**Sediment Contamination**

[19] Oliveira H Jr, Moreira BA, Damasceno JJR, Arouca FO. Obtaining constitutive equations for thickening and filtration non-Newtonian fluids. Materials Science Forum. 2014;802:

[20] Moreira BA, Arouca FO, Damasceno JJR. Avaliação da permeabilidade de meios porosos constituídos por carbonato de cálcio utilizado como agente obturante em processos de perfuração de poços de petróleo. Exacta, São Paulo. 2012;10(3):341-348. DOI: 10.5585/

[21] d'Ávilla JS. Um modelo matemático para a sedimentação. [thesis]. Rio de Janeiro-RJ,

[22] Tiller FM, Leu W. Basic data fitting in filtration. Journal of the Chinese Institute of

[23] Endo Y, Chen D, Pui DYH. Effects of particle polydispersity and shape factor during dust cake loading on air filters. Powder Technology. 1998;98:241-249. DOI: 10.1016/S0032-5910

[24] Grace HP. Resistance and compressibility of filter cake. Chemical Engineering Progress.

[25] Ruth BF. Correlation filtration theory with industrial practice. Industrial & Engineering

[26] Tiller FM, Haynes S Jr, Lu W. The role of porosity in filtration VII—Effect of side-wall friction in compression—Permeability cells. AIChE Journal. 1972;18:13-20. DOI: 10.1002/

[27] Gardner RP, Ely RL Jr. Radioisotope Measurement Applications in Engineering. New

Brazil: Universidade Federal do Rio de Janeiro—COPPE/UFRJ; 1978

274-279. DOI: 10.4028/www.scientific.net/MSF.802.274

Exacta.v10n3.3908

128 Sedimentation Engineering

Engineers. 1980;1:61-70

Chemistry. 1946;38(6):564-571

York, EUA: Reinhold Publishing Corporation; 1967

(98)00063-1

1953;49:303-318

aic.690180104

**Chapter 8**

**Provisional chapter**

**Contamination of Selected Persistent Organic**

**Contamination of Selected Persistent Organic** 

**Vietnam**

**Vietnam**

Vu Duc Toan and Ngo Tra Mai

Vu Duc Toan and Ngo Tra Mai

http://dx.doi.org/10.5772/intechopen.70425

**Abstract**

**1. Introduction**

using the modeling method.

sediment in Vietnam.

Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

**Pollutants (POPs) in Sediment of Some Areas in**

**Pollutants (POPs) in Sediment of Some Areas in** 

DOI: 10.5772/intechopen.70425

This chapter evaluates the contamination of selected persistent organic pollutants (S-POPs) in the sediment of some typical areas in Vietnam. S-POPs are composed of dichlorodiphenyltrichloroethanes (DDTs), hexachlorocyclohexanes (HCHs), polychlorinated biphenyl (PCBs), and polybrominated diphenyl ethers (PBDEs). The collected data and analyzed results indicated the wide occurrence of significant S-POPs residues in studied areas. The main sources of S-POPs are discussed by using composition analyses and diagnostic ratios of S-POPs indicator. Ecotoxicological risk of S-POPs is assessed. The obtained results have contributed to the assessment of S-POPs fate in the environmental

**Keywords:** sediment, persistent organic pollutants, residues, ecological risk assessment

Persistent organic pollutants (POPs) have low solubility in water and dissolve well in nonpolar solvents. Therefore, when penetrating into the river, POPs tend to accumulate in creatures in the river (such as fish, shellfish…), suspended solids, and sediment. In sediment, most POPs accumulate in organic phases and persist for a long time. A part of POPs is transformed through chemical reactions, decomposed, and diffused back into the rivers. Flowing from the river to the sea, POPs are transmitted along with suspended solids and creatures. POPs distribution in the river water-sediment is a continuous process, which is considered to be important for detailed valuation in studies about POPs in the environment; it can be simulated

> © 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution,

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

distribution, and reproduction in any medium, provided the original work is properly cited.

and reproduction in any medium, provided the original work is properly cited.

**Provisional chapter**

### **Contamination of Selected Persistent Organic Pollutants (POPs) in Sediment of Some Areas in Vietnam Pollutants (POPs) in Sediment of Some Areas in Vietnam**

**Contamination of Selected Persistent Organic** 

DOI: 10.5772/intechopen.70425

Vu Duc Toan and Ngo Tra Mai Additional information is available at the end of the chapter

Vu Duc Toan and Ngo Tra Mai

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.70425

#### **Abstract**

This chapter evaluates the contamination of selected persistent organic pollutants (S-POPs) in the sediment of some typical areas in Vietnam. S-POPs are composed of dichlorodiphenyltrichloroethanes (DDTs), hexachlorocyclohexanes (HCHs), polychlorinated biphenyl (PCBs), and polybrominated diphenyl ethers (PBDEs). The collected data and analyzed results indicated the wide occurrence of significant S-POPs residues in studied areas. The main sources of S-POPs are discussed by using composition analyses and diagnostic ratios of S-POPs indicator. Ecotoxicological risk of S-POPs is assessed. The obtained results have contributed to the assessment of S-POPs fate in the environmental sediment in Vietnam.

**Keywords:** sediment, persistent organic pollutants, residues, ecological risk assessment

### **1. Introduction**

Persistent organic pollutants (POPs) have low solubility in water and dissolve well in nonpolar solvents. Therefore, when penetrating into the river, POPs tend to accumulate in creatures in the river (such as fish, shellfish…), suspended solids, and sediment. In sediment, most POPs accumulate in organic phases and persist for a long time. A part of POPs is transformed through chemical reactions, decomposed, and diffused back into the rivers. Flowing from the river to the sea, POPs are transmitted along with suspended solids and creatures. POPs distribution in the river water-sediment is a continuous process, which is considered to be important for detailed valuation in studies about POPs in the environment; it can be simulated using the modeling method.

Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons

Studies about POPs residue in sediment are mostly about the surface layer. The selected depths of sampling in the surface layer vary depending on the viewpoint of research groups in the world (usually 2, 3, and 10 cm in depth). Several studies also evaluate POPs residue according to depth and carry analysis for numerous segments (which can be tens of centimeters, depending on the substance in POP group and characteristics of the waste source). However, in many cases, it is very difficult to compare the obtained results of studies because of the difference in the quantity of POPs used for analysis. For example, total polychlorinated biphenyl (PCB) residue can consist of 6, 7, 10, or 13 PCBs congeners, depending on the research conditions of standard substances, equipment, procedures, and capability of the research group. Still, within its research conditions and obtained results, each study about POPs residue in sediment contributes to the overall picture of POPs in the environment.

reported that the sediment levels of PCBs measured in their study in 2006 revealed a clear increase compared to 0.79–40 ng/g (mean 13 ng/g) in 1997 and 15–120 ng/g (mean 45 ng/g) in 1999 [3, 4]. Until 2015, sediment levels of PCBs decreased compared to 31.72–167.32 ng/g [5]. Toan et al. reported that the main source of contamination in Hanoi city could originate from the dielectric oil used in old hanging transformers and capacitors [6]. From such equipment, PCBs could penetrate into the environment by re-filling of dielectric oil, mechanical damage, electrical accident, and fire. Statistics until 2006 show that the total amount of dielectric oil containing PCBs in the entire country is approximately 19,000 tons [7]. This clearly indicates a huge contamination source of PCBs in the environment in Vietnam. In central Vietnam, PCBs were found in the environmental sediment of Hue city (Phu Da, A Luoi, and Tam Giang-Cau Hai Lagoon), Quy Nhon city (Thi Nai Lagoon). PCBs penetrated into the lagoons and canals near paddy fields or municipal sewage at low levels (<25 ng/g). In southern Vietnam, PCBs were also found in Mekong River Delta (Tra Vinh), Can Tho city, and Hochiminh city. PCBs were distributed in wide spaces such as drainage from rice fields, rivers near ferry harbors, river near the mouth of Mekong, shrimp farming areas, and canals in the densely populated areas. Highest PCBs concentrations were found in sediment of Saigon River, Hochiminh city (590.5 ng/g) [8]. According to typical data about PCB residues in sediment in Vietnam in **Table 1**, we can draw a number of general conclusions about

Contamination of Selected Persistent Organic Pollutants (POPs) in Sediment of Some Areas...

http://dx.doi.org/10.5772/intechopen.70425

133

• Within 23 years (1994–2016), about 143 typical sediment samples in several areas of Vietnam were analyzed. Obtained results had a great effort to show the PCB residues level in a number of studied areas. However, the database of PCBs is still limited and further assessment

• Studies about total PCBs are quantified according to various PCBs standards. Several studies do not report the depth of sediment sampling, and the component of total PCBs is not the same (total PCBs can be the sum of 6, 7, 22, 53, 93, or even more than 100 PCBs isomers and congeners). Therefore, the comparisons of total PCBs of different studies are relative and are not precise. This calls for a unified standard about PCBs research for application and further study in the future. We recommend that the researchers can analyze only six indicator congeners (PCB 28, 52, 101, 138, 180). After, the sum of six PCBs can be multiplied by five relatively to get the value of total PCBs. This recommendation

• Published studies about PCBs in sediment only provide an initial evaluation about the residue in a point in time without assessments about the time trend variation or in-depth studies about the consequences of PCBs residue in the studied areas. These problems can

Concerning the PCB congeners, PCBs could be detected from tri-CB to octa-CB in the collected sediment samples. The mean percentages of six selected PCB indicators in the collected sediment samples from several studies (**Table 1**) followed the order PCB138 > PCB153 > PCB101 > PCB52 > PCB180 > PCB28. This order can be explained by physical and chemical properties of PCBs.

be additional research directions for PCBs in Vietnam in the future.

studies of PCB residues in sediment in Vietnam (**Figures 1** and **2**):

is required in the future.

is in good agreement with Kohler et al. [16].

**2.3. Composition analyses of PCBs**

Among POPs, dichlorodiphenyltrichloro-ethane (DDTs), hexachlorocyclohexane (HCHs), polychlorinated biphenyl (PCBs), and polybrominated diphenyl ethers (PBDEs) are found in sediment from big cities to remote areas. This chapter will focus on contamination status, composition analyses, and ecological risk assessment of these selected POPs (S-POPs).

### **2. PCBs in sediment in Vietnam**

#### **2.1. General characteristics of PCBs**

PCBs are industrial products, which constitute a global environmental health hazard of solely anthropogenic origin. Theoretically, there are 209 PCB isomers and congeners with 1–10 chlorine atoms attached to the biphenyl molecule.

The term "PCBs homolog" is used to refer to all PCBs with the same number of chlorines. Homolog with different substitution patterns is referred to as isomer. The numbering system for the PCBs is shown above. Positions 2, 2′, 6, and 6′ are called ortho positions, positions 3, 3′, 5, and 5′ are called meta positions, and positions 4 and 4′ are called para positions. The benzene rings can rotate around the bond connecting them. The two extreme configurations are planar and the nonplanar in which the benzene rings are at a 90° angle to each other [1]. The benzene rings of non-ortho substituted PCBs, as well as monoortho substituted PCBs, may assume a planar configuration and are referred to as planar or coplanar congeners. The PCBs congeners are arranged in ascending numerical order using a numbering system that follow the IUPAC rules.

#### **2.2. Contamination status of PCBs**

Monitoring surveys of PCBs residue in sediment have been conducted during the early 1994s. In the northern Vietnam, PCBs were found in environmental sediment of Thaibinh province (Ba Lat Estuary, coast lines of Thai Binh province), Quangninh province (Halong Bay), and Hanoi city (Set, Kim Nguu, CauBay River, Yen So Lake). PCBs penetrated into the estuaries, urban rivers, lakes, and coastal areas. High PCB concentrations were found in sediment of Kim Nguu River (328 ng/g) and Yen So Lake of Hanoi city (384 ng/g) in 2006 [2]. Hoai et al. [2] reported that the sediment levels of PCBs measured in their study in 2006 revealed a clear increase compared to 0.79–40 ng/g (mean 13 ng/g) in 1997 and 15–120 ng/g (mean 45 ng/g) in 1999 [3, 4]. Until 2015, sediment levels of PCBs decreased compared to 31.72–167.32 ng/g [5]. Toan et al. reported that the main source of contamination in Hanoi city could originate from the dielectric oil used in old hanging transformers and capacitors [6]. From such equipment, PCBs could penetrate into the environment by re-filling of dielectric oil, mechanical damage, electrical accident, and fire. Statistics until 2006 show that the total amount of dielectric oil containing PCBs in the entire country is approximately 19,000 tons [7]. This clearly indicates a huge contamination source of PCBs in the environment in Vietnam. In central Vietnam, PCBs were found in the environmental sediment of Hue city (Phu Da, A Luoi, and Tam Giang-Cau Hai Lagoon), Quy Nhon city (Thi Nai Lagoon). PCBs penetrated into the lagoons and canals near paddy fields or municipal sewage at low levels (<25 ng/g). In southern Vietnam, PCBs were also found in Mekong River Delta (Tra Vinh), Can Tho city, and Hochiminh city. PCBs were distributed in wide spaces such as drainage from rice fields, rivers near ferry harbors, river near the mouth of Mekong, shrimp farming areas, and canals in the densely populated areas. Highest PCBs concentrations were found in sediment of Saigon River, Hochiminh city (590.5 ng/g) [8]. According to typical data about PCB residues in sediment in Vietnam in **Table 1**, we can draw a number of general conclusions about studies of PCB residues in sediment in Vietnam (**Figures 1** and **2**):


#### **2.3. Composition analyses of PCBs**

Studies about POPs residue in sediment are mostly about the surface layer. The selected depths of sampling in the surface layer vary depending on the viewpoint of research groups in the world (usually 2, 3, and 10 cm in depth). Several studies also evaluate POPs residue according to depth and carry analysis for numerous segments (which can be tens of centimeters, depending on the substance in POP group and characteristics of the waste source). However, in many cases, it is very difficult to compare the obtained results of studies because of the difference in the quantity of POPs used for analysis. For example, total polychlorinated biphenyl (PCB) residue can consist of 6, 7, 10, or 13 PCBs congeners, depending on the research conditions of standard substances, equipment, procedures, and capability of the research group. Still, within its research conditions and obtained results, each study about POPs residue in sediment contributes to the overall picture of POPs in the environment.

Among POPs, dichlorodiphenyltrichloro-ethane (DDTs), hexachlorocyclohexane (HCHs), polychlorinated biphenyl (PCBs), and polybrominated diphenyl ethers (PBDEs) are found in sediment from big cities to remote areas. This chapter will focus on contamination status,

PCBs are industrial products, which constitute a global environmental health hazard of solely anthropogenic origin. Theoretically, there are 209 PCB isomers and congeners with 1–10 chlo-

The term "PCBs homolog" is used to refer to all PCBs with the same number of chlorines. Homolog with different substitution patterns is referred to as isomer. The numbering system for the PCBs is shown above. Positions 2, 2′, 6, and 6′ are called ortho positions, positions 3, 3′, 5, and 5′ are called meta positions, and positions 4 and 4′ are called para positions. The benzene rings can rotate around the bond connecting them. The two extreme configurations are planar and the nonplanar in which the benzene rings are at a 90° angle to each other [1]. The benzene rings of non-ortho substituted PCBs, as well as monoortho substituted PCBs, may assume a planar configuration and are referred to as planar or coplanar congeners. The PCBs congeners are arranged in ascending numerical order using a numbering system that

Monitoring surveys of PCBs residue in sediment have been conducted during the early 1994s. In the northern Vietnam, PCBs were found in environmental sediment of Thaibinh province (Ba Lat Estuary, coast lines of Thai Binh province), Quangninh province (Halong Bay), and Hanoi city (Set, Kim Nguu, CauBay River, Yen So Lake). PCBs penetrated into the estuaries, urban rivers, lakes, and coastal areas. High PCB concentrations were found in sediment of Kim Nguu River (328 ng/g) and Yen So Lake of Hanoi city (384 ng/g) in 2006 [2]. Hoai et al. [2]

composition analyses, and ecological risk assessment of these selected POPs (S-POPs).

**2. PCBs in sediment in Vietnam**

rine atoms attached to the biphenyl molecule.

**2.1. General characteristics of PCBs**

132 Sedimentation Engineering

follow the IUPAC rules.

**2.2. Contamination status of PCBs**

Concerning the PCB congeners, PCBs could be detected from tri-CB to octa-CB in the collected sediment samples. The mean percentages of six selected PCB indicators in the collected sediment samples from several studies (**Table 1**) followed the order PCB138 > PCB153 > PCB101 > PCB52 > PCB180 > PCB28. This order can be explained by physical and chemical properties of PCBs.

**Location Year of** 

**A. Northern Vietnam**

Ba Lat Estuary, coast lines of Thai Binh province

Ha Long Bay, Quang Ninh province

Nhue River, suburb of Hanoi city

Set River, Hanoi city

Kim Nguu River, Hanoi city

Yen So Lake, Hanoi city

CauBay River, Hanoi city

**B. Central Vietnam**

Phu Da, Hue city **sampling**

**Number of samples**

**Depth of sampling (cm)**

1995/1996 1 0–5 Aroclor 1254, Aroclor

2003–2004 10 –c 8, 18, 28, 29, 44, 52, 66, 87,

1997 1 0–5 Aroclor 1254, Aroclor

1998 1 – Aroclor 1254, Aroclor

2003–2004 16 – 8, 18, 28, 29, 44, 52, 66, 87,

1997 2 0–5 Aroclor 1254, Aroclor

1997 1 0–5 Aroclor 1254, Aroclor

2006 2 – 28, 52, 101, 118, 138,

2006 2 – 28, 52, 101, 118, 138,

2006 2 – 28, 52, 101, 118, 138,

2006 6 – 28, 52, 101, 118, 138,

2015 10 – 4, 5, 6, 7, 8, 9, 10, 12, 13, 15,

1990 1 No data KC-300, KC-400, KC-500,

KC-600e

1260b

1260

1260

1260

1260

153, 180

153, 180

153, 180

153, 180

16, 17, 19, 21, 22, 26, 28, 31, 32, 37, 41, 42, 44, 45, 47, 48, 49, 52, 53, 56, 60, 61, 64, 66, 70, 71, 74, 77, 81, 83, 84, 85, 86, 87, 89, 91, 92, 95, 99, 100, 101, 105, 110, 114, 118, 119, 123, 126, 128, 131, 132, 135, 138, 144, 149, 153, 156, 157, 163, 167, 169, 170, 171, 172, 174, 180, 189, 194, 199, 200, 202, 205, 206, 207

**Component of analyzed PCBs/PCBs standards**

Contamination of Selected Persistent Organic Pollutants (POPs) in Sediment of Some Areas...

