**3. Studied area**

Metallurgy activities produce gas, wastewater and waste containing pollutants that can be sources of risk under normal handling, and especially for irresponsible handling of equipment. The main resulted pollutants are: CO2, CO, NO, SO, VOCs (e.g. BaP, PAHs, dioxins, Freon), particulate heavy metals (Pb, Cu, Zn, As, Cr), cyanides, phenols, heavy metals and sometimes toxic organic compounds in waste material.

Annual average concentrations exceed the maximum permitted levels in many localities (Baia Mare, Copsa Mica, Medias, Targoviste, Arad, Deva, etc.), for both particulate matter and for sediment, coming mainly from industry of steel.

The main polluter from industrial zone of Targoviste city was SC Mechel Targoviste SA, located in the south of the city. By the metallurgical activity, emissions were resulting, with significant concentrations of pollutants, including heavy metals. In the process of obtaining steels at SC Mechel SA, technological flow was served by Electric steelmaking 2, EBT electric oven with a capacity of 70 tons/hour and Continuous casting plant (in billets) with a maximum capacity of production of 2.5 tons/hour. The activity SC Mechel Targoviste SA was assisted by filtration systems so that the environmental impact to be reduced to a lower limit.

During the elaboration of steel in Electric steelmaking no. 2, total dust are emitted to air, metals (Cd 0.05 mg/Nm3 , Pb 0.3 mg/Nm3 and Cr + Cu + Mn + Ni + Zn 5.0 mg/Nm3 ), organic compounds, nitrogen oxides (NOx), carbon monoxide (CO) and sulphur oxides (SOx) [21]. In addition to these emissions of heavy metal particulates, SC Mechel SA polluted the soil by the waste and slag dumps generated during the metallurgical processes and stored in an open deposit.

Dispersion of pollutants in the atmosphere largely depends on emission characteristics, meteorological factors, topography, soil roughness, the height of buildings, especially the stack height. Among the meteorological factors, wind direction, intensity, and thereof frequency, are the dominant factors on which we can determine the wind rose indicating the direction of predominant movement of air masses. Based on the wind rose [22] can be designed the Assessment of Historical Heavy Metal Pollution of Land in the Proximity of Industrial Area of Targoviste, Romania http://dx.doi.org/10.5772/58304 265

In discussions about soil protection and remediation, pollutant limits for various elements have been established only under certain conditions and soil parameters. It was not taken into account the specific conditions such as the fact that on low-carbon light soils there is strong influence of rainfall leading to a strong acid mobilization and uptake into plants of toxic heavy

The solubility of Zn in soil was studied by Herms and Brummer [20], which demonstrated the extent to which this element is dissolved by increasing acidity of the soil and became available for plants uptake. A pH value of 5 of low-Zn soil could lead to lasting effect of uptake large amounts of Zn, with all the negative consequences that result. The balance of Zn in the soil solution is carried out according to the pH of soil: at 1200 mg/kg of Zn and a pH of 7, at 100 mg/kg of Zn and pH of 6, and at only 40 mg/kg Zn and a pH of 5. This indicates that also the

Metallurgy activities produce gas, wastewater and waste containing pollutants that can be sources of risk under normal handling, and especially for irresponsible handling of equipment. The main resulted pollutants are: CO2, CO, NO, SO, VOCs (e.g. BaP, PAHs, dioxins, Freon), particulate heavy metals (Pb, Cu, Zn, As, Cr), cyanides, phenols, heavy metals and sometimes

Annual average concentrations exceed the maximum permitted levels in many localities (Baia Mare, Copsa Mica, Medias, Targoviste, Arad, Deva, etc.), for both particulate matter and for

The main polluter from industrial zone of Targoviste city was SC Mechel Targoviste SA, located in the south of the city. By the metallurgical activity, emissions were resulting, with significant concentrations of pollutants, including heavy metals. In the process of obtaining steels at SC Mechel SA, technological flow was served by Electric steelmaking 2, EBT electric oven with a capacity of 70 tons/hour and Continuous casting plant (in billets) with a maximum capacity of production of 2.5 tons/hour. The activity SC Mechel Targoviste SA was assisted by

During the elaboration of steel in Electric steelmaking no. 2, total dust are emitted to air, metals

nitrogen oxides (NOx), carbon monoxide (CO) and sulphur oxides (SOx) [21]. In addition to these emissions of heavy metal particulates, SC Mechel SA polluted the soil by the waste and slag dumps generated during the metallurgical processes and stored in an open deposit.

Dispersion of pollutants in the atmosphere largely depends on emission characteristics, meteorological factors, topography, soil roughness, the height of buildings, especially the stack height. Among the meteorological factors, wind direction, intensity, and thereof frequency, are the dominant factors on which we can determine the wind rose indicating the direction of predominant movement of air masses. Based on the wind rose [22] can be designed the

and Cr + Cu + Mn + Ni + Zn 5.0 mg/Nm3

), organic compounds,

filtration systems so that the environmental impact to be reduced to a lower limit.

metals. This does not happen on heavier soils rich in limestone.

