in saturated soils and high fines content. Is a commercially available technology that works well in soil conditions of high permeability. The exhaust gases require treatment and liquid waste treatment and disposal. The removal efficiency of some VOCs is limited in dry soils and high organic content.

Incineration (Ex-situ):

Undergoes soil contaminated with hydrocarbons at high temperatures (1200 C) for pollutants to evaporate and then burn under controlled conditions. Required gas cleaning. The final disposal of contaminated soils can be done in cement kilns for waste recovery technique called enabling safe disposal of environmental liabilities. Bioremediation:
Bioremediation is the process that use microorganisms, plants or enzymes to reduce contamination by petroleum hydrocarbons and derivatives, heavy metals and pesticides. Fortunately, biotechnology has allowed the development various strategies that can be used to restore soil and environmental quality, according to the needs and dimensions of the problem to solve. Here are some, but in general there is no "secret formula" that ensures the success of bioremediation.

Biostimulation: As the name suggests, is to encourage native soil microorganisms adding nutrients such as nitrogen or phosphorus.
Bioaeration: a form of stimulation performed with gas such as oxygen and methane, these are added passively in the soil to stimulate microbial activity.

Bioaugmentation: the inoculation of a high concentration of microorganisms in contaminated soil for facilitate biodegradation. As will inoculate these microorganisms must be selected from the soil that will be treated.

Composting: this strategy of bioremediation uses thermophilic aerobic microorganisms forming material piles to be mixed and moistened regularly to promote microbial activity. Phytoremediation: the use of plants to remove, contain or transform a contaminant.

Mexican Legislation