101, 105, 110, 118, 128, 138, 153, 170, 180, 187, 195, 200, 206, 209

101, 105, 110, 118, 128, 138, 153, 170, 180, 187, 195, 200, 206, 209

**Total PCBs (ng/g)**

1.7 (0.97–2.51)<sup>d</sup> **Reference Remark**

intertidal mudflat areas

135

intertidal mudflat areas

sediment

sediment

sediment

canal, densely populated

canal, rural area

river

river

river

lake

river

near paddy field

[3] Sediment,

1.1/0.7a [9] Sediment,

http://dx.doi.org/10.5772/intechopen.70425

0.04–0.26 [10] Sediment,

11 [9] Marine

37 [4] Estuary

0.74 [3] Sediment,

22–153 [2] Sediment,

36–139 [2] Sediment,

237–328 [2] Sediment,

20–384 [2] Sediment,

31.72–167.32 [5] Sediment,

0.65 [11] Sediment,

0.11–10.1 [10] Surface

**Figure 1.** The five sampling stations along the coast of northern Vietnam [3].

**Figure 2.** The sampling stations along the Tam Giang-Cau Hai Lagoon, Central Vietnam [12].

According to Toan et al., lightly chlorinated PCBs are less persistent, have lower log Kow, and are more volatile than heavily chlorinated PCBs. Therefore, heavily chlorinated PCBs are more accumulative in the sediment, whereas lightly chlorinated PCBs are degraded and volatilized faster [6].


According to Toan et al., lightly chlorinated PCBs are less persistent, have lower log Kow, and are more volatile than heavily chlorinated PCBs. Therefore, heavily chlorinated PCBs are more accumulative in the sediment, whereas lightly chlorinated PCBs are degraded and volatilized faster [6].

**Figure 2.** The sampling stations along the Tam Giang-Cau Hai Lagoon, Central Vietnam [12].

**Figure 1.** The five sampling stations along the coast of northern Vietnam [3].

134 Sedimentation Engineering


Another explanation could be related to the compositions of PCB mixtures that probably escaped from the dielectric oil. Up to April 1998, 48.3% of the total quantity of dielectric oils in Vietnam was imported from the Soviet Union. Japan and China contributed with smaller percentages of 7.5 and 3.6%, respectively [6, 17]. According to Falandysz et al., the percentages of PCB138, PCB153, PCB101 (along with PCB90), PCB52, PCB180, and PCB28 (along with PCB31) in Sovol (trade name of Soviet Union dielectric oil) were 11.4, 7.0, 6.5, 3.6, 0.4, and 0.8%, respectively [18]. It seems that the predominance of heavily chlorinated PCBs, PCB138, and PCB153, still remained when they penetrated the sediment. In general, low percentages of lightly chlorinated PCBs and a high percentage of heavily chlorinated PCBs in the analyzed sediment samples reflect their long-time

Contamination of Selected Persistent Organic Pollutants (POPs) in Sediment of Some Areas...

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137

To evaluate the ecotoxicological significance of PCBs contamination, total PCBs in collected sediments were compared with the NOAA sediment quality guideline (SQG) [19]. This guideline specifies the "effects range low" (ERL) and the "effects range median" (ERM). The ERL represents the chemical concentration below which an adverse effect would rarely be observed. The ERM represents the concentration above which adverse effect would frequently occur [20]. Only total PCBs of sediment samples in two big cities (Hanoi and Ho Chi Minh cities) exceeded ERM levels (ERM of total PCBs is 180 ng/g). The other sediment samples listed in **Table 1** that were collected from the estuaries, coastal areas, lagoons, canals near paddy field or municipal sewage, drainage from rice fields, rivers near ferry harbors, river near the mouth of Mekong, shrimp-farming areas, were lower than ERL levels (ERL of total PCBs is 22.7 ng/g). This finding raises the concern on PCBs impact in the two big cities of Vietnam. Thus, further investigation is required in Hanoi and Hochiminh cities to assess possible toxic effects on human health and ecologi-

**Figure 3.** Mean percentages of PCB congeners in sediment samples in CauBay River [5].

release **Figure 3** [6].

cal system.

**2.4. Ecological risk assessment of PCBs**

a Dry season/rainy season.

b PCB mixture from the US; Aroclor 1254 and Aroclor 1260 contain more than 100 PCBs isomers and congeners. c Not reported.

dMean (range).

e PCB mixture from Japan. KC-300, KC-400, KC-500, and KC-600 contain more than 100 PCBs isomers and congeners. f Not detected.

**Table 1.** Concentrations of PCBs (ng/g) in sediment from Vietnam.

Another explanation could be related to the compositions of PCB mixtures that probably escaped from the dielectric oil. Up to April 1998, 48.3% of the total quantity of dielectric oils in Vietnam was imported from the Soviet Union. Japan and China contributed with smaller percentages of 7.5 and 3.6%, respectively [6, 17]. According to Falandysz et al., the percentages of PCB138, PCB153, PCB101 (along with PCB90), PCB52, PCB180, and PCB28 (along with PCB31) in Sovol (trade name of Soviet Union dielectric oil) were 11.4, 7.0, 6.5, 3.6, 0.4, and 0.8%, respectively [18]. It seems that the predominance of heavily chlorinated PCBs, PCB138, and PCB153, still remained when they penetrated the sediment. In general, low percentages of lightly chlorinated PCBs and a high percentage of heavily chlorinated PCBs in the analyzed sediment samples reflect their long-time release **Figure 3** [6].

#### **2.4. Ecological risk assessment of PCBs**

**Location Year of** 

136 Sedimentation Engineering

A Luoi, Hue city

Tam Giang, Hue city

Thi Nai Lagoon, Quy Nhon city

**C. Southern Vietnam**

Tra Vinh, Mekong River Delta

Can Tho city, Mekong River delta

Hau River, Mekong River delta

Saigon River, Hochiminh city

a

b

c

e

f

Dry season/rainy season.

Not reported. dMean (range).

Not detected.

**sampling**

**Number of samples**

2002 10 0–2; 2–4;

**Depth of sampling (cm)**

8–10; 20–23; 23–26; 32–35; 38–41; 47–50

1990 1 No data KC-300, KC-400, KC-500,

2010 18 – 11, 16, 19, 18, 17, 24, 27, 16,

1998 1 – 44, 49, 52, 101, 105, 118,

2003–2004 4 No data KC-300, KC-400, KC-500,

2003–2004 7 No data KC-300, KC-400, KC-500,

**Table 1.** Concentrations of PCBs (ng/g) in sediment from Vietnam.

KC-600

detail)

**Component of analyzed PCBs/PCBs standards**

53 congener (no data in

32, 34, 29, 26, 25, 31, 28, 20, 33, 22, 20, 45, 46, 52, 49, 47, 48, 44, 42, 59, 41, 64, 71, 40, 67, 63, 74, 70, 66, 56, 60, 104, 93, 95, 91, 92, 84, 90, 101, 99, 97, 87, 115, 85, 110, 82, 107, 123, 118, 105, 136, 151, 135, 144, 147, 149, 146, 153, 132, 141, 138, 164, 158, 128, 167, 156, 157, 169, 13, 179, 176, 178, 187, 183, 174, 177, 171, 172, 180, 193, 170, 190, 199, 196, 203, 194, 208, 209

128, 138, 149, 153, 170,

2004 5 No data No data 81 [15] Canals,

180, 200

KC-600

KC-600

1996 11 – 28, 52, 101, 138, 153, 180 N.D

PCB mixture from the US; Aroclor 1254 and Aroclor 1260 contain more than 100 PCBs isomers and congeners.

PCB mixture from Japan. KC-300, KC-400, KC-500, and KC-600 contain more than 100 PCBs isomers and congeners.

**Total PCBs (ng/g)**

**Reference Remark**

municipal sewage

sediment, lagoon

Tam Giang-Cau Hai Lagoon

0.18 [11] Sediment,

2.03–24.7 [12] Sediment,

0.47–6.40 [13] Surficial

0.985 [14] Sediment,

1.8 (0.12–3.7)

0.21 (0.12–0.54)

– 590.5<sup>f</sup>

canal

canals in Cantho city

densely populated areas

densely populated areas

[11] Sediment,

[11] Sediment, river

[8] Canals,

To evaluate the ecotoxicological significance of PCBs contamination, total PCBs in collected sediments were compared with the NOAA sediment quality guideline (SQG) [19]. This guideline specifies the "effects range low" (ERL) and the "effects range median" (ERM). The ERL represents the chemical concentration below which an adverse effect would rarely be observed. The ERM represents the concentration above which adverse effect would frequently occur [20]. Only total PCBs of sediment samples in two big cities (Hanoi and Ho Chi Minh cities) exceeded ERM levels (ERM of total PCBs is 180 ng/g). The other sediment samples listed in **Table 1** that were collected from the estuaries, coastal areas, lagoons, canals near paddy field or municipal sewage, drainage from rice fields, rivers near ferry harbors, river near the mouth of Mekong, shrimp-farming areas, were lower than ERL levels (ERL of total PCBs is 22.7 ng/g). This finding raises the concern on PCBs impact in the two big cities of Vietnam. Thus, further investigation is required in Hanoi and Hochiminh cities to assess possible toxic effects on human health and ecological system.

**Figure 3.** Mean percentages of PCB congeners in sediment samples in CauBay River [5].

### **3. PBDEs in sediment in Vietnam**

#### **3.1. General characteristics of PBDEs**

Polybrominated diphenyl ethers (PBDEs) are used commercially as additives in plastics and textiles, building materials, carpets, and vehicles and aircraft with half-lives in the order of 2–10 years. In computers, these compounds are commonly used in printed circuit boards, components such as connectors, cables, plastic covers, and parts of keyboards and monitors. Theoretically, there are 209 PBDEs isomers and congeners with 1–10 bromine atoms attached to the biphenyl molecule.

PBDEs are highly resistant to heat, light, oxidizing, and reducing compounds. Thus, PBDEs are extremely persistent when released into the environment. The use of PBDEs has increased over the last 30 years with production estimated to be about 3000–5000 tons in Europe. Deca-BDE is the largest mix on the market and makes up over 80% of the total PBDE production, whereas penta-BDE and octa-BDE products constitute about 12 and 6%, respectively, of the total PBDE production [21]. The presence of high levels of these compounds in samples from remote areas suggests that they may now have been distributed worldwide as a result of long-range atmospheric transport. PBDEs have been associated with endocrine disruption, neurotoxicity, and cancer. Sediments are major sinks for these contaminants in aquatic environments, and their study is an important step in mapping possible pollution sources and exposure pathways that facilitate PBDE bioavailability to sediment-dwelling organisms [21].

#### **3.2. Contamination status of PBDEs**

From the north to the south of Vietnam, PBDEs was found in environmental sediment of Hanoi city (CauBay river), Quy Nhon city (Thi Nai Lagoon), Hochiminh city (canals), and Saigon-Dongnai River. PBDEs penetrated in the environmental sediment of rivers, lagoon urban canals, urban sewer systems, and estuary. Data about PBDE residue in sediment in these areas of Vietnam are presented in **Table 2**.

**3.3. Composition analyses of PBDEs**

**Table 2.** Concentrations of PBDEs (ng/g) in sediment from Vietnam.

**Location Year of** 

**A. Northern Vietnam** CauBay River, Hanoi city

**B. Central Vietnam** Thi Nai lagoon, Quy Nhon city

**C. Southern Vietnam** Hochiminh city canals

Hochiminh city canals

Not reported.

Not detected.

Saigon-Dongnai estuary

a

b

**sampling**

**Number of samples**

**Depth of sampling (cm)**

2014 10 –a 28, 47, 99, 100,

2010 18 – 17, 28, 47, 66,

2004 5 0–5 28, 47, 99, 100,

2004 6 0–5 28, 47, 99, 100,

2004 3 0–5 28, 47, 99, 100,

**Component of analyzed PBDEs**

153, 154, 209

100, 99, 85, 153, 183

153, 154, 183, 196, 197, 206, 207

153, 154, 183, 196, 197, 206, 207

153, 154, 183, 196, 197, 206, 207

**Concentration PBDEs (ng/g)**

Contamination of Selected Persistent Organic Pollutants (POPs) in Sediment of Some Areas...

**Reference Remark**

river

sediment, lagoon

139

sediment, sewer system

sediments

sediment

15.39–25.64 [21] Sediment,

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N.D – 9.62b [13] Surficial

54.5–119 [22] Urban

<0.2–10.63 [22] Sub-urban

<0.02–0.065 [22] Estuary

tors to explain the predominance of BDE-209.

**3.4. Ecological risk assessment of PBDEs**

mixtures.

Concerning the composition analyses, PBDEs congeners could be detected from tri-BDE to deca-BDE in the collected sediment samples (**Table 2**). BDE-209 was a predominant congener in sediment samples. In the past, BDE-209 is the largest mix on the market and makes up over 8% of the total PBDE production, whereas penta-BDE and octa-BDE products constitute about 12 and 6%, respectively, of the total PBDE production [24]. This is one of important fac-

The mean percentages of six PBDEs indicators in the collected sediment samples followed the order: BDE-47 > BDE-99 > BDE-100 > BDE-154 > BDE-153 > BDE-27. This order is in agreement with chemical properties of PBDEs as well as the percentages of PBDEs in the commercial

It has been suggested that PBDEs biomagnified as they move along a food web. In addition, PBDEs can inhibit growth in colonies of algae as well as depress the reproduction of zooplankton. Based on the toxicity data of benthic organisms, the multiple species have no observed effect on the concentrations of ΣPBDEs which is 3.1 mg/kg of sediment

A number of general conclusions can be drawn from studies about PBDE in Vietnam:


When compared with other regions in the world, the residues of total PBDEs in Hanoi and Hochiminh are lower than those in Dianchi lake, China and and higher than residues found in Hongfeng and Chenghai lake, China [23].


**Table 2.** Concentrations of PBDEs (ng/g) in sediment from Vietnam.

#### **3.3. Composition analyses of PBDEs**

**3. PBDEs in sediment in Vietnam**

Polybrominated diphenyl ethers (PBDEs) are used commercially as additives in plastics and textiles, building materials, carpets, and vehicles and aircraft with half-lives in the order of 2–10 years. In computers, these compounds are commonly used in printed circuit boards, components such as connectors, cables, plastic covers, and parts of keyboards and monitors. Theoretically, there are 209 PBDEs isomers and congeners with 1–10 bromine atoms attached to the biphenyl molecule.

PBDEs are highly resistant to heat, light, oxidizing, and reducing compounds. Thus, PBDEs are extremely persistent when released into the environment. The use of PBDEs has increased over the last 30 years with production estimated to be about 3000–5000 tons in Europe. Deca-BDE is the largest mix on the market and makes up over 80% of the total PBDE production, whereas penta-BDE and octa-BDE products constitute about 12 and 6%, respectively, of the total PBDE production [21]. The presence of high levels of these compounds in samples from remote areas suggests that they may now have been distributed worldwide as a result of long-range atmospheric transport. PBDEs have been associated with endocrine disruption, neurotoxicity, and cancer. Sediments are major sinks for these contaminants in aquatic environments, and their study is an important step in mapping possible pollution sources and exposure pathways that facilitate PBDE bioavailability to

From the north to the south of Vietnam, PBDEs was found in environmental sediment of Hanoi city (CauBay river), Quy Nhon city (Thi Nai Lagoon), Hochiminh city (canals), and Saigon-Dongnai River. PBDEs penetrated in the environmental sediment of rivers, lagoon urban canals, urban sewer systems, and estuary. Data about PBDE residue in sediment in

• At present, there is a lack of studies about PBDE in Vietnam. In three representative studies presented in **Table 2**, the numbers of samples and research areas are not enough to represent PBDE residue in sediment in Vietnam. Published studies do not report the depth of sampling. There are also different viewpoints about the total PBDE value. Components of total PBDE can be the sum of 7, 9, or 11 PBDEs. Therefore, it is difficult to compare research results.

• Published studies about PBDE in sediment are mainly about initial evaluation of residue in a point in time. There is no assessment about the change in trend or in-depth research about the consequences of PBDE residue in the studied areas. Further studies about PBDE

When compared with other regions in the world, the residues of total PBDEs in Hanoi and Hochiminh are lower than those in Dianchi lake, China and and higher than residues found

A number of general conclusions can be drawn from studies about PBDE in Vietnam:

**3.1. General characteristics of PBDEs**

138 Sedimentation Engineering

sediment-dwelling organisms [21].

**3.2. Contamination status of PBDEs**

these areas of Vietnam are presented in **Table 2**.

residue and its impact on the environment are necessary.

in Hongfeng and Chenghai lake, China [23].

Concerning the composition analyses, PBDEs congeners could be detected from tri-BDE to deca-BDE in the collected sediment samples (**Table 2**). BDE-209 was a predominant congener in sediment samples. In the past, BDE-209 is the largest mix on the market and makes up over 8% of the total PBDE production, whereas penta-BDE and octa-BDE products constitute about 12 and 6%, respectively, of the total PBDE production [24]. This is one of important factors to explain the predominance of BDE-209.

The mean percentages of six PBDEs indicators in the collected sediment samples followed the order: BDE-47 > BDE-99 > BDE-100 > BDE-154 > BDE-153 > BDE-27. This order is in agreement with chemical properties of PBDEs as well as the percentages of PBDEs in the commercial mixtures.