264 Environmental Risk Assessment of Soil Contamination

low-Zn soil can store dangerous amounts of available Zn.

toxic organic compounds in waste material.

sediment, coming mainly from industry of steel.

, Pb 0.3 mg/Nm3

**3. Studied area**

(Cd 0.05 mg/Nm3

**Figure 3.** Dispersion and transport of pollutants particles according to the pollution direction compass, relative to the most significant pollution source, the furnace of the Electric steelmaking no. 2 belonging to SC Mechel SA

pollution direction compass which indicates the direction of dispersion and transport of pollutants particles (Figure 3). In the middle of pollution direction compass is the most significant pollution source, the furnace of the Electric steelmaking no. 2 belonging to SC Mechel SA. East was one of the predominant directions of pollutants transport and the particles have deposited on the ground (agricultural fields) during the process of steel elaboration.

In addition to the pollution produced by ground deposition of particles emitted by the SC Mechel SA chimney, these soils are affected by deposit of slag and skim from the same plant. The dumps that are within walking distance (less than 10 m) of agricultural land of residents from Colanu, Romania, are subject to a continuous process of erosion and transport by wind, smaller particles from the surface of stockpiles being transported up to 10 km. Dispersion of the slag particles is due to transport activities to and from the place of storage of metal waste.

Characteristic types of soils for studied area are gray luvisol and gray brown luvisol (Figure 4) according SRTS-2003 (reddish brown after SRCS 1980), soils of a reddish hue, quite evident in the upper horizon and really evident in the middle horizon. Water and air permeability of the soil was moderate. Humus content was about 3%, nutrient supply was moderate, the soil reaction was low-acid with pH values in the range of 6.0 to 6.4, and the degree of base saturation was 80% to 85%.

**Figure 4.** Gray brown luvisol profile (a) and brown-yellowish-rusty upper horizon (b)

Bioaccumulation in upper and middle horizon was low; plant debris was mostly decomposed by the action of fungi, and could be observed the formation of small amounts of humus with predominating fulvic acids. Due to intense alteration of mineral component occurs removal of clay colloid from the surface, with accumulation in the Bt horizon, where the profile shows a textural differentiation.

In soils with alluvial B horizon, such as soil in the industrial area of the Targoviste city, colloidal order mineral fraction of this horizon contains large amounts of colloidal hydroxides (e.g. Fe(OH)3 and Al(OH)3) and various hydrated iron and aluminium sesquioxides free-form the profile shows a textural differentiation. Assessment of Historical Heavy Metal Pollution of Land in the Proximity of Industrial Area of Targoviste, Romania http://dx.doi.org/10.5772/58304 267

degree of base saturation was 80% to 85%.

Characteristic types of soils for studied area are gray luvisol and gray brown luvisol

Bioaccumulation in upper and middle horizon was low; plant debris was mostly

(Figure 4) according SRTS-2003 (reddish brown after SRCS 1980), soils of a reddish hue,

quite evident in the upper horizon and really evident in the middle horizon. Water and air

permeability of the soil was moderate. Humus content was about 3%, nutrient supply was

moderate, the soil reaction was low-acid with pH values in the range of 6.0 to 6.4, and the

decomposed by the action of fungi, and could be observed the formation of small amounts

of humus with predominating fulvic acids. Due to intense alteration of mineral component

occurs removal of clay colloid from the surface, with accumulation in the Bt horizon, where

deposited.

respectively. Land at NE, E and SE from the source of pollution, are grouped according with

the use category in Zone II – agricultural fields sensitive to high concentrations of heavy

of pollution, from five different points, chosen according to triangle method. The results of

metal concentration represent the average of these five samples. From each sampling point,

samples were taken from three layers: the upper layer (0-5 cm depth), middle layer (5-20 cm

depth) and lower layer (20-40 cm depth). These layers were chosen according with the

Sampling of soil was done at distances between 50 and 1000 meters from the source

Figure 5. Iron hydroxides **Figure 5.** Iron hydroxides

(mR2O3 nH2O) [23]. Large amounts of iron hydroxides in the humus horizon could be observed for the brown and reddish-brown soils from the industrial zone of Targoviste (Figure 5). The presence of these hydroxides is manifested by brown-yellowish, brown, reddish-brown, yellowish-rusty or rusty lit of the horizon where they are deposited. **4. Material and method** 

*4.1 Experimental design* 

### **4. Material and method** Sampling points were chosen

### **4.1. Experimental design** to reflect a snapshot of the impact of

metals.

Bioaccumulation in upper and middle horizon was low; plant debris was mostly decomposed by the action of fungi, and could be observed the formation of small amounts of humus with predominating fulvic acids. Due to intense alteration of mineral component occurs removal of clay colloid from the surface, with accumulation in the Bt horizon, where the profile shows a

**Figure 4.** Gray brown luvisol profile (a) and brown-yellowish-rusty upper horizon (b)

In soils with alluvial B horizon, such as soil in the industrial area of the Targoviste city, colloidal order mineral fraction of this horizon contains large amounts of colloidal hydroxides (e.g. Fe(OH)3 and Al(OH)3) and various hydrated iron and aluminium sesquioxides free-form

textural differentiation.