#### **3.4. Ecological risk assessment of PBDEs**

It has been suggested that PBDEs biomagnified as they move along a food web. In addition, PBDEs can inhibit growth in colonies of algae as well as depress the reproduction of zooplankton. Based on the toxicity data of benthic organisms, the multiple species have no observed effect on the concentrations of ΣPBDEs which is 3.1 mg/kg of sediment [21, 25]. Most of the collected sediment samples in **Table 2** had residues of PBDEs lower than 3.1 mg/kg. However, the values of PBDEs in the urban canals and urban sewer system of Hochiminh city are very high (maximal 119 ng/g). Due to the propensity of PBDEs to highly accumulate in various compartments of wildlife and human food webs, further evaluation of ecological risk assessment in Hochiminh city should be undertaken as a high priority.

**Location Year of** 

**A. Northern Vietnam**

Diem Dien Estuary, Thai Binh coast lines

Set River, Hanoi city

Kim Nguu River, Hanoi city

Yen So Lake, Hanoi city

CauBay River, Hanoi city

**B. Central Vietnam**

Phu Da, Hue city

**sampling**

**Number of samples**

Ha Long Bay 1997 1 0–5 *p,p'*-DDT; *p,p'*-

**Depth of sampling (cm)**

1995/1996 1 0–5 *p,p'*-DDT; *p,p'*-

1998 1 –a *p,p'*-DDT; *p,p'*-

2003–2004 16 – *p,p'*-DDT; *o,p'*-

2006 2 – *p,p'*-DDT; *o,p'*-

2006 2 – *p,p'*-DDT; *o,p'*-

2006 6 – *p,p'*-DDT; *o,p'*-

2012 10 – *p,p'*-DDT; *p,p'*-

1990 1 No data *p,p'*-DDT; *p,p'*-

**Component of analyzed DDTs;** 

DDE; *p,p'*-DDD; ϒ-HCH, α-HCH, β-HCH, δ-HCH

DDE; *p,p'*-DDD; ϒ-HCH, α-HCH, β-HCH, δ-HCH

DDE; *p,p'*-DDD; ϒ-HCH, α-HCH, β-HCH, δ-HCH

DDT; *p,p'*-DDE; *o,p'*-DDE; *p,p'*- DDD; *o,p'*-DDD; ϒ-HCH, α-HCH, β-HCH, δ-HCH

DDT; *p,p'*-DDE; *o,p'*-DDE; *p,p'*- DDD; *o,p'*-DDD; ϒ-HCH, α-HCH, β-HCH, δ-HCH

DDT; *p,p'*-DDE; *o,p'*-DDE; *p,p'*- DDD; *o,p'*-DDD; ϒ-HCH, α-HCH, β-HCH, δ-HCH

DDT; *p,p'*-DDE; *o,p'*-DDE; *p,p'*- DDD; *o,p'*-DDD; ϒ-HCH, α-HCH, β-HCH, δ-HCH

DDE; *p,p'*-DDD; ϒ-HCH, α-HCH, β-HCH, δ-HCH

DDE; *p,p'*-DDD; ϒ-HCH, α-HCH, β-HCH

**Concentration DDTs; HCHs (ng/g)**

Contamination of Selected Persistent Organic Pollutants (POPs) in Sediment of Some Areas...

1.60–274; N.D<sup>b</sup> – 0.85

> 82–1100; <0.2–17

17–109; <0.2–36

51.84–92.76; 4.65–11.39

**Reference Remark**

intertidal mudflat areas

141

sediment

sediment

sediment

river

[2] Sediment, river

[2] Sediment, lake

[27] Sediment, river

> paddy field

0.52; 0.43 [11] Sediment,

6.2; 0.36 [3] Sediment,

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7.2; 1.8 [3] Marine

28; 6.1 [4] Estuary

215–680; <0.2 [2] Sediment,

[3] Surface

**HCHs**

### **4. DDT and HCH in sediment in Vietnam**

#### **4.1. General characteristics of DDTs and HCHs**

#### *4.1.1. General characteristics of DDTs*

Chemical formula of DDT is C14H9 C15. Technical DDT is prepared by the Bayer condensation of chlorobenzene with trichloroacetaldehyde in oleum (fuming sulfuric acid), and the reaction is carried out with an excess of chlorobenzene (recommended molar ratio 3:1). Technical grade DDT is composed of up to 14 chemical compounds of which only 65–80% is the active ingredient, *p,p'*-DDT and included 15–21% of the nearly inactive *o,p'*-DDT. DDT is transformed by metabolism or by degradation in the environment [26]. The most common metabolites are DDE (1,1-dichloro-2,2-*bis*(*p*-chlorophenyl)ethylene) and DDD (1,1-dichloro-2,2-*bis*(*p*-chlorophenyl) ethane), which usually are found together with DDT in environmental samples. Thus, actually, people and animal are poisoned by these compounds at the same time. Each compound has three isomers and their primary isomers are *p,p'*-DDT; *p,p'*-DDE; *p,p'*-DDD [26]. Total concentration of DDTs can be evaluated by the sum of *p,p'*- DDT; *o,p'*-DDT; *p,p'*-DDE; *o,p'*-DDE; *p,p'*-DDD, and *o,p'*-DDD.

#### *4.1.2. General characteristics of HCHs*

1,2,3,4,5,6-Hexachlorocyclohexane (HCH), also called benzene hexachloride (BHC), is an organochlorine insecticide used throughout the world. HCH is available in two formulations: technical HCH and lindane. A total of eight HCH isomers have been identified in technical HCH. However, only the γ-HCH, α-HCH, β-HCH, and δ-HCH and ε-HCH isomers are stable, and these are the ones commonly identified in technical formulations [26]. Generally, technical HCH consists of approximately 60–70% α-HCH, 5–12% β-HCH, 10–15% γ-HCH, 6–10% δ-HCH, and 3–4% ε-HCH. Lindane contains more than 90% of γ-HCH, but lindane used in many countries is almost pure γ-HCH [27]. Total concentration HCH can be evaluated by the sum of ϒ-HCH, α-HCH, β-HCH, and δ-HCH.

#### **4.2. Contamination status of DDT and HCH**

Data about DDT and HCH residues in sediment in Vietnam are relatively adequate, including sediment in freshwater, brackish water, and seawater. There are research results about DDT and HCH in sediment from 1994 up to now (**Table 3**). According to data in **Table 3**,


[21, 25]. Most of the collected sediment samples in **Table 2** had residues of PBDEs lower than 3.1 mg/kg. However, the values of PBDEs in the urban canals and urban sewer system of Hochiminh city are very high (maximal 119 ng/g). Due to the propensity of PBDEs to highly accumulate in various compartments of wildlife and human food webs, further evaluation of ecological risk assessment in Hochiminh city should be under-

tion of chlorobenzene with trichloroacetaldehyde in oleum (fuming sulfuric acid), and the reaction is carried out with an excess of chlorobenzene (recommended molar ratio 3:1). Technical grade DDT is composed of up to 14 chemical compounds of which only 65–80% is the active ingredient, *p,p'*-DDT and included 15–21% of the nearly inactive *o,p'*-DDT. DDT is transformed by metabolism or by degradation in the environment [26]. The most common metabolites are DDE (1,1-dichloro-2,2-*bis*(*p*-chlorophenyl)ethylene) and DDD (1,1-dichloro-2,2-*bis*(*p*-chlorophenyl) ethane), which usually are found together with DDT in environmental samples. Thus, actually, people and animal are poisoned by these compounds at the same time. Each compound has three isomers and their primary isomers are *p,p'*-DDT; *p,p'*-DDE; *p,p'*-DDD [26]. Total concentration of DDTs can be evaluated by the sum of *p,p'*-

1,2,3,4,5,6-Hexachlorocyclohexane (HCH), also called benzene hexachloride (BHC), is an organochlorine insecticide used throughout the world. HCH is available in two formulations: technical HCH and lindane. A total of eight HCH isomers have been identified in technical HCH. However, only the γ-HCH, α-HCH, β-HCH, and δ-HCH and ε-HCH isomers are stable, and these are the ones commonly identified in technical formulations [26]. Generally, technical HCH consists of approximately 60–70% α-HCH, 5–12% β-HCH, 10–15% γ-HCH, 6–10% δ-HCH, and 3–4% ε-HCH. Lindane contains more than 90% of γ-HCH, but lindane used in many countries is almost pure γ-HCH [27]. Total concentration HCH can be evalu-

Data about DDT and HCH residues in sediment in Vietnam are relatively adequate, including sediment in freshwater, brackish water, and seawater. There are research results about DDT and HCH in sediment from 1994 up to now (**Table 3**). According to data in **Table 3**,

C15. Technical DDT is prepared by the Bayer condensa-

taken as a high priority.

140 Sedimentation Engineering

**4. DDT and HCH in sediment in Vietnam**

DDT; *o,p'*-DDT; *p,p'*-DDE; *o,p'*-DDE; *p,p'*-DDD, and *o,p'*-DDD.

ated by the sum of ϒ-HCH, α-HCH, β-HCH, and δ-HCH.

**4.2. Contamination status of DDT and HCH**

**4.1. General characteristics of DDTs and HCHs**

*4.1.1. General characteristics of DDTs*

Chemical formula of DDT is C14H9

*4.1.2. General characteristics of HCHs*


low residues in most of the sediment samples. Besides, high DDTs concentrations were found in the sediment of Kim Nguu River (1100 ng/g) and Set River of Hanoi city (680 ng/g) in 2006 [2]. This can be explained by the usage of DDTs in the big cities of Vietnam in the past. Both DDTs and HCHs have been used in Vietnam in considerable amounts as pesticides for crop protection and as vector control for public health purposes. DDT had been imported and used

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143

In Central Vietnam, DDTs and HCHs were found in the environmental sediment of Hue city (Phu Da, A Luoi). DDTs and HCHs penetrated into the canals near paddy fields or municipal sewage at medium levels. In southern Vietnam, DDTs and HCHs also found in Mekong River Delta (Duyen Hai and Tra Vinh), Can Tho city, and Hochiminh city. DDTs and HCHs are distributed in wide spaces such as drainage from rice fields, river near ferry harbor, river near the mouth of Mekong, shrimp-farming areas, and canals in the densely populated areas. Highest DDTs concentrations were found in the sediment of Saigon River, Hochiminh city (253.6 ng/g) [8].

Composition differences of HCHs isomers or DDTs metabolites in the environment could indicate different contamination sources. DDT can be biodegraded in the environment to DDD under anaerobic conditions and DDE under aerobic conditions. Thus, *p,p'*-DDD was a major breakdown product of DDT in sediment from different places in Vietnam. With regards to DDT metabolites, the ratio of (*p,p'-*DDE + *p,p'-*DDD)/ΣDDT in the sediment samples collected in 2012 from CauBay River ranged between 0.77 and 0.89 (mean 0.80). The obtained ratios indicated that the degradation of DDT occurred significantly, and there is no recent input of DDT in the study areas [28]. This conclusion was suitable with the fact of usage of DDTs and other studies since 2006 in Vietnam. Among the isomers, β-HCH has the lowest water solubility and vapor pressure, which is the most stable and relatively resistant to microbial degradation. Besides, there is the isomerization of α- to β-HCH and of γ- via α- to the more stable β-HCH, which is energetically more favorable in the environment [28]. Therefore, the β-HCH predominance reflects an old source of input of HCH in the environment. Low ratios of α-HCH/γ-HCH may represent the use of lindane, whereas high ratios of these isomers may depict the use of technical HCH [28]. An α-HCH/γ-HCH ratio in areas where lindane has been typically used ranges from 0.2 to 1 compared to a range from 4 to 15 for technical HCH. According to Toan et al., the mean percentages of HCH isomers analyzed in sediment samples from CauBay River followed the order of β-HCH (43.2%) > α-HCH (39.3%) > γ-HCH (10.7%) > δ-HCH (6.9%) [28, 29]. Therefore, the predominance of β-HCH reflects an old source of input of HCH in the environment. Besides, the ratio of α-HCH/γ-HCH in the analyzed sediment samples of CauBay River ranged between 2.68 and 4.09 (mean 3.73). It means that the use of technical HCH is the major source and lindane

To evaluate the ecotoxicological significance of DDTs and HCHs contamination in collected sediments, our data in **Table 3** were compared with the interim sediment quality guideline

in Vietnam from 1957 up to 1994.

**4.3. Composition analyses of DDTs and HCHs**

is the minor source in the study areas.

**4.4. Ecological risk assessment of DDTs and HCHs**

**Table 3.** Concentration of DDTs and HCHs (ng/g) in sediment from Vietnam.

DDT and HCH have deposited in the sediment in Vietnam in a wide range and for a long time with considerable extent. DDT and HCH residue in sediment in Vietnam is on the decreasing trend.

Monitoring surveys of DDTs and HCHs residue in sediment have been conducted during the early 1994s. In northern Vietnam, DDTs and HCHs were found in environmental sediment of Thaibinh province (Diem Dien Estuary, coast lines of Thai Binh province), Quangninh province (Halong Bay) and Hanoi city (Set, Kim Nguu, CauBay River; Yen So Lake). DDTs and HCHs have penetrated into the estuaries, urban rivers, lakes, and coastal areas. HCHs had low residues in most of the sediment samples. Besides, high DDTs concentrations were found in the sediment of Kim Nguu River (1100 ng/g) and Set River of Hanoi city (680 ng/g) in 2006 [2]. This can be explained by the usage of DDTs in the big cities of Vietnam in the past. Both DDTs and HCHs have been used in Vietnam in considerable amounts as pesticides for crop protection and as vector control for public health purposes. DDT had been imported and used in Vietnam from 1957 up to 1994.

In Central Vietnam, DDTs and HCHs were found in the environmental sediment of Hue city (Phu Da, A Luoi). DDTs and HCHs penetrated into the canals near paddy fields or municipal sewage at medium levels. In southern Vietnam, DDTs and HCHs also found in Mekong River Delta (Duyen Hai and Tra Vinh), Can Tho city, and Hochiminh city. DDTs and HCHs are distributed in wide spaces such as drainage from rice fields, river near ferry harbor, river near the mouth of Mekong, shrimp-farming areas, and canals in the densely populated areas. Highest DDTs concentrations were found in the sediment of Saigon River, Hochiminh city (253.6 ng/g) [8].

### **4.3. Composition analyses of DDTs and HCHs**

Composition differences of HCHs isomers or DDTs metabolites in the environment could indicate different contamination sources. DDT can be biodegraded in the environment to DDD under anaerobic conditions and DDE under aerobic conditions. Thus, *p,p'*-DDD was a major breakdown product of DDT in sediment from different places in Vietnam. With regards to DDT metabolites, the ratio of (*p,p'-*DDE + *p,p'-*DDD)/ΣDDT in the sediment samples collected in 2012 from CauBay River ranged between 0.77 and 0.89 (mean 0.80). The obtained ratios indicated that the degradation of DDT occurred significantly, and there is no recent input of DDT in the study areas [28]. This conclusion was suitable with the fact of usage of DDTs and other studies since 2006 in Vietnam. Among the isomers, β-HCH has the lowest water solubility and vapor pressure, which is the most stable and relatively resistant to microbial degradation. Besides, there is the isomerization of α- to β-HCH and of γ- via α- to the more stable β-HCH, which is energetically more favorable in the environment [28]. Therefore, the β-HCH predominance reflects an old source of input of HCH in the environment. Low ratios of α-HCH/γ-HCH may represent the use of lindane, whereas high ratios of these isomers may depict the use of technical HCH [28]. An α-HCH/γ-HCH ratio in areas where lindane has been typically used ranges from 0.2 to 1 compared to a range from 4 to 15 for technical HCH. According to Toan et al., the mean percentages of HCH isomers analyzed in sediment samples from CauBay River followed the order of β-HCH (43.2%) > α-HCH (39.3%) > γ-HCH (10.7%) > δ-HCH (6.9%) [28, 29]. Therefore, the predominance of β-HCH reflects an old source of input of HCH in the environment. Besides, the ratio of α-HCH/γ-HCH in the analyzed sediment samples of CauBay River ranged between 2.68 and 4.09 (mean 3.73). It means that the use of technical HCH is the major source and lindane is the minor source in the study areas.

#### **4.4. Ecological risk assessment of DDTs and HCHs**

DDT and HCH have deposited in the sediment in Vietnam in a wide range and for a long time with considerable extent. DDT and HCH residue in sediment in Vietnam is on the

Monitoring surveys of DDTs and HCHs residue in sediment have been conducted during the early 1994s. In northern Vietnam, DDTs and HCHs were found in environmental sediment of Thaibinh province (Diem Dien Estuary, coast lines of Thai Binh province), Quangninh province (Halong Bay) and Hanoi city (Set, Kim Nguu, CauBay River; Yen So Lake). DDTs and HCHs have penetrated into the estuaries, urban rivers, lakes, and coastal areas. HCHs had

decreasing trend.

**Location Year of** 

142 Sedimentation Engineering

**C. Southern Vietnam**

A Luoi, Hue city

Can Tho city, Mekong River delta

Duyen Hai, Mekong River delta

Tra Vinh, Mekong River delta

Saigon River, Hochiminh city

a

b

c

Not reported.

Not detected.

Mean value.

**sampling**

**Number of samples**

**Depth of sampling (cm)**

1990 1 No data *p,p'*-DDT; *p,p'*-

2003–2004 4 No data *p,p'*-DDT; *p,p'*-

1998 1 – *p,p'*-DDT; *o,p'*-

1998 1 – *p,p'*-DDT; *o,p'*-

2004 5 No data *p,p'*-DDT; *o,p'*-

1996 11 – *p,p'*-DDT; *p,p'*-

**Table 3.** Concentration of DDTs and HCHs (ng/g) in sediment from Vietnam.

**Component of analyzed DDTs;** 

DDE; *p,p'*-DDD; ϒ-HCH, α-HCH, β-HCH

DDE; *p,p'*-DDD; ϒ-HCH, α-HCH, β-HCH

DDT; *p,p'*-DDE; *o,p'*-DDE; *p,p'*- DDD; *o,p'*-DDD; ϒ-HCH, α-HCH, β-HCH

DDT; *p,p'*-DDE; *o,p'*-DDE; *p,p'*- DDD; *o,p'*-DDD; ϒ-HCH, α-HCH, β-HCH

DDT; *p,p'*-DDE; *o,p'*-DDE; *p,p'*- DDD; *o,p'*-DDD;

DDE; *p,p'*-DDD

**Concentration DDTs; HCHs (ng/g)**

> 1.8–4.3; <0.02–0.11

**Reference Remark**

[11] Sediment,

municipal sewage

canals in Can Tho city

mouth of Mekong, shrimp farming area

canals

canals, densely populated areas

canals, densely populated areas

68; 2.4 [11] Sediment,

0.48; 0.113 [14] Near the

67.49; 0.65 [14] Sediment,

37c [15] Sediment,

1.76–253.6 [8] Sediment,

**HCHs**

To evaluate the ecotoxicological significance of DDTs and HCHs contamination in collected sediments, our data in **Table 3** were compared with the interim sediment quality guideline

as lower than PEL values. With regards to HCHs, no values of ISQG and PEL were reported in the international guidelines. Due to the propensity of DDTs to highly accumulate in various compartments of wildlife and human food webs, further evaluation of ecological risk assess-

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This work investigated the contamination status of S-POPs in sediment of some areas in Vietnam. Wide occurrence and remarkable residue levels of S-POPs have been found in the sediment of study areas. Composition analyses show that S-POPs penetrated in the sediment for a long time. The main sources of S-POPs are from mix sources that have origin form old industrial and agricultural sources. Ecotoxicological of S-POPs is found at low levels. Due to the propensity of S-POPs to accumulate in various compartments of environment, further

2 Institute of Physics, Viet Nam Academy of Science and Technology, Hanoi, Vietnam

[1] Agency for Toxic Substances and Disease Registry (ATSDR). Toxicological Profile for Polychlorinated Biphenyls (PCBs). ATSDR's Toxicological Profiles Web Version. 2002; Available from: https://www.atsdr.cdc.gov/toxprofiles/TP.asp?id=142&tid=26 [Accessed:

[2] Hoai PM, Giger W, Ngoc NT, Minh NH, Viet PH, Berg M, Alder C. A. Recent levels of organochlorine pesticides and polychlorinated biphenyls in sediments of the sewer sys-

[3] Nhan DD, Carvalho FP, Am NM, Tuan NQ, Yen NTH, Villeuneve J-P, Cattini C. Chlorinated pesticides and PCBs in sediments and molluscs from freshwater canals

[4] Viet PH, Hoai PM, Minh NH, Ngoc NT, Hung PT. Persistent organochlorine pesticides and polychlorinated biphenyls in some agricultural and industrial areas in northern

tem in Hanoi, Vietnam. Environmental Pollution. 2010;**158**:913-920

in the Hanoi region. Environmental Pollution. 2001;**112**:311-320

Vietnam. Water Science and Technology. 2000;**42**:223-229

ment in Hanoi and Hochiminh city should be undertaken **Figures 4** and **5**.

evaluation of ecotoxicological should be undertaken as a high priority.

\* and Ngo Tra Mai2

1 Thuyloi University, Hanoi, Vietnam

\*Address all correspondence to: vuductoan2001@yahoo.com

**5. Conclusion**

**Author details**

Vu Duc Toan1

**References**

2017.07.19]

**Figure 4.** Mean percentages of DDT and its metabolites in sediment samples [28].

(ISQG) and the probable effective level (PEL), issued by the Canadian Council of Ministers of Environment [30]. Hoai et al. [2] reported that the concentrations of DDE, DDD, and DDT in all the Hanoi sediment samples were higher than the ISQG values (1.42, 3.54, and 1.19 ng/g, respectively). The DDE, DDD, and DDT generally exceed the PEL values (6.75 ng/g for DDE, 8.51 ng/g for DDD, and 4.77 ng/g for DDT) but vary among the sediment samples [2]. This conclusion is in agreement with DDTs residues in CauBay River and Hochiminh city [22, 28]. In general, most of the collected sediment samples in **Table 3** had DDTs at low levels as well

**Figure 5.** Mean percentages of HCH isomers in sediment samples [28].

as lower than PEL values. With regards to HCHs, no values of ISQG and PEL were reported in the international guidelines. Due to the propensity of DDTs to highly accumulate in various compartments of wildlife and human food webs, further evaluation of ecological risk assessment in Hanoi and Hochiminh city should be undertaken **Figures 4** and **5**.

### **5. Conclusion**

This work investigated the contamination status of S-POPs in sediment of some areas in Vietnam. Wide occurrence and remarkable residue levels of S-POPs have been found in the sediment of study areas. Composition analyses show that S-POPs penetrated in the sediment for a long time. The main sources of S-POPs are from mix sources that have origin form old industrial and agricultural sources. Ecotoxicological of S-POPs is found at low levels. Due to the propensity of S-POPs to accumulate in various compartments of environment, further evaluation of ecotoxicological should be undertaken as a high priority.

### **Author details**

(ISQG) and the probable effective level (PEL), issued by the Canadian Council of Ministers of Environment [30]. Hoai et al. [2] reported that the concentrations of DDE, DDD, and DDT in all the Hanoi sediment samples were higher than the ISQG values (1.42, 3.54, and 1.19 ng/g, respectively). The DDE, DDD, and DDT generally exceed the PEL values (6.75 ng/g for DDE, 8.51 ng/g for DDD, and 4.77 ng/g for DDT) but vary among the sediment samples [2]. This conclusion is in agreement with DDTs residues in CauBay River and Hochiminh city [22, 28]. In general, most of the collected sediment samples in **Table 3** had DDTs at low levels as well

**Figure 4.** Mean percentages of DDT and its metabolites in sediment samples [28].

144 Sedimentation Engineering

**Figure 5.** Mean percentages of HCH isomers in sediment samples [28].

Vu Duc Toan1 \* and Ngo Tra Mai2

\*Address all correspondence to: vuductoan2001@yahoo.com

1 Thuyloi University, Hanoi, Vietnam

2 Institute of Physics, Viet Nam Academy of Science and Technology, Hanoi, Vietnam

### **References**


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[17] Electricity of Vietnam (EVN). Strategy and Environmental Protection Program (in

Contamination of Selected Persistent Organic Pollutants (POPs) in Sediment of Some Areas...

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[18] Falandysz J, Wyrzykowska B, Bochentin I, Hanari N, Orlikowska A, Yuichi H, Yamashita N. Source determination of highly chlorinated biphenyl isomers in pine needles— Comparison to several PCB preparations. Environmental Pollution. 2006;**143**:46-59 [19] Long ER, MacDonald DD, Smith SL, Calder FD. Incidence of adverse biological effects within ranges of chemical concentrations in marine and estuarine sediments.

[20] Hong SH, Yim UH, Shim WJ, Li DH, Oh JR. Nationwide monitoring of polychlorinated biphenyls and organochlorine pesticides in sediments from coastal environment of

[21] Toan VD, Son HV. Residue and ecological risk assessment of polybrominated diphenyl ethers (PBDEs) in sediment from CauBay River, Vietnam. World Academy of Science, Engineering and Technology International Journal of Environmental, Chemical,

[22] Minh NH, Minh TB, Isobe T, Tanabe S. Contamination of Polybrominated diphenylethers in the sewer system of Hochiminh city and estuary of Saigon – Dongnai river. Fifth International Symposium on Brominated Flame Retardants; Kyoto; April 2010. pp. 41-49

[23] Wu F, Guo J, Chang H, Liao H, Zhao X, Mai B, Xing B. Polybrominated diphenyl ethers and decabromodiphenylethane in sediments from twelve lakes in China. Environmental

[24] De Wit C.An overview of brominated flame retardants in the environment. Chemosphere.

[25] Renzi M.Organic Pollutants—Monitoring, Risk and Treatment—Chapter 5—Perfluorinated Organic Compounds and Polybrominated Diphenyl Ethers Compounds—Levels and

[26] Agency for Toxic Substances and Disease Registry (ATSDR). Toxicological Profile for DDT, DDE and DDD, ATSDR's Toxicological Profiles Web Version, 2002. Available from: https://www.atsdr.cdc.gov/toxprofiles/tp.asp?id=81&tid=20 [Accessed: 2017.07.19] [27] Toan VD. Chapter 14: Time trend variation of selected pesticides residues in soil from some regions in Vietnam. In: Jokanović M, editor. The Impact of Pesticide. Cheyenne,

[28] Toan VD. Contamination of selected organochlorine pesticides (OCPs) in sediment from CauBay river. Bulletin of Environmental Contamination and Toxicology. 2012;**89**:516-520

[29] Toan VD. Residue of select organochlorine pesticides (OCPs) in sediment from Vietnam's CauBay River and their impact on agricultural soil and human health. Polish Journal of

[30] Canadian Council of Minister of the Environment (CCME). Canadian Quality Guidelines for the Protection of Aquatic Life-Summary Tables. 2002. Available from: http://www.

Toxicity in Aquatic Environments: A Review. Germany. Intech Publisher; 2013

USA: Academy Publish; 2012. pp. 286-320. ISBN: 978-0-9835850-9-1

ccme.ca/assets/pdf/sedqg\_summary\_table.pdf [Accessed: 2010.07.19]

Environmental Studies. 2015;**24**(1):301-306

Ecological, Geological and Geophysical Engineering. 2014;**8**(5):292-295

Vietnamese). Electricity of Vietnam. Hanoi, Vietnam; 2003

Environmental Management. 1995;**19**:81-97

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[17] Electricity of Vietnam (EVN). Strategy and Environmental Protection Program (in Vietnamese). Electricity of Vietnam. Hanoi, Vietnam; 2003

[5] Toan VD, Quy NP. Residues of polychlorinated biphenyls (PCBs) in sediment from CauBay River and their impacts on agricultural soil, human health risk in KieuKy area, Vietnam. Bulletin of Environmental Contamination and Toxicology. 2015;**95**:177-182

[6] Toan VD, Thao VD, Walder J, Schmutz H-R, Ha CT. Level and distribution of polychlorinated biphenyls (PCBs) in surface soils from Hanoi, Vietnam. Bulletin of Environmental

[7] Vietnam National Environment Agency (NEA), (2006) Vietnam National Plan for Treatment of Persistent Organic Pollutant (in Vietnamese). Available from: http://www.

[8] Phuong PK, Son CPN, Sauvain J, Tarradellas J. Contamination by PCB's, DDT's, and heavy metals in sediments of Ho Chi Minh City's canals, Vietnam. Bulletin of Environmental

[9] Nhan DD, Am NM, Carvalho FP, Villeuneve JP, Cattini C. Organochlorine pesticides and PCBs along the coast of North Vietnam. Science of The Total Environment.

[10] Hong SH, Kim UH, Shim WJ, Oh JR, Viet PH, Park PS. Persistent organochlorine residues in estuarine and marine sediments from Ha Long Bay, Hai Phong Bay, and Ba Lat

[11] Iwata H, Tanabe S, Sakai N, Nishimura A, Tatsukawa R. Geographical distribution of persistent organochlorines in air, water and sediments from Asia and Oceania and their implication for global redistribution from lower latitudes. Environmental Pollution.

[12] Frignani M, Piazza R, Bellucci LG, Cu NH, Zangrando R, Albertazzi S, Moret I, Romano S, Gambaro A. Polychlorinated biphenyls in sediments of the tam Giang-Cau Hai lagoon,

[13] Romano S, Piazza R, Mugnai C, Giuliani S, Bellucci LG, Huu CH, Vecchiato M, Zambon S, Hoai ND, Frignani M. PBDEs and PCBs in sediments of the Thi Nai lagoon (Central Vietnam)

[14] Carvalho FP, Villeneuve JP, Cattini C, Tolosa I, Thuan DD, Nhan DD. Agrochemical and polychlorobyphenyl (PCB) residues in the Mekong River delta, Vietnam. Marine

[15] Minh TB, Iwata H, Agusa T, Minh NH, Inoue S, Kubota R, Tu NPC, Kajiwara N, Kunisue T, Subramanian A, Viet PH, Tuyen BC, Chamnan C, Tana TS, Tanabe S. Contamination by arsenic and persistent organic pollutants in Mekong River: Geographical distribution, patterns of accumulation and implications for environmental quality and human health. In Proceedings of the 2nd International Symposium on the Development of Water Resource Management

[16] Kohler M, Zennegg M, Waeber R. Coplanar polychlorinated biphenyls (PCB) in indoor

nea.gov.vn/thong-tinmt/noidung/vnn\_14\_08\_06.htm [Accessed: 2008.12.01]

Contamination and Toxicology. 2007;**78**:211-216

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estuary, Vietnam. Chemosphere. 2008;**72**:1193-1202

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System in Mekong Watershed. Bangkok, Thailand; 2005. pp. 15-23

air. Environmental Science & Technology. 2002;**36**:4735-4740

1999;**237**:363-371

146 Sedimentation Engineering

1994;**85**:15-33


**Chapter 9**

**Provisional chapter**

**Spatio-Temporal Evolution of Sediments Pollution with**

The present chapter focuses on spatio-temporal evolution of sediments pollution with mobile heavy metals in five sampling campaigns, in an abandoned gold-bearing mining area from Certeju de Jos, Hunedoara County. The investigated zone is situated in a region where for a long period intense activities of mining exploitation was conducted. For determination of total metals content, sediment samples were dissolved with ultrapure nitric acid to microwave digestion. For the determination of mobile metals concentrations, it used the first step of BCR 701 sequential extraction scheme in a modified form, by reducing the extraction time from 16 hours to 20 minutes by sonication. The total and mobile concentrations of metals were determined by using ICP-MS. The concentrations of the mobile fractions of Cd, As and Cu are between 60 and 98% for Cd, 10 and 38% for As and up to 44% for Cu, indicating their presence in a bioavailable form. Due to the high mobility, these metals can pass from sediment to surface water and, implicitly, to the aquatic ecosystems. The pollution indices, calculated for the total content of As, Cd, Cu, Ni and Pb, indicate the presence of a strong environmental risk

**Spatio-Temporal Evolution of Sediments Pollution with** 

DOI: 10.5772/intechopen.70749

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution,

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

distribution, and reproduction in any medium, provided the original work is properly cited.

and reproduction in any medium, provided the original work is properly cited.

**Keywords:** sediments, heavy metals, mining area, index pollution, spatio-temporal

**Mobile Heavy Metals in an Abandoned Mining Area**

**Mobile Heavy Metals in an Abandoned Mining Area** 

**from Romania**

Nicolae Ionut Cristea

**Abstract**

evolution

**from Romania**

Lidia Kim, Geanina-Gabriela Vasile,

http://dx.doi.org/10.5772/intechopen.70749

Luoana Florentina Pascu, Bogdan Stanescu, Alina-Maria Muresan, Adriana Cuciureanu, Gheorghe Batrinescu and Nicolae Ionut Cristea

Pascu, Bogdan Stanescu, Alina-Maria Muresan, Adriana Cuciureanu, Gheorghe Batrinescu and

Lidia Kim, Geanina-Gabriela Vasile, Luoana Florentina

Additional information is available at the end of the chapter

of sediment degradation in most investigated site.

Additional information is available at the end of the chapter

**Provisional chapter**

#### **Spatio-Temporal Evolution of Sediments Pollution with Mobile Heavy Metals in an Abandoned Mining Area from Romania Mobile Heavy Metals in an Abandoned Mining Area from Romania**

**Spatio-Temporal Evolution of Sediments Pollution with** 

DOI: 10.5772/intechopen.70749

Lidia Kim, Geanina-Gabriela Vasile, Luoana Florentina Pascu, Bogdan Stanescu, Alina-Maria Muresan, Adriana Cuciureanu, Gheorghe Batrinescu and Nicolae Ionut Cristea Pascu, Bogdan Stanescu, Alina-Maria Muresan, Adriana Cuciureanu, Gheorghe Batrinescu and Nicolae Ionut Cristea Additional information is available at the end of the chapter

Lidia Kim, Geanina-Gabriela Vasile, Luoana Florentina

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.70749

#### **Abstract**

The present chapter focuses on spatio-temporal evolution of sediments pollution with mobile heavy metals in five sampling campaigns, in an abandoned gold-bearing mining area from Certeju de Jos, Hunedoara County. The investigated zone is situated in a region where for a long period intense activities of mining exploitation was conducted. For determination of total metals content, sediment samples were dissolved with ultrapure nitric acid to microwave digestion. For the determination of mobile metals concentrations, it used the first step of BCR 701 sequential extraction scheme in a modified form, by reducing the extraction time from 16 hours to 20 minutes by sonication. The total and mobile concentrations of metals were determined by using ICP-MS. The concentrations of the mobile fractions of Cd, As and Cu are between 60 and 98% for Cd, 10 and 38% for As and up to 44% for Cu, indicating their presence in a bioavailable form. Due to the high mobility, these metals can pass from sediment to surface water and, implicitly, to the aquatic ecosystems. The pollution indices, calculated for the total content of As, Cd, Cu, Ni and Pb, indicate the presence of a strong environmental risk of sediment degradation in most investigated site.

**Keywords:** sediments, heavy metals, mining area, index pollution, spatio-temporal evolution

Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons

### **1. Introduction**

Nowadays, aquatic sediments contamination with heavy metals is a major environmental problem at both national and global level [1–3]. One of the main sources leading to heavymetal pollution of the aquatic environment is represented by a series of industrial activities associated with mining exploitations processes [4–7].

concentrations, it was proposed to determine the chemical species associated with the metal using sequential extraction schemes in order to ensure the characterization of the metals'

Spatio-Temporal Evolution of Sediments Pollution with Mobile Heavy Metals in an Abandoned…

http://dx.doi.org/10.5772/intechopen.70749

151

In Romania, there are several areas affected by heavy metals contamination such as Baia Mare, Rosia Montana, Certej and Tara Oasului, where gold-mining activities have been car-

The present chapter focuses on spatio-temporal evolution of sediments pollution with mobile heavy metals as Cd, As, Cu, Ni and Pb in five sampling campaigns, in an abandoned goldbearing mining area from Certeju de Jos, Hunedoara County. For estimation level pollution of sediments with heavy metals, pollution indexes were calculated. The investigated zone is situated in an region where for a long period intense activities of mining exploitation was

The analyzed sector (Bajaga River) is located on the territory of Certeju de Jos village,

In the central area of the studied perimeter, the main collector is represented by the Certej Valley. Its main tributaries are Faerag and Mures streams on the right side, and Bocsa Mica

After crossing the mountain area, it has a large reception basin powered by a well-developed torrential network, known as the Baiaga Valley and completed downstream by the Hondol

chemical forms found in sediments, soils and muds [28–31].