266 Environmental Risk Assessment of Soil Contamination

Sampling points were chosen to reflect a snapshot of the impact of metallurgical activities in this area by particles emissions. Based on weather conditions and pollution direction compass of Dâmboviţa County (Figure 6), were determined that areas found at SW and W towards the emission source are the most affected. In that location have been chosen the harvest area Zone I – industrial fields, with two subzones, for SW and W directions respectively. Land at NE, E and SE from the source of pollution, are grouped according with the use category in Zone II – agricultural fields sensitive to high concentrations of heavy metals. metallurgical activities in this area by particles emissions. Based on weather conditions and pollution direction compass of Dâmboviţa

County (Figure 6), were determined

that areas found at SW and W

towards the emission source are the

most affected. In that location have

been chosen the harvest area Zone I

– industrial fields, with two

subzones, for SW and W directions

depth to which the roots of culture plant normally develop.

Figure 6. Sampling directions from industrial area of

In soils with alluvial B horizon, such as soil in

the industrial area of the Targoviste city, colloidal

order mineral fraction of this horizon contains large

amounts of colloidal hydroxides (e.g. Fe(OH)3 and

Al(OH)3) and various hydrated iron and aluminium

sesquioxides free-form (mR2O3·nH2O) [23]. Large

amounts of iron hydroxides in the humus horizon

could be observed for the brown and reddish-brown

soils from the industrial zone of Targoviste (Figure 5).

The presence of these hydroxides is manifested by

brown-yellowish, brown, reddish-brown, yellowish-

rusty or rusty lit of the horizon where they are

Targoviste city according to the pollution rose

deposited.

Characteristic types of soils for studied area are gray luvisol and gray brown luvisol

Bioaccumulation in upper and middle horizon was low; plant debris was mostly

(Figure 4) according SRTS-2003 (reddish brown after SRCS 1980), soils of a reddish hue, quite evident in the upper horizon and really evident in the middle horizon. Water and air permeability of the soil was moderate. Humus content was about 3%, nutrient supply was moderate, the soil reaction was low-acid with pH values in the range of 6.0 to 6.4, and the

decomposed by the action of fungi, and could be observed the formation of small amounts of humus with predominating fulvic acids. Due to intense alteration of mineral component occurs removal of clay colloid from the surface, with accumulation in the Bt horizon, where

degree of base saturation was 80% to 85%.

the profile shows a textural differentiation.

**4. Material and method**  *4.1 Experimental design* 

Figure 5. Iron hydroxides

to reflect a snapshot of the impact of metallurgical activities in this area by particles emissions. Based on weather conditions and pollution direction compass of Dâmboviţa County (Figure 6), were determined that areas found at SW and W towards the emission source are the most affected. In that location have been chosen the harvest area Zone I – industrial fields, with two subzones, for SW and W directions

metals.

Sampling points were chosen

In soils with alluvial B horizon, such as soil in

the industrial area of the Targoviste city, colloidal order mineral fraction of this horizon contains large amounts of colloidal hydroxides (e.g. Fe(OH)3 and Al(OH)3) and various hydrated iron and aluminium sesquioxides free-form (mR2O3·nH2O) [23]. Large amounts of iron hydroxides in the humus horizon could be observed for the brown and reddish-brown soils from the industrial zone of Targoviste (Figure 5). The presence of these hydroxides is manifested by brown-yellowish, brown, reddish-brown, yellowish-

Targoviste city according to the pollution rose respectively. Land at NE, E and SE from the source of pollution, are grouped according with **Figure 6.** Sampling directions from industrial area of Targoviste city according to the pollution rose

the use category in Zone II – agricultural fields sensitive to high concentrations of heavy Sampling of soil was done at distances between 50 and 1000 meters from the source of pollution, from five different points, chosen according to triangle method. The results of metal concentration represent the average of these five samples. From each sampling point, Sampling of soil was done at distances between 50 and 1000 meters from the source of pollution, from five different points, chosen according to triangle method. The results of metal concentration represent the average of these five samples. From each sampling point, samples were taken from three layers: the upper layer (0-5 cm depth), middle layer (5-20 cm depth) and lower layer (20-40 cm depth). These layers were chosen according with the depth to which the roots of culture plant normally develop.

Figure 6. Sampling directions from industrial area of

samples were taken from three layers: the upper layer (0-5 cm depth), middle layer (5-20 cm depth) and lower layer (20-40 cm depth). These layers were chosen according with the The soil samples were processed in the laboratory for elemental analysis by ICP-AES. The soil samples were dried at 40 °C for 24 hours, ground to a fine powder, sieved at 250 µm (according to SR ISO 11464).