Hunedoara County, about 20 km north of Deva City (**Figure 1**).

(Ciongani) and Nojag Valley streams on the left side.

**Figure 1.** Sampling points location – Certej, Hunedoara County.

ried out for a long time [32–35].

conducted.

**2. The study area**

Due to certain conditions imposed by the legislation in force, mining companies are trying to reduce the emission of effluents resulting from operating activities, but despite all the efforts and safety procedures, accidental pollution is still common within this industry.

Also, near abandoned metal mines, high levels of heavy metals can be found as a result of the discharge and dispersion of waste tailings both the aquatic environment and the soils surrounding the mining areas [8–12].

Depending on the geochemical characteristics and the mineral waste tailing loading, the degree of heavy metals contamination recorded in mining areas varies within a large range [13]. Heavy metals concentrations exceeding the permitted limits regulated by the legislation in force are the main source of aquatic toxicity [14, 15]. The sediments coming from metallic mining areas as main feature of the acid pH value that strongly influences the transport of contaminants from sediment to surface water [16–19]. Drainage of both acid mines and also discharged sediments from abandoned metal mines represents a serious threat to the biota and human health [20].

Heavy metals accumulation in sediments occurs through five major processes: precipitation of certain compounds; binding of fine solid particles having active surface points (encountered in discharges or resuspended during turbulence); coprecipitation together with Fe or Mn oxides or in form of carbonates; association with organic molecules and incorporation into mineral crystals [20]. Therefore, these processes are represented by precipitation and adsorption processes. The balance between these two process categories depends on the metal concentrations, the size of the available surfaces and also the concentrations of the complexing agents found in the water [21]. Inorganic precipitates are formed by oxides, hydroxides, carbonates, sulfates and sulfides [22]. Within aquatic systems having high mineral loading, carbonates and hydroxides are reactive species [20]. The heavy metals as Zn, Ag, Hg, Cu, Cd, or Pb have a strong affinity for sulfide ions thus forming precipitates with very low solubility, so association as sulfide is predominant in reducing conditions as well as when sulfide is released as a result of organic matter decomposition [23].

It is important to underline that heavy metals are not biologically degradable and thus can be accumulated by plants or animals by entering in biochemical where they are transformed into various organometallic compounds [14, 24]. In recent years, more and more attention has been paid for the determination of species in which metals are found, taking in account that toxicity, bioavailability, mobility and other properties depend on the chemical forms of the metals within sample [25–27]. Due to this fact, in addition to determining the total metal concentrations, it was proposed to determine the chemical species associated with the metal using sequential extraction schemes in order to ensure the characterization of the metals' chemical forms found in sediments, soils and muds [28–31].

In Romania, there are several areas affected by heavy metals contamination such as Baia Mare, Rosia Montana, Certej and Tara Oasului, where gold-mining activities have been carried out for a long time [32–35].

The present chapter focuses on spatio-temporal evolution of sediments pollution with mobile heavy metals as Cd, As, Cu, Ni and Pb in five sampling campaigns, in an abandoned goldbearing mining area from Certeju de Jos, Hunedoara County. For estimation level pollution of sediments with heavy metals, pollution indexes were calculated. The investigated zone is situated in an region where for a long period intense activities of mining exploitation was conducted.

### **2. The study area**

**1. Introduction**

150 Sedimentation Engineering

associated with mining exploitations processes [4–7].

rounding the mining areas [8–12].

and human health [20].

position [23].

Nowadays, aquatic sediments contamination with heavy metals is a major environmental problem at both national and global level [1–3]. One of the main sources leading to heavymetal pollution of the aquatic environment is represented by a series of industrial activities

Due to certain conditions imposed by the legislation in force, mining companies are trying to reduce the emission of effluents resulting from operating activities, but despite all the efforts

Also, near abandoned metal mines, high levels of heavy metals can be found as a result of the discharge and dispersion of waste tailings both the aquatic environment and the soils sur-

Depending on the geochemical characteristics and the mineral waste tailing loading, the degree of heavy metals contamination recorded in mining areas varies within a large range [13]. Heavy metals concentrations exceeding the permitted limits regulated by the legislation in force are the main source of aquatic toxicity [14, 15]. The sediments coming from metallic mining areas as main feature of the acid pH value that strongly influences the transport of contaminants from sediment to surface water [16–19]. Drainage of both acid mines and also discharged sediments from abandoned metal mines represents a serious threat to the biota

Heavy metals accumulation in sediments occurs through five major processes: precipitation of certain compounds; binding of fine solid particles having active surface points (encountered in discharges or resuspended during turbulence); coprecipitation together with Fe or Mn oxides or in form of carbonates; association with organic molecules and incorporation into mineral crystals [20]. Therefore, these processes are represented by precipitation and adsorption processes. The balance between these two process categories depends on the metal concentrations, the size of the available surfaces and also the concentrations of the complexing agents found in the water [21]. Inorganic precipitates are formed by oxides, hydroxides, carbonates, sulfates and sulfides [22]. Within aquatic systems having high mineral loading, carbonates and hydroxides are reactive species [20]. The heavy metals as Zn, Ag, Hg, Cu, Cd, or Pb have a strong affinity for sulfide ions thus forming precipitates with very low solubility, so association as sulfide is predominant in reducing conditions as well as when sulfide is released as a result of organic matter decom-

It is important to underline that heavy metals are not biologically degradable and thus can be accumulated by plants or animals by entering in biochemical where they are transformed into various organometallic compounds [14, 24]. In recent years, more and more attention has been paid for the determination of species in which metals are found, taking in account that toxicity, bioavailability, mobility and other properties depend on the chemical forms of the metals within sample [25–27]. Due to this fact, in addition to determining the total metal

and safety procedures, accidental pollution is still common within this industry.

The analyzed sector (Bajaga River) is located on the territory of Certeju de Jos village, Hunedoara County, about 20 km north of Deva City (**Figure 1**).

In the central area of the studied perimeter, the main collector is represented by the Certej Valley. Its main tributaries are Faerag and Mures streams on the right side, and Bocsa Mica (Ciongani) and Nojag Valley streams on the left side.

After crossing the mountain area, it has a large reception basin powered by a well-developed torrential network, known as the Baiaga Valley and completed downstream by the Hondol

**Figure 1.** Sampling points location – Certej, Hunedoara County.

Valley, the Certej Valley forms a narrow meadow that gradually spreads until it flows into the Mures River.

From a topographic point of view, the studied area is part of the small mountains group, which has rounded or flat ridges with heights which do not exceed 1300 m. These kinds of mountains groups surround andesite lava beds or quaternary depressions.

Within these types of areas, the water courses are usually short, with steep slopes and insignificant average annual flows. During torrential rains, drift on the slopes occurs rapidly and facilitates the occurrence of impetuous floods, often with catastrophic effects. In these areas, the water courses are short having quick slopes and average annual flows are insignificant as values (**Figure 2**). The river flows undergo major changes during torrential rains when the slopes leakage occurs with high speeds thus facilitating the occurrence of impetuous floods, often with catastrophic effects.

In order to study the spatio-temporal evolution of heavy metal sediment pollution, five sampling campaigns were carried out over 3 years in different periods of the year. In each sampling campaign 10 samples of sediment and surface water associated with sediment within the Certej catchment were taken. In order to compare the results obtained from the polluted sediments, a blank sample was also collected. The location of the sampling points is shown in **Figure 1**, and the GPS coordinates and sample indices are shown in the **Table 1**.

**3. Materials and methods**

(Bs)

**Table 1.** GPS coordinates and description of sampling points.

sediment blank sample

**No. GPS coordinates Sample type/indicative Observations**

The sampling techniques were used in accordance with SR ISO 5667-12/2000 – Guidance on the Sampling of Bottom Sediments the standard in force. The sediment harvested samples were taken from 0 to 5 cm depths using a Van Veen (Wagtech) scrubber. The samples were placed into polypropylene containers which were pre-washed with dilute hydrochloric acid

S1 Sampling point situated on Coranda Stream – upstream

S3 Sampling point situated at the exit Nicodim gallery

Baiaga Stream

with Baiaga Stream

from the quarry area.

S2 Sampling point situated on Baiaga Stream, downstream of the confluence with Coranda stream

Spatio-Temporal Evolution of Sediments Pollution with Mobile Heavy Metals in an Abandoned…

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153

S4 Sampling point situated on Baiaga Stream, downstream of the

S5 Sampling point situated on Baiaga Stream, upstream of the confluence with career water

S6 Sampling point from career water, before of the confluence with

S7 Sampling point situated on Baiaga Stream, downstream of the

S9 Sampling point situated on Baiaga Stream, downstream of the confluence with Ciongani Stream

S10 Sampling point situated on Baiaga Stream, in the Hondol Village

S8 Sampling point situated on Ciongani Stream before of the confluence with Baiaga Stream

confluence with career water from Nicodim gallery

confluence with career water and upstream of the confluence

Sampling point situated on Baiaga Stream – 2 kilometers away

Samples were transported to the test laboratory in refrigerated boxes and stored at 4°C until

*Total content* – A part of each sediment sample collected from these sampling points was first prepared before the actual analysis by air-drying and homogenization. For evaluation of the

**3.1. Sampling**

1 45°

2 45°

3 45°

4 45°

5 45°

6 45°

7 45°

8 45°

9 45°

10 45°

11 46°

23°

23°

23°

22°

22°

22°

22°

22°

22°

22°

23°

59′84.3″ N

00′25.9″ E

59′81.9″ N

00′13.1″ E

59′80.1″ N

00′06.3″ E

59′67.7″ N

59′96.6″ E

59′41.8″ N

59′74.0″ E

59′41.7″ N

59′73.9″ E

59′39.8″ N

59′74.1″ E

59′41.0″ N

59′72.2″ E

59′39.8″ N

59′68.3″ E

59′20.7″ N

59′06.5″ E

00′29.6″ N

00′51.3″ E

solution.

the analysis was done.

**3.2. Sediment pretreatment**

**Figure 2.** Acid mine water – Baiaga stream.


**Table 1.** GPS coordinates and description of sampling points.

### **3. Materials and methods**

#### **3.1. Sampling**

Valley, the Certej Valley forms a narrow meadow that gradually spreads until it flows into

From a topographic point of view, the studied area is part of the small mountains group, which has rounded or flat ridges with heights which do not exceed 1300 m. These kinds of

Within these types of areas, the water courses are usually short, with steep slopes and insignificant average annual flows. During torrential rains, drift on the slopes occurs rapidly and facilitates the occurrence of impetuous floods, often with catastrophic effects. In these areas, the water courses are short having quick slopes and average annual flows are insignificant as values (**Figure 2**). The river flows undergo major changes during torrential rains when the slopes leakage occurs with high speeds thus facilitating the occurrence of impetuous floods,

In order to study the spatio-temporal evolution of heavy metal sediment pollution, five sampling campaigns were carried out over 3 years in different periods of the year. In each sampling campaign 10 samples of sediment and surface water associated with sediment within the Certej catchment were taken. In order to compare the results obtained from the polluted sediments, a blank sample was also collected. The location of the sampling points is shown in

**Figure 1**, and the GPS coordinates and sample indices are shown in the **Table 1**.

mountains groups surround andesite lava beds or quaternary depressions.

the Mures River.

152 Sedimentation Engineering

often with catastrophic effects.

**Figure 2.** Acid mine water – Baiaga stream.

The sampling techniques were used in accordance with SR ISO 5667-12/2000 – Guidance on the Sampling of Bottom Sediments the standard in force. The sediment harvested samples were taken from 0 to 5 cm depths using a Van Veen (Wagtech) scrubber. The samples were placed into polypropylene containers which were pre-washed with dilute hydrochloric acid solution.

Samples were transported to the test laboratory in refrigerated boxes and stored at 4°C until the analysis was done.

#### **3.2. Sediment pretreatment**

*Total content* – A part of each sediment sample collected from these sampling points was first prepared before the actual analysis by air-drying and homogenization. For evaluation of the total content of heavy metals from each soil probe, after this pre-treatment was subjected to the final analysis, only the fraction having smaller dimensions than 63 μm. Through sieving process and using a Fritsch Analysette 3 Spartan Vibratory Sieve Shaker, the sediment samples were separated and finally 2 g of probe were digested in a microwave oven (Berghof, Germany) at 175°C in a 1:3 (v/v) ratio mixture formed by nitric acid (65%):hydrochloric acid (37%) mixture.

*Mobile fraction* – In order to perform mobile fraction determinations, the remaining part of each sediment sample was first sieved in wet condition using surface water from same sampling point in order to maintain the same structure existing in its natural condition. In this case, similar to total content analysis, the fraction having smaller dimensions than 63 μm was also collected.

#### **3.3. Dry matter content**

A separate portion of 1 g was taken from each sample at the same time with the experiments and was dried in an oven at 105 ± 2°C for 3–4 h until constant mass in order to measure dry matter. The results of metals were corrected according to dry matter (d.m.) content.

#### **3.4. Mobile fraction determining methods**

#### *3.4.1. The BCR method*

In order to correlate the existing analysis methods connected to metals deposition within sediments, an European researcher group conducted a collaboration with the Community Reference Materials Office (CRM). As a result of their common work and a viable alternative to the Tessier method [36], a sequential extraction scheme in three stages (BCR scheme) was proposed [37, 38]. Acetic acid (0.11 M, pH = 2.8), hydroxylamine hydrochloride (0.5 M, pH = 2) and ammonium acetate (1 M, pH = 2) were used as extraction agents. Thus three fractions were separated:

**1.** The changeable (mobile) fraction for metals having low adsorption rate that are released by ion exchange processes and carbonate-linked metals.

The metals concentrations obtained by applying BCR sequential extraction scheme were verified using a certified reference material (BCR-701 – lake sediment produced by the Standards, Measurements and Testing Program – European Commission) with a recovery rate between

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The mobile fraction of arsenic was determined using a cold extraction treatment (**Figure 4**). In order to verify the single chemical extraction of these two metals, this procedure was also applied on a certified reference material WQB-1: lake sediment (with a recovery rate between

The BCR method and cold extraction procedures were performed three times per each sediment sample. The final results were reported as an average. To ensure the quality control of the extraction (decreasing contamination during procedure), a blank extraction (without sedi-

99.65 and 99.90%.

*3.4.2. Cold extraction procedure*

**Figure 3.** Scheme BCR modified.

ment) was also used for each set of analysis.

99.70 and 99.88%) [43].


Currently, this extraction procedure is being used on a large scale performing sediment, soil, muddy soil and also waste analysis [39–41].

The exchangeable (mobile) fraction for cadmium, copper, nickel and lead was determined through a modified BCR method that allowed the extraction time reduction from 16 hours to 20 minutes by using ultrasonic shaking [42] for 20 minutes at 50 KHz and 25°C (**Figure 3**).

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**Figure 3.** Scheme BCR modified.

total content of heavy metals from each soil probe, after this pre-treatment was subjected to the final analysis, only the fraction having smaller dimensions than 63 μm. Through sieving process and using a Fritsch Analysette 3 Spartan Vibratory Sieve Shaker, the sediment samples were separated and finally 2 g of probe were digested in a microwave oven (Berghof, Germany) at 175°C in a 1:3 (v/v) ratio mixture formed by nitric acid (65%):hydrochloric acid

*Mobile fraction* – In order to perform mobile fraction determinations, the remaining part of each sediment sample was first sieved in wet condition using surface water from same sampling point in order to maintain the same structure existing in its natural condition. In this case, similar to total content analysis, the fraction having smaller dimensions than 63 μm was

A separate portion of 1 g was taken from each sample at the same time with the experiments and was dried in an oven at 105 ± 2°C for 3–4 h until constant mass in order to measure dry

In order to correlate the existing analysis methods connected to metals deposition within sediments, an European researcher group conducted a collaboration with the Community Reference Materials Office (CRM). As a result of their common work and a viable alternative to the Tessier method [36], a sequential extraction scheme in three stages (BCR scheme) was proposed [37, 38]. Acetic acid (0.11 M, pH = 2.8), hydroxylamine hydrochloride (0.5 M, pH = 2) and ammonium acetate (1 M, pH = 2) were used as extraction agents. Thus three fractions

**1.** The changeable (mobile) fraction for metals having low adsorption rate that are released

**2.** The fraction linked to Fe and Mn oxide, also called the "reducible fraction" due to the fact

**3.** The organic matter fraction, also called the "oxidizable fraction" due to the fact that these

Currently, this extraction procedure is being used on a large scale performing sediment, soil,

The exchangeable (mobile) fraction for cadmium, copper, nickel and lead was determined through a modified BCR method that allowed the extraction time reduction from 16 hours to 20 minutes by using ultrasonic shaking [42] for 20 minutes at 50 KHz and 25°C (**Figure 3**).

by ion exchange processes and carbonate-linked metals.

kinds of metals are released by oxidation.

muddy soil and also waste analysis [39–41].

that these kinds of metals are released when this fraction is reduced.

matter. The results of metals were corrected according to dry matter (d.m.) content.

(37%) mixture.

154 Sedimentation Engineering

also collected.

**3.3. Dry matter content**

*3.4.1. The BCR method*

were separated:

**3.4. Mobile fraction determining methods**

The metals concentrations obtained by applying BCR sequential extraction scheme were verified using a certified reference material (BCR-701 – lake sediment produced by the Standards, Measurements and Testing Program – European Commission) with a recovery rate between 99.65 and 99.90%.

#### *3.4.2. Cold extraction procedure*

The mobile fraction of arsenic was determined using a cold extraction treatment (**Figure 4**). In order to verify the single chemical extraction of these two metals, this procedure was also applied on a certified reference material WQB-1: lake sediment (with a recovery rate between 99.70 and 99.88%) [43].

The BCR method and cold extraction procedures were performed three times per each sediment sample. The final results were reported as an average. To ensure the quality control of the extraction (decreasing contamination during procedure), a blank extraction (without sediment) was also used for each set of analysis.

The spatio-temporal evolution of the cadmium mobile content in all five sampling campaigns

**Sampling S1 S2 S3 S4 S5 S6 S7 S8 S9 S10** March 2013 Cd total 1.96 2.85 4.09 3.05 3.31 4.38 4.88 6.45 6.22 6.33

January 2014 Cd total 1.82 2.76 4.82 1.35 3.88 3.06 4.98 1.35 3.21 5.46

July 2014 Cd total 3.15 3.82 8.19 3.09 2.85 5.08 2.85 3.23 3.71 2.16

October 2014 Cd total 0.98 3.98 1.76 1.1 5.23 1.51 1.39 1.52 2.24 1.82

March 2015 Cd total 2.01 1.03 3.98 2.93 1.12 3.43 1.74 2.52 1.62 2.21

**Table 2.** Total and mobile content of CADMIUM in sediments samples (mg/kg d.m.).

**Figure 5.** Spatio-temporal evolution of cadmium mobile content.

Cd mobile 1.93 2.11 3.64 2.79 2.54 3.09 4.20 5.57 5.37 4.22

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Cd mobile 1.08 1.25 3.76 1.26 1.08 1.43 4.35 1.09 3.00 5.15

Cd mobile 2.32 3.35 7.72 2.76 1.99 2.89 2.32 3.01 3.50 1.99

Cd mobile 0.38 2.82 1.07 0.58 3.10 0.8 0.84 0.72 1.49 1.09

Cd mobile 1.73 0.54 2.65 2.58 0.74 2.61 1.29 2.02 1.35 1.43

In all five sampling campaigns, mobile cadmium concentrations represent at least 35% of the total cadmium content recorded in the analyzed sediments. In most samples, it was observed that the mobile cadmium content ranges between 60 and 98% of total content. Also, due to the

is given in **Figure 5**.

**Figure 4.** Cold extraction procedure scheme for arsenic mobile content.

The total and mobile content of arsenic in sediment samples were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) (Bruker: Aurora M90). All the chemicals and extraction agents were analytical reagents grade provided by Merck. Calibration curve was performed using a Certified Reference Material ICP multi-element standard solution XXI for MS (Merck quality).

#### *3.4.3. Results and discussion*

For all five sampling campaigns, the entire study area indicates an acid pH, both in sediment and in surface water ranging between 3 and 4 pH units.

The results obtained in our study were correlated to the existing limits imposed by the Romanian Order no. 161/2006 on surface water quality and sediments. In **Table 2**, the results for the total and mobile concentrations of cadmium in sediments are shown. Maximum admissible value for total cadmium in sediment according to Romanian Legislation [44] is set to 0.8 mg/kg.

After analyzing the collected data, it was found that in all sampling campaigns total cadmium content exceeded the maximum admissible concentration.

The lowest points of both total and mobile cadmium concentrations were recorded in S1 sampling point located upstream of the quarry and tailings dumps. In the same line, the highest total and mobile cadmium concentrations were recorded in S3 sampling point corresponding to the Nicodim gallery.

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**Table 2.** Total and mobile content of CADMIUM in sediments samples (mg/kg d.m.).

The spatio-temporal evolution of the cadmium mobile content in all five sampling campaigns is given in **Figure 5**.

In all five sampling campaigns, mobile cadmium concentrations represent at least 35% of the total cadmium content recorded in the analyzed sediments. In most samples, it was observed that the mobile cadmium content ranges between 60 and 98% of total content. Also, due to the

**Figure 5.** Spatio-temporal evolution of cadmium mobile content.

The total and mobile content of arsenic in sediment samples were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) (Bruker: Aurora M90). All the chemicals and extraction agents were analytical reagents grade provided by Merck. Calibration curve was performed using a Certified Reference Material ICP multi-element standard solution XXI for MS (Merck quality).

For all five sampling campaigns, the entire study area indicates an acid pH, both in sediment

The results obtained in our study were correlated to the existing limits imposed by the Romanian Order no. 161/2006 on surface water quality and sediments. In **Table 2**, the results for the total and mobile concentrations of cadmium in sediments are shown. Maximum admissible value for total cadmium in sediment according to Romanian Legislation [44] is set to 0.8 mg/kg.

After analyzing the collected data, it was found that in all sampling campaigns total cadmium

The lowest points of both total and mobile cadmium concentrations were recorded in S1 sampling point located upstream of the quarry and tailings dumps. In the same line, the highest total and mobile cadmium concentrations were recorded in S3 sampling point corresponding

*3.4.3. Results and discussion*

156 Sedimentation Engineering

to the Nicodim gallery.

and in surface water ranging between 3 and 4 pH units.

**Figure 4.** Cold extraction procedure scheme for arsenic mobile content.

content exceeded the maximum admissible concentration.

high mobility percentage, cadmium could induce strong pollution upon aquatic environment by passing from sediment within surface water.

The results obtained for total and mobile arsenic concentrations in sediments are presented in **Table 3**.

Maximum admissible value for As in sediment samples is set to 29 mg/kg, limit imposed by the Romanian legislation in force. In all sampling campaigns, total and mobile arsenic content exceeded the maximum admissible concentration. Sampling points S3 and S4 were the ones in which in all sampling campaigns, the total arsenic concentration was 10 times higher than the maximum admissible concentration.

The elevated arsenic concentrations in these points are due to the water intake from the Nicodim gallery and the water coming from the Coranda River that transports contaminants from the North Dump. It was also noted that in the spring campaigns (March 2013 and March 2015) the values obtained are comparative. This behavior confirms that metals are not biodegradable and were accumulated in aquatic systems over extended periods of time.

The spatio-temporal evolution of the mobile arsenic content in all five sampling campaigns is given in **Figure 6**.

The mobile arsenic concentrations reported to the total arsenic content varied between 10 and 38%. March 2015 sampling campaign corresponded to the highest mobile arsenic concentrations.

**Figure 6.** Spatio-temporal evolution of arsenic mobile content.

total

Cu mobil

total

Cu mobil

total

Cu mobil

total

Cu mobil

total

Cu mobil

**Table 4.** Total and mobile content of COPPER in sediments samples (mg/kg d.m.).

March 2013 Cu

January 2014 Cu

July 2014 Cu

October 2014 Cu

March 2015 Cu

**Sampling S1 S2 S3 S4 S5 S6 S7 S8 S9 S10**

75.2 38.9 48.2 57.6 35.4 18.8 47.1 52.6 37.5 42.1

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16.9 12.8 8.27 15.6 8.91 3.56 10.44 12.35 11.9 10.8

28.4 32.2 43.5 70.2 29.1 48.3 35.8 36.8 26.1 25.1

6.85 14.2 9.43 18.7 4.88 19.5 6.61 5.88 7.22 5.47

54.2 105 57 36.4 54.9 139 29.7 54.5 35.5 32.7

11.5 25.7 13.1 8.88 12.5 30.1 5.86 12.9 8.39 8.64

40.4 29.6 51.4 42.8 102 64.1 44.6 109 62.2 40.3

9.6 10.8 7.8 11.4 14.7 7.37 10.5 19.2 8.6 9.6

66.3 15.5 40.4 25.1 48.3 20.6 37.2 33.2 20.8 50.5

6.52 4.92 7.08 2.4 4.08 7.32 1.39 1.76 1.12 1.2

The average arsenic concentration obtained from all five sampling campaigns was 23%, value which represents almost a quarter of the total arsenic content. The high content of mobile arsenic induces significant sediment and aquatic ecosystem pollution.

In **Table 4** the results obtained for total and mobile copper concentrations in sediments for all five sampling campaigns are presented.


**Table 3.** Total and mobile content of ARSENIC in sediments samples (mg/kg d.m.).

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**Figure 6.** Spatio-temporal evolution of arsenic mobile content.

high mobility percentage, cadmium could induce strong pollution upon aquatic environment

The results obtained for total and mobile arsenic concentrations in sediments are presented

Maximum admissible value for As in sediment samples is set to 29 mg/kg, limit imposed by the Romanian legislation in force. In all sampling campaigns, total and mobile arsenic content exceeded the maximum admissible concentration. Sampling points S3 and S4 were the ones in which in all sampling campaigns, the total arsenic concentration was 10 times higher than

The elevated arsenic concentrations in these points are due to the water intake from the Nicodim gallery and the water coming from the Coranda River that transports contaminants from the North Dump. It was also noted that in the spring campaigns (March 2013 and March 2015) the values obtained are comparative. This behavior confirms that metals are not biodegradable and were accumulated in aquatic systems over extended periods of

The spatio-temporal evolution of the mobile arsenic content in all five sampling campaigns is

The mobile arsenic concentrations reported to the total arsenic content varied between 10 and 38%. March 2015 sampling campaign corresponded to the highest mobile arsenic

The average arsenic concentration obtained from all five sampling campaigns was 23%, value which represents almost a quarter of the total arsenic content. The high content of mobile

In **Table 4** the results obtained for total and mobile copper concentrations in sediments for all

**Sampling S1 S2 S3 S4 S5 S6 S7 S8 S9 S10** March 2013 As total 282 176 658 485 386 184 312 356 331 215

January 2014 As total 202 144 588 405 289 218 222 316 209 217

July 2014 As total 378 285 710 512 406 173 296 411 399 381

October 2014 As total 198 129 775 386 276 197 189 345 277 289

March 2015 As total 274 159 614 449 298 175 294 326 246 191

**Table 3.** Total and mobile content of ARSENIC in sediments samples (mg/kg d.m.).

As mobil 65.4 42.1 168 89.5 74.9 57.8 56.1 98.5 88.2 55.8

As mobil 60.9 55.1 129 105 36.1 32.6 42.8 52.4 41.6 35.6

As mobil 71.9 51.6 145 140 93.8 59.6 43.3 91.5 94.5 92.7

As mobil 35.6 25.8 186 81.1 52.4 49.3 29.8 75.9 49.9 46.2

As mobil 29.7 35.4 152 110 81.1 60.3 49.2 88.6 104 56.9

arsenic induces significant sediment and aquatic ecosystem pollution.

by passing from sediment within surface water.

the maximum admissible concentration.

five sampling campaigns are presented.

in **Table 3**.

158 Sedimentation Engineering

time.

given in **Figure 6**.

concentrations.

**Table 4.** Total and mobile content of COPPER in sediments samples (mg/kg d.m.).

Regarding copper concentrations, 56% from the sediment samples has the total content above the maximum admissible concentration limit with is set to 40 mg/kg d.m. No mobile content over the limit has been recorded.

The highest concentrations exceeding twice the maximum admissible concentration are recorded at S5 and S8 (October 2014) and S2 (July 2014).

The spatio-temporal evolution of the mobile copper content in all sampling campaigns is given in **Figure 7**.

Analyzing the data presented in **Figure 7**, a decrease regarding copper content throughout the investigated route was noticed as follows: January 2014 > March 2013 > Oct 2014 > March 2015. The bioavailable content was ranged between 2 and 44%. In the same time, it was also recorded a peak in mobile copper concentration, the highest values were found in S2 (44%) and S6 (41%), corresponding to samples collected in January 2014.

All these concentrations exceeded the maximum admissible concentration according to Order 61/2006. In all the other campaigns, the mobile copper concentrations found in the investigated samples were below the maximum admissible value.

In **Table 5**, the results obtained for total and mobile nickel concentrations in sediments collected in all five sampling campaigns are presented. The data were compared with maximum admissible value, which is 35 mg/kg.

> The highest total nickel concentration was recorded in S3 sampling point associated with Nicodim gallery (two times higher than limit). Also nickel exceedings in S5 and S8 (July 2014),

**Sampling S1 S2 S3 S4 S5 S6 S7 S8 S9 S10**

32.3 16.7 62.3 18.2 33.9 16.5 8.44 43.9 30.5 30.9

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8.05 6.55 14.8 8.04 19.2 8.63 2.60 8.40 9.32 10.6

24.3 20.5 38.6 23.1 30.8 14.2 26.2 25.2 17.6 18.6

7.35 6.28 10.7 9.84 16.5 6.82 5.86 4.79 5.88 11.7

34.7 25.8 75.9 29.1 40.6 24.2 19.7 38.5 32.8 27.4

7.25 8.64 17.9 5.33 11.9 9.26 3.81 4.56 7.62 6.25

19.1 15.2 45.1 23.4 26.9 8.03 43.9 6.58 30.1 22.9

2.83 2.60 7.94 6.83 11.9 2.17 4.56 1.79 8.28 9.71

27.6 22.8 65.4 25.2 30.9 12.7 15.4 25.8 22.7 31.9

5.41 6.33 20.8 7.82 6.49 4.21 8.52 10.4 13.1 16.9

At all the other sampling points, both total and mobile nickel concentrations were below the

The spatio-temporal evolution of nickel mobile content in the all sampling campaigns is given

After the results were collected, we could conclude that in all sampling campaigns the mobile nickel concentrations varied between 10 and 63%.The highest mobile Ni concentrations were determined in the samples coming from S5, S6, S7, S9 and S10 points. In these cases, the values determined exceeded the maximum admitted concentration and represent more than 50% of

The intake of contaminants accumulating in the upstream from Nicodim gallery, mine water and career water could be the main sources of these overtakings. In March 2015, the sampling campaign recorded a decrease of the Ni mobile concentrations for the majority of the investigated sediments. Sediments can change their composition, so they could be more diluted or

loaded, depending on the volume of precipitation and weather conditions [43].

S8 (March 2013) and S7 (October 2014) were found.

**Table 5.** Total and mobile content of NICKEL in sediments samples (mg/kg d.m.).

maximum admissible value.

March 2013 Ni

January 2014 Ni

July 2014 Ni

October 2014 Ni

March 2015 Ni

total

Ni mobil

total

Ni mobil

total

Ni mobil

total

Ni mobil

total

Ni mobil

the total nickel content.

in **Figure 8**.

**Figure 7.** Spatio-temporal evolution of copper mobile content.

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**Table 5.** Total and mobile content of NICKEL in sediments samples (mg/kg d.m.).

Regarding copper concentrations, 56% from the sediment samples has the total content above the maximum admissible concentration limit with is set to 40 mg/kg d.m. No mobile content

The highest concentrations exceeding twice the maximum admissible concentration are

The spatio-temporal evolution of the mobile copper content in all sampling campaigns is

Analyzing the data presented in **Figure 7**, a decrease regarding copper content throughout the investigated route was noticed as follows: January 2014 > March 2013 > Oct 2014 > March 2015. The bioavailable content was ranged between 2 and 44%. In the same time, it was also recorded a peak in mobile copper concentration, the highest values were found in S2 (44%)

All these concentrations exceeded the maximum admissible concentration according to Order 61/2006. In all the other campaigns, the mobile copper concentrations found in the investi-

In **Table 5**, the results obtained for total and mobile nickel concentrations in sediments collected in all five sampling campaigns are presented. The data were compared with maximum

over the limit has been recorded.

admissible value, which is 35 mg/kg.

**Figure 7.** Spatio-temporal evolution of copper mobile content.

given in **Figure 7**.

160 Sedimentation Engineering

recorded at S5 and S8 (October 2014) and S2 (July 2014).

and S6 (41%), corresponding to samples collected in January 2014.

gated samples were below the maximum admissible value.

The highest total nickel concentration was recorded in S3 sampling point associated with Nicodim gallery (two times higher than limit). Also nickel exceedings in S5 and S8 (July 2014), S8 (March 2013) and S7 (October 2014) were found.

At all the other sampling points, both total and mobile nickel concentrations were below the maximum admissible value.

The spatio-temporal evolution of nickel mobile content in the all sampling campaigns is given in **Figure 8**.

After the results were collected, we could conclude that in all sampling campaigns the mobile nickel concentrations varied between 10 and 63%.The highest mobile Ni concentrations were determined in the samples coming from S5, S6, S7, S9 and S10 points. In these cases, the values determined exceeded the maximum admitted concentration and represent more than 50% of the total nickel content.

The intake of contaminants accumulating in the upstream from Nicodim gallery, mine water and career water could be the main sources of these overtakings. In March 2015, the sampling campaign recorded a decrease of the Ni mobile concentrations for the majority of the investigated sediments. Sediments can change their composition, so they could be more diluted or loaded, depending on the volume of precipitation and weather conditions [43].

**Sampling S1 S2 S3 S4 S5 S6 S7 S8 S9 S10**

129 111 235 109 254 120 266 28.8 64.9 103

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10.3 10.1 8.50 3.72 9.98 3.36 11.8 4.77 3.72 4.51

152 144 354 127 103 66.5 185 113 48.4 36.6

10.8 6.42 15.9 9.53 6.87 5.45 10.4 8.70 4.02 6.21

205 157 426 135 79.2 87.8 223 151 88.4 75.9

6.82 4.16 24.5 8.68 3.21 6.17 12.9 18.7 15.9 10.8

213 127 539 115 174 284 165 244 364 131

14.5 2.35 16.3 5.15 2.18 9.89 5.48 8.52 6.92 3.56

145 74.3 382 151 183 219 148 76.9 297 154

12.8 3.85 23.9 8.82 6.14 12.4 8.22 5.44 16.9 8.24

March 2013 Pb

January 2014 Pb

July 2014 Pb

October 2014 Pb

March 2015 Pb

total

Pb mobil

total

Pb mobil

total

Pb mobil

total

Pb mobil

total

Pb mobil

**Figure 9.** Spatio-temporal evolution of lead mobile content.

**Table 6.** Total and mobile content of LEAD in sediments samples (mg/kg d.m.).

**Figure 8.** Spatio-temporal evolution of nickel mobile content.

In **Table 6**, the results obtained for the total and mobile lead concentrations within sediments are presented for the five sampling campaigns:

Regarding Pb content, the results obtained from the most sampling points indicate that the maximum admissible concentration, which is 85 mg/kg, was exceeded.

The highest lead concentrations were recorded at sampling point S3 where the total lead concentration ranges between 235 mg/kg d.m. (March 2013) and 539 mg/kg d.m. (October 2014).

The spatio-temporal evolution of mobile lead content in all five sampling campaigns is shown in **Figure 9**.

Although within the majority of the analyzed sediments the total lead content exceeds the maximum admissible concentration, the mobile content of Pb is below the maximum admissible value and thus in almost all investigated samples does not exceed 15 mg/kg d.m.

This behavior confirms that lead is link in a lower share within oxides, carbonates and organic matter and a greater share within residual fraction.

### **3.5. Estimation the pollution degree by pollution indexes**

In order to assess the pollution degree of the aquatic environment with these toxic metals, we proposed the determination of two pollution indices: the contamination factor (CF) and the geoaccumulation index (Igeo).

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**Table 6.** Total and mobile content of LEAD in sediments samples (mg/kg d.m.).

In **Table 6**, the results obtained for the total and mobile lead concentrations within sediments

Regarding Pb content, the results obtained from the most sampling points indicate that the

The highest lead concentrations were recorded at sampling point S3 where the total lead concentration ranges between 235 mg/kg d.m. (March 2013) and 539 mg/kg d.m. (October

The spatio-temporal evolution of mobile lead content in all five sampling campaigns is shown

Although within the majority of the analyzed sediments the total lead content exceeds the maximum admissible concentration, the mobile content of Pb is below the maximum admissible value and thus in almost all investigated samples does not exceed

This behavior confirms that lead is link in a lower share within oxides, carbonates and organic

In order to assess the pollution degree of the aquatic environment with these toxic metals, we proposed the determination of two pollution indices: the contamination factor (CF) and the

maximum admissible concentration, which is 85 mg/kg, was exceeded.

are presented for the five sampling campaigns:

**Figure 8.** Spatio-temporal evolution of nickel mobile content.

matter and a greater share within residual fraction.

**3.5. Estimation the pollution degree by pollution indexes**

2014).

in **Figure 9**.

162 Sedimentation Engineering

15 mg/kg d.m.

geoaccumulation index (Igeo).

**Figure 9.** Spatio-temporal evolution of lead mobile content.

The contamination factor (CF) (**Table 7**)—is given by the ratio between the metal concentration within the sediment and the metal concentration in the natural background. CF is calculated according to Hakanson's formula (Eq. (1)) [45]:

$$CF = \frac{Cs}{Bs} \tag{1}$$

**No. Metal UM Concentration within the natural background**

**No. Metal** *S1 S2 S3 S4 S5 S6 S7 S8 S9 S10* Cd 4.61 6.72 10.6 5.36 7.62 8.12 7.37 7.01 7.91 8.36 As 28.6 19.1 71.6 47.9 35.4 20.3 28.1 37.6 31.3 27.7 Cu 2.26 1.89 2.06 1.98 2.31 2.49 1.66 2.45 1.56 1.63 Ni 0.72 0.53 1.50 0.62 0.85 0.39 0.59 0.73 0.70 0.69 Pb 10.1 7.34 23.2 7.63 9.50 9.31 11.8 7.35 10.3 6.00

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**No. Metal** *S1 S2 S3 S4 S5 S6 S7 S8 S9 S10* Cd 1.62 2.16 2.82 1.84 2.35 2.44 2.30 2.22 2.40 2.48 As 4.25 3.67 5.58 5.00 4.56 3.76 4.23 4.65 4.38 4.21 Cu 0.59 0.33 0.45 0.40 0.62 0.73 0.15 0.71 0.05 0.12 Ni −1.10 −1.50 0.00 −1.30 −0.80 −1.90 −1.30 −1.00 −1.10 −1.10 Pb 2.75 2.29 3.95 2.35 2.66 2.63 2.98 2.29 2.78 2.00

**No. Metal** *S1 S2 S3 S4 S5 S6 S7 S8 S9 S10* Cd 4.61 6.72 10.6 5.36 7.62 8.12 7.37 7.01 7.91 8.36 As 28.6 19.1 71.6 47.9 35.4 20.3 28.1 37.6 31.3 27.7 Cu 2.26 1.89 2.06 1.98 2.31 2.49 1.66 2.45 1.56 1.63 Ni 0.72 0.53 1.50 0.62 0.85 0.39 0.59 0.73 0.70 0.69 Pb 10.1 7.34 23.2 7.63 9.50 9.31 11.8 7.35 10.3 6.00

**No. Metal** *S1 S2 S3 S4 S5 S6 S7 S8 S9 S10* Cd 1.62 2.16 2.82 1.84 2.35 2.44 2.30 2.22 2.40 2.48 As 4.25 3.67 5.58 5.00 4.56 3.76 4.23 4.65 4.38 4.21 Cu 0.59 0.33 0.45 0.40 0.62 0.73 0.15 0.71 0.05 0.12 Ni −1.10 −1.50 0.00 −1.30 −0.80 −1.90 −1.30 −1.00 −1.10 −1.10 Pb 2.75 2.29 3.95 2.35 2.66 2.63 2.98 2.29 2.78 2.00

**Table 10.** Contamination factor (CF) and geoaccumulation index (Igeo) values within sediments.

 Cadmium mg/kg dm 0.43 Arsenic mg/kg dm 9.34 Copper mg/kg dm 23.4 Nickel mg/kg dm 38.3 Lead mg/kg dm 16.7

**Concentration factor CF**

**Geoaccumulation index (I**geo**)**

**Concentration factor CF**

**Geoaccumulation index (I**geo**)**

**Table 9.** Metal concentration within the natural background (Bs).

where *Cs* is the metal concentration within the sample and *Bs* is the metal concentration within the natural background (**Figure 1**).

The geoaccumulation index (Igeo) (**Table 8**) was introduced by Müller [46] and is widely used [15, 47, 48] to determine the pollution degree with heavy metal in surface sediments:

$$Igeo = \log\_2\left[\left(\frac{Cs}{K \times Bs}\right)\right] \tag{2}$$

where *Cs* is the metal concentration within the sample, *Bs* is the metal concentration within the natural background and *K* is the correction factor that takes into account the variation of metal traces in the natural background as a result of the lithogenic effects (*K* = 1.5).

The geoaccumulation index provides a classification system for the pollution degree in relation to the sediment quality [46].

In **Table 9**, the concentrations of metals within the natural background are given.

The determination of contamination factor (CF) and geoaccumulation index (Igeo) involved assuming that each metal concentration introduced in the formulas was the average value obtained after the five sampling campaigns.

Contamination factor (CF) and geoaccumulation index (Igeo) values are shown in **Tables 10** and **11**.


**Table 7.** Contamination factor (CF) and contamination level.


**Table 8.** The relationship between Igeo and the pollution level.

#### Spatio-Temporal Evolution of Sediments Pollution with Mobile Heavy Metals in an Abandoned… http://dx.doi.org/10.5772/intechopen.70749 165


**Table 9.** Metal concentration within the natural background (Bs).

The contamination factor (CF) (**Table 7**)—is given by the ratio between the metal concentration within the sediment and the metal concentration in the natural background. CF is calcu-

where *Cs* is the metal concentration within the sample and *Bs* is the metal concentration

The geoaccumulation index (Igeo) (**Table 8**) was introduced by Müller [46] and is widely used

where *Cs* is the metal concentration within the sample, *Bs* is the metal concentration within the natural background and *K* is the correction factor that takes into account the variation of

The geoaccumulation index provides a classification system for the pollution degree in rela-

The determination of contamination factor (CF) and geoaccumulation index (Igeo) involved assuming that each metal concentration introduced in the formulas was the average value

Contamination factor (CF) and geoaccumulation index (Igeo) values are shown in **Tables 10**

\_\_\_\_\_ *Cs*

[15, 47, 48] to determine the pollution degree with heavy metal in surface sediments:

metal traces in the natural background as a result of the lithogenic effects (*K* = 1.5).

In **Table 9**, the concentrations of metals within the natural background are given.

*Cs*

*Bs* (1)

*<sup>K</sup>* <sup>×</sup> *Bs*)] (2)

lated according to Hakanson's formula (Eq. (1)) [45]:

*CF* = \_\_\_

*Igeo* = log2[(

within the natural background (**Figure 1**).

164 Sedimentation Engineering

tion to the sediment quality [46].

and **11**.

obtained after the five sampling campaigns.

**Igeo value Class of pollution in relation to Igeo Sediment quality** ≤0 0 Unpolluted level

**Table 7.** Contamination factor (CF) and contamination level.

**Contamination factor (CF) Contamination level** CF < 1 Low contamination 1 ≤ CF < 3 Medium contamination 3 ≤ CF < 6 Significant contamination CF > 6 Very high contamination

1–2 2 Moderate pollution level

>5 6 Very high pollution level

3–4 4 High pollution level

**Table 8.** The relationship between Igeo and the pollution level.

0–1 1 Unpolluted level to moderate pollution

2–3 3 Moderate pollution level to high pollution

4–5 5 High pollution level to very high pollution level


**Table 10.** Contamination factor (CF) and geoaccumulation index (Igeo) values within sediments.


From the point of view of metal mobile fraction, Cd and As are predominantly present in a bioavailable form within the analyzed sediments, thus inducing a high degree of pollution

Spatio-Temporal Evolution of Sediments Pollution with Mobile Heavy Metals in an Abandoned…

http://dx.doi.org/10.5772/intechopen.70749

167

The pollution degree of the water depends on the amount of precipitation in the area, a heavy rain implies a less dilution and also the opposite case. Therefore, all the values recorded at most sampling points may be momentary, associated with the place and time

The pollution indexes, calculated for the total content of As, Cd, Cu, Ni and Pb, indicate the

Alina-Maria Muresan, Adriana Cuciureanu, Gheorghe Batrinescu and Nicolae Ionut Cristea

National Research and Development Institute for Industrial Ecology ECOIND, Bucharest,

[1] Lee P-K, Kang M-J, Yu S, Ko K-S, Ha K, Shin S-C, Park JH. Enrichment and geochemical mobility of heavy metals in bottom sediment of the Hoedong reservoir, Korea and their source apportionment. Chemosphere. 2017;**184**:74-85. DOI: 10.1016/j.

[2] El Azhari A, Rhoujjati A, Hachimi MLE. Assessment of heavy metals and arsenic contamination in the sediments of the Moulouya River and the Hassan II Dam downstream of the abandoned mine Zeïda (High Moulouya, Morocco). Journal of African Earth

[3] Kim L, Vasile GG, Stanescu B, Calinescu S, Batrinescu G. Distribution and bioavailability of mobile arsenic in sediments from a mining catchment area. Journal of Environmental

[4] Rieuwerts J, Mighanetara K, Braungardt C, Rollinson G, Pirrie D, Azizi F. Geochemistry and mineralogy of arsenic in mine wastes and stream sediments in a historic metal mining area in the UK. Science of the Total Environment. 2014;**472**:226-234. DOI: 10.1016/j.

[5] Gao Z. Evaluation of heavy metal pollution and its ecological risk in one river reach of a gold mine in Inner Mongolia, Northern China. International Biodeterioration &

Sciences. 2016;**119**:279-288. DOI: 10.1016/j.jafrearsci.2016.04.011

Biodegradation. 2017;**xxx**:1-6. DOI: 10.1016/j.ibiod.2017.01.001

Protection and Ecology. 2015;**16**:1227-1236

upon the aquatic environment by passing from sediments within surface water.

Lidia Kim\*, Geanina-Gabriela Vasile, Luoana Florentina Pascu, Bogdan Stanescu,

presence of a strong environmental risk of sediment degradation.

\*Address all correspondence to: lidiakim17@yahoo.com

of sampling.

**Author details**

Romania

**References**

chemosphere.2017.05.124

scitotenv.2013.11.029

**Table 11.** The quality class for each sediment according to geoaccumulation indexes.

Both arsenic and lead induce a very high contamination (CF > 6). The same behavior was also observed for cadmium, which induces very high contamination with the exception of samples S1 and S4 where the sediments exhibit only considerable contamination. In case of nickel, we could conclude that it induces low contamination in sediments, except for the S3 sediment that also enters into moderate contamination category. In all sediments that were analyzed, copper induced moderate contamination.

Taking in consideration that each of the analyzed sediments had very high concentrations of As, Cd and Pb and without taking into account the contribution that other metals could imply on the samples, the samples were introduce in very high contamination category.

According to the classification given in **Table 8**, the geoaccumulation indexes calculated for Cd in sediments classified sediments S1 and S4 into class 2 (moderate pollution level) and all the other sediments into class 3 (moderately to high polluted).

In the same time, geoaccumulation indexes calculated for As, classified sediments S2 and S6 into class 4 (highly polluted), sediments S1, S2 and S7 into class 4 (highly polluted), sediments S1, S5, S7, S8, S9, S10 into class 5 (from highly polluted to very highly polluted) and sediment S3 and S4 into class 6 (very highly polluted).

In Cu case, the geoaccumulation index values obtained classified all sediments into class 1 (from unpolluted to moderately polluted). Regarding Ni, the geoaccumulation index values obtained classified all sediments into class 0 (unpolluted level). Geoaccumulation index values obtained for Pb, classified sediment S3 into class 4 (heavily polluted) and all other sediments into class 3 (moderately to highly polluted).

Based on the results given in **Table 11**, we could conclude that the most contaminated area is at sampling point S3, the point near Nicodim gallery exit.

### **4. Conclusion**

In all sampling campaigns, the area investigated indicates an acid pH, both in sediment and in surface water. Concerning the total of heavy metal content, from all five metals investigated, Cd, Pb and As induce high sediment contamination with concentrations exceeding the limits imposed by the legislation in force.

From the point of view of metal mobile fraction, Cd and As are predominantly present in a bioavailable form within the analyzed sediments, thus inducing a high degree of pollution upon the aquatic environment by passing from sediments within surface water.

The pollution degree of the water depends on the amount of precipitation in the area, a heavy rain implies a less dilution and also the opposite case. Therefore, all the values recorded at most sampling points may be momentary, associated with the place and time of sampling.

The pollution indexes, calculated for the total content of As, Cd, Cu, Ni and Pb, indicate the presence of a strong environmental risk of sediment degradation.

### **Author details**

Both arsenic and lead induce a very high contamination (CF > 6). The same behavior was also observed for cadmium, which induces very high contamination with the exception of samples S1 and S4 where the sediments exhibit only considerable contamination. In case of nickel, we could conclude that it induces low contamination in sediments, except for the S3 sediment that also enters into moderate contamination category. In all sediments that were analyzed,

Taking in consideration that each of the analyzed sediments had very high concentrations of As, Cd and Pb and without taking into account the contribution that other metals could imply

According to the classification given in **Table 8**, the geoaccumulation indexes calculated for Cd in sediments classified sediments S1 and S4 into class 2 (moderate pollution level) and all

In the same time, geoaccumulation indexes calculated for As, classified sediments S2 and S6 into class 4 (highly polluted), sediments S1, S2 and S7 into class 4 (highly polluted), sediments S1, S5, S7, S8, S9, S10 into class 5 (from highly polluted to very highly polluted) and sediment

In Cu case, the geoaccumulation index values obtained classified all sediments into class 1 (from unpolluted to moderately polluted). Regarding Ni, the geoaccumulation index values obtained classified all sediments into class 0 (unpolluted level). Geoaccumulation index values obtained for Pb, classified sediment S3 into class 4 (heavily polluted) and all other sedi-

Based on the results given in **Table 11**, we could conclude that the most contaminated area is

In all sampling campaigns, the area investigated indicates an acid pH, both in sediment and in surface water. Concerning the total of heavy metal content, from all five metals investigated, Cd, Pb and As induce high sediment contamination with concentrations exceeding the limits

on the samples, the samples were introduce in very high contamination category.

**Sediment Igeo Sediment Igeo S1** 4 **S6** 4 **S2** 4 **S7** 4 **S3** 6 **S8** 5 **S4** 5 **S9** 5 **S5** 5 **S10** 5

**Table 11.** The quality class for each sediment according to geoaccumulation indexes.

the other sediments into class 3 (moderately to high polluted).

copper induced moderate contamination.

166 Sedimentation Engineering

S3 and S4 into class 6 (very highly polluted).

ments into class 3 (moderately to highly polluted).

**4. Conclusion**

imposed by the legislation in force.

at sampling point S3, the point near Nicodim gallery exit.

Lidia Kim\*, Geanina-Gabriela Vasile, Luoana Florentina Pascu, Bogdan Stanescu, Alina-Maria Muresan, Adriana Cuciureanu, Gheorghe Batrinescu and Nicolae Ionut Cristea

\*Address all correspondence to: lidiakim17@yahoo.com

National Research and Development Institute for Industrial Ecology ECOIND, Bucharest, Romania

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**Chapter 10**

**Provisional chapter**

**Marine Sediments as Fundamental Repository of**

**Radioactive Contaminants in Aquatic Ecosystems**

**Marine Sediments as Fundamental Repository of** 

DOI: 10.5772/intechopen.72053

**Radioactive Contaminants in Aquatic Ecosystems**

In the last three decades, the studies of artificial radionuclides concentration have attracted attention, bringing in the most significant long-term threat to the biosphere. In aquatic ecosystems, the main indicators of pollution are contaminated sediments, which are the primary repository of radionuclides and chemical elements in the marine environment. Radioactive contamination factor (RCF) has been proposed as a suitable unit to measure the magnitude of radioactive contamination at global scale, caused mainly by more than 2000 nuclear explosion tests performed during the 1945–1965 period. It is obtained as percentage of contaminant radioactivity (137Cs) compared to natural radioactivity (40K), both expressed in Bq/g of marine sediments conditioned in Marinelli containers and detected in both NaI(Tl) and HPGe detectors. So, in this paper, samples of marine sediments were taken up along the occidental Cuban coasts and analyzed by gamma spectrometry for the determination of gamma-emitting radioisotopes with energies between 60 and 2000 keV. The results proved that the proposed method is simple and suitable to evaluate radioactive contamination. Also, the RCF values provide an appropriate indicator to predict which will be the future pollution levels and if the rate will go

**Keywords:** Cuba, gamma spectrometry, marine sediments, radioactive pollution

Marisé García Batlle and Juan Manuel Navarrete Tejero

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution,

© 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,

distribution, and reproduction in any medium, provided the original work is properly cited.

and reproduction in any medium, provided the original work is properly cited.

Marine sediments constitute radionuclides and toxic elements repository in aquatic ecosystems. For many years, sediment composition has been studied with the purpose of identifying the contamination zones and to research the anthropogenic causing sources. In addition, sediments studies help to predict the pollutant effects on the ecosystem and the possible risks

Marisé García Batlle and

**Abstract**

**1. Introduction**

that can bring for human health.

Juan Manuel Navarrete Tejero

http://dx.doi.org/10.5772/intechopen.72053

Additional information is available at the end of the chapter

down when only have passed 2,4 half-lives of 137Cs.

Additional information is available at the end of the chapter

**Provisional chapter**

### **Marine Sediments as Fundamental Repository of Radioactive Contaminants in Aquatic Ecosystems Marine Sediments as Fundamental Repository of Radioactive Contaminants in Aquatic Ecosystems**

DOI: 10.5772/intechopen.72053

Marisé García Batlle and Juan Manuel Navarrete Tejero Marisé García Batlle and Juan Manuel Navarrete Tejero Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/intechopen.72053

#### **Abstract**

In the last three decades, the studies of artificial radionuclides concentration have attracted attention, bringing in the most significant long-term threat to the biosphere. In aquatic ecosystems, the main indicators of pollution are contaminated sediments, which are the primary repository of radionuclides and chemical elements in the marine environment. Radioactive contamination factor (RCF) has been proposed as a suitable unit to measure the magnitude of radioactive contamination at global scale, caused mainly by more than 2000 nuclear explosion tests performed during the 1945–1965 period. It is obtained as percentage of contaminant radioactivity (137Cs) compared to natural radioactivity (40K), both expressed in Bq/g of marine sediments conditioned in Marinelli containers and detected in both NaI(Tl) and HPGe detectors. So, in this paper, samples of marine sediments were taken up along the occidental Cuban coasts and analyzed by gamma spectrometry for the determination of gamma-emitting radioisotopes with energies between 60 and 2000 keV. The results proved that the proposed method is simple and suitable to evaluate radioactive contamination. Also, the RCF values provide an appropriate indicator to predict which will be the future pollution levels and if the rate will go down when only have passed 2,4 half-lives of 137Cs.

**Keywords:** Cuba, gamma spectrometry, marine sediments, radioactive pollution

#### **1. Introduction**

Marine sediments constitute radionuclides and toxic elements repository in aquatic ecosystems. For many years, sediment composition has been studied with the purpose of identifying the contamination zones and to research the anthropogenic causing sources. In addition, sediments studies help to predict the pollutant effects on the ecosystem and the possible risks that can bring for human health.

© 2016 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2018 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

The geochemical cycle of these pollutants from urban areas is largely determined by how they interact or are trapped in the sediments. Sediments act as integrators and amplifiers of the chemical elements concentrations in waters and play an important role in estuary areas and shallow waters. So, this subject becomes an interesting and important factor to diagnose the environmental quality of marine ecosystems [1]. The isotope variation concentrations in sediments happens according to the deposition rate, particle sedimentation rate, nature and particle size, as well as the presence or absence of organic matter [2, 3]. However, it is important to mention that the sediments are considered contaminated when the concentration levels are above the established limits according to the region and the type of sediment. This chapter shows how radioactive contamination can be measured by radioactive detection of marine sediments. In this type of samples, an appreciable concentration of natural radioactive isotopes such as 40K can be observed. Therefore, by comparing the fission product radioactivity of 137Cs with natural radioactivity from 40K, this magnitude can be evaluated, and the percentage of radioactive contamination in marine sediments can be obtained (*where R***<sup>1</sup>** *and R***<sup>2</sup>** *are the disintegrations per second of Cs-137 and K-40, respectively*) [4].

$$RCF = \frac{R\_i(Cs - 137) \times 100}{R\_i(K - 40)} \tag{1}$$

In 2014, minimal values of 137Cs compared to natural radioactivity were found in Mexican sea waters. The researchers used Eq. (1) and estimated values of about 1% of contamination with 137Cs. They also stated that the variations were due to the characteristics of the sample area, the sea currents and the depth of sampling. **Figure 1** shows the location of the study in Mexico Gulf [4]. So, by taking up samples of marine sediments along the occidental Cuban coasts and analyzing gamma spectrometry for the determination of gamma-emitting radioisotopes with energies between 60 and 2000 keV, it is possible to evaluate the radioactive contamination of this area.

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A fundamental question to be solved in sediment sampling is related to the choice of the sampling point. Logically, it is necessary that a point represents the zone conditions; however, given the unstable and seasonal character of the sedimentary deposit, especially in the case of shore sediments, this choice is not always simple and sometimes a point considered as repre-

To mitigate the possible lack of representativeness from given sample, it has been considered to take up one composite sample, being a topic of discussion the number of subsamples that must conform it. Sampling points are generally defined by their coordinates and depth, in this case, four key points were selected, two on the North coast and two on the South coast, both

**Guanabo beach:** a populated place that belongs to East Havana municipality in Havana province, located at 23.171° North latitude and −82.127° West longitude (in decimal degrees)

**Nautico beach**: a populated place that belongs to Revolution square municipality, in Havana

**Bibijagua beach**: a populated place that belongs to Youth Island municipality, located at

province, located at 23,097° North latitude and −82,451° West longitude (**Figure 3**).

21.889° North latitude and −82.727° West longitude (**Figure 4**).

**2. Experimental**

(**Figure 2**).

sentative for certain time, may cease to be so [7, 8].

located in the Western part of the Cuban island.

**Figure 2.** North western coast location of Guanabo beach.

In Cuba, from the 1990s, research starts to take place in coastal ecosystems. Dating studies of 210Pb in sediments were made in the bays of Havana and Cienfuegos and in the Sagua la Grande estuary. But in contrast to the international situation, studies of radionuclide contamination in marine sediments in Cuba are very few, because research has been conducted to the study of atmospheric artificial flows of radionuclides, as reports flow of 137Cs in Cienfuegos between 1994 and 2002 [5, 6].

**Figure 1.** RCF values obtained by Navarrete et al. [4] (left). Location of the sampling sites in Mexico Gulf (right).

In 2014, minimal values of 137Cs compared to natural radioactivity were found in Mexican sea waters. The researchers used Eq. (1) and estimated values of about 1% of contamination with 137Cs. They also stated that the variations were due to the characteristics of the sample area, the sea currents and the depth of sampling. **Figure 1** shows the location of the study in Mexico Gulf [4]. So, by taking up samples of marine sediments along the occidental Cuban coasts and analyzing gamma spectrometry for the determination of gamma-emitting radioisotopes with energies between 60 and 2000 keV, it is possible to evaluate the radioactive contamination of this area.

### **2. Experimental**

The geochemical cycle of these pollutants from urban areas is largely determined by how they interact or are trapped in the sediments. Sediments act as integrators and amplifiers of the chemical elements concentrations in waters and play an important role in estuary areas and shallow waters. So, this subject becomes an interesting and important factor to diagnose the environmental quality of marine ecosystems [1]. The isotope variation concentrations in sediments happens according to the deposition rate, particle sedimentation rate, nature and particle size, as well as the presence or absence of organic matter [2, 3]. However, it is important to mention that the sediments are considered contaminated when the concentration levels are above the established limits according to the region and the type of sediment. This chapter shows how radioactive contamination can be measured by radioactive detection of marine sediments. In this type of samples, an appreciable concentration of natural radioactive isotopes such as 40K can be observed. Therefore, by comparing the fission product radioactivity of 137Cs with natural radioactivity from 40K, this magnitude can be evaluated, and the percentage of radioactive contamination in marine sediments can be obtained (*where R***<sup>1</sup>** *and R***<sup>2</sup>** *are the disintegrations per second of Cs-137 and* 

(*Cs* <sup>−</sup> **<sup>137</sup>**) <sup>×</sup> **<sup>100</sup>** \_\_\_\_\_\_\_\_\_\_\_\_\_

(*<sup>K</sup>* <sup>−</sup> **<sup>40</sup>**) (1)

*R***2**

In Cuba, from the 1990s, research starts to take place in coastal ecosystems. Dating studies of 210Pb in sediments were made in the bays of Havana and Cienfuegos and in the Sagua la Grande estuary. But in contrast to the international situation, studies of radionuclide contamination in marine sediments in Cuba are very few, because research has been conducted to the study of atmospheric artificial flows of radionuclides, as reports flow of 137Cs in Cienfuegos

**Figure 1.** RCF values obtained by Navarrete et al. [4] (left). Location of the sampling sites in Mexico Gulf (right).

*K-40, respectively*) [4].

174 Sedimentation Engineering

between 1994 and 2002 [5, 6].

*RCF* <sup>=</sup> *<sup>R</sup>***<sup>1</sup>**

A fundamental question to be solved in sediment sampling is related to the choice of the sampling point. Logically, it is necessary that a point represents the zone conditions; however, given the unstable and seasonal character of the sedimentary deposit, especially in the case of shore sediments, this choice is not always simple and sometimes a point considered as representative for certain time, may cease to be so [7, 8].

To mitigate the possible lack of representativeness from given sample, it has been considered to take up one composite sample, being a topic of discussion the number of subsamples that must conform it. Sampling points are generally defined by their coordinates and depth, in this case, four key points were selected, two on the North coast and two on the South coast, both located in the Western part of the Cuban island.

**Guanabo beach:** a populated place that belongs to East Havana municipality in Havana province, located at 23.171° North latitude and −82.127° West longitude (in decimal degrees) (**Figure 2**).

**Nautico beach**: a populated place that belongs to Revolution square municipality, in Havana province, located at 23,097° North latitude and −82,451° West longitude (**Figure 3**).

**Bibijagua beach**: a populated place that belongs to Youth Island municipality, located at 21.889° North latitude and −82.727° West longitude (**Figure 4**).

**Figure 2.** North western coast location of Guanabo beach.

**Batabano Gulf**: a populated place located to the West south of the island capital, which belongs to Batabano municipality in Mayabeque province, located at 22.698° latitude and −82.293° longitude. It is the main coastal and fishing port on the southern coast of the Mayabeque province (**Figure 5**).

average of the marine sediments using a mixture of samples that represent several points. Sampling was carried out following one-star design; this method allows to obtain representative fractions of the place. Another important point is the instrument, which must be in accordance with the study that is to be carried out [8]. In this instance, the sampling was carried out at an approximately distance of 100 m from the coast and 1–1.5 m deep. Since this procedure allows the sediment surface layer sampling, the instruments are the simplest on the market. Therefore, the most appropriate would be the "picker type," which is the most affordable [8]. Samples were collected and stored in previously labeled flasks washed with distilled water.

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For the samples drying, a conventional LAB-LINE Inc. oven was used. The sediments were

Subsequently, the samples were sieved in a 2000-μm sieve, to remove some remains of shells and stones that do not allow the correct Marinelli filling. Then, they were transferred to the

The radioactive contaminants analysis of environmental samples has shown interesting results obtained both by the radiometric study of marine sediments samples from western Cuban coasts performed by Gamma Spectrometry with low background scintillation detector [NaI (Tl) crystal] as well as those obtained with one Hyperpure Germanium detector (HPGe).

containers and proceeded with the gamma measurement (**Figure 6**).

**Figure 6.** (a) Marine sediments, (b) drying oven, (c) 2000-μm sieve, and (d) Marinelli container.

**2.1. Drying and sifting samples**

**2.2. Gamma spectrometry analysis**

dried for 3 days at 40°C until total dryness.

At sampling time, and for our purposes, it is sometimes best to analyze mixtures samples taken simultaneously, at different points, or as close as possible. This allows to evaluate the composition

**Figure 3.** North western coast location of Nautico beach.

**Figure 4.** South western coast location of Bibijagua beach.

**Figure 5.** South western coast location of Batabano gulf.

average of the marine sediments using a mixture of samples that represent several points. Sampling was carried out following one-star design; this method allows to obtain representative fractions of the place. Another important point is the instrument, which must be in accordance with the study that is to be carried out [8]. In this instance, the sampling was carried out at an approximately distance of 100 m from the coast and 1–1.5 m deep. Since this procedure allows the sediment surface layer sampling, the instruments are the simplest on the market. Therefore, the most appropriate would be the "picker type," which is the most affordable [8]. Samples were collected and stored in previously labeled flasks washed with distilled water.

#### **2.1. Drying and sifting samples**

**Batabano Gulf**: a populated place located to the West south of the island capital, which belongs to Batabano municipality in Mayabeque province, located at 22.698° latitude and −82.293° longitude. It is the main coastal and fishing port on the southern coast of the Mayabeque

At sampling time, and for our purposes, it is sometimes best to analyze mixtures samples taken simultaneously, at different points, or as close as possible. This allows to evaluate the composition

province (**Figure 5**).

176 Sedimentation Engineering

**Figure 5.** South western coast location of Batabano gulf.

**Figure 4.** South western coast location of Bibijagua beach.

**Figure 3.** North western coast location of Nautico beach.

For the samples drying, a conventional LAB-LINE Inc. oven was used. The sediments were dried for 3 days at 40°C until total dryness.

Subsequently, the samples were sieved in a 2000-μm sieve, to remove some remains of shells and stones that do not allow the correct Marinelli filling. Then, they were transferred to the containers and proceeded with the gamma measurement (**Figure 6**).

#### **2.2. Gamma spectrometry analysis**

The radioactive contaminants analysis of environmental samples has shown interesting results obtained both by the radiometric study of marine sediments samples from western Cuban coasts performed by Gamma Spectrometry with low background scintillation detector [NaI (Tl) crystal] as well as those obtained with one Hyperpure Germanium detector (HPGe).

**Figure 6.** (a) Marine sediments, (b) drying oven, (c) 2000-μm sieve, and (d) Marinelli container.

### *2.2.1. Gamma spectrometry with low background scintillation detector NaI (Tl)*

For scintillation system measurement, a sodium iodide scintillation equipment, Bicron 3 × 3 well Labtech brand with shielding lead distributed by Industrial and Medical Physicians S.A, was used. The results processing was done in the radioactive detection program *Maestro-32 Software Version 6.0 A65-B32 1997* distributed by ORTEC company.

A radionuclide homogeneous mixture also known as a standard certified sample (EG-ML 733- 99 Isotope Products Laboratories, Burbank, CA, USA, 91504) was used for the equipment energies calibration. That is to say, an active sample containing a series of photon emitting nuclei with known activity and energy has been used. The positions (channel number) of each energy peak are determined accurately, and the efficiency is plotted as a function of the γ rays energy.

Finally, to obtain the disintegrations per second (dps = Bq), the obtained counts per second value must be divided by the detection efficiency determined for each radionuclide. That was

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**Sample Marinelli weight (g) Sample weight (g)**

Guanabo beach 135 561.1 Nautico beach 135 551.1 Bibijagua beach 136 558.2 Batabano gulf 138 552

The activity in Bq/g, for each sample, is obtained by dividing the activity in Bq, between the weights of each sample in the Marinelli container. In **Table 1**, each sample weights are reported.

The measurement procedure is similar. In this type of detector, there is a cryostat system that contains a double wall and a vacuum that guarantees thermal insulation. It also has an extension at the top where the detector is cooled with a liquefied gas, generally liquid nitrogen. Before performing the measurement, the liquid nitrogen system must be filled to ensure that

For the HPGe detector, the energy calibration is performed using *Gamma Vision program* with radioactive sources of 241Am (60 keV), 137Cs (662 keV), 60Co (1173, 1332 keV), and 40K

The efficiency calibration is performed with a known specific activity of KCl standard sample (Potassium Chloride Sigma P9541-500 g). The detection efficiency for 40K was 0.25% and for 137Cs was 0.47%. These values are sensibly lower than those obtained with the scintillation

**Figure 8.** Hyperpure germanium detector (HPGe), ORTEC company. A-23 Lab, Physics Institute, UNAM.

previously determined with the certified references samples.

it is at the proper working temperature.

**Table 1.** Each sample weights in the Marinelli container.

(1460 keV)) for 900 s (**Figure 11**).

*2.2.2. Gamma spectrometry with hyperpure germanium detector (HPGe)*

Besides, a known activity of KCl (Potassium Chloride Sigma P9541-500 g) prepared in the laboratory was used. The efficiency value for 40K was 2.9% and for 137Cs of 5.6%. It is important to note that the efficiency value depends on the sample geometry, size, density, and detector distance. For both detectors used in the gamma analysis, the efficiency varies significantly depending on these parameters. Therefore, each counting geometry requires an efficiency calibration, using a known standard sample, with the same geometry.

For the measurement, the samples must be dried, sieved, and weighed. They should be transferred to Marinelli containers (made of polypropylene with a cylindrical shape and an annular space to hold the sample), taking care not to exceed the filling mark and avoiding any areas with empty spaces that may affect the measurement. The detection time was 24 h.

In **Figure 7**, the system described to obtain the gamma spectra of a sample by scintillation is shown.

The spectrum allows to calculate the area under curve of the peak and therefore the net accounts value in 24 h (accounts/24 h). To obtain the counts per second (counts/seconds or cps), the obtained value in the spectrum corresponding to each selected peak area must be divided by the detection time, which in this case was 24 h (86,400 s).

**Figure 7.** Low background scintillation detector NaI (Tl), 325 Lab, D building, Faculty of Chemistry, UNAM.


**Table 1.** Each sample weights in the Marinelli container.

*2.2.1. Gamma spectrometry with low background scintillation detector NaI (Tl)*

*Software Version 6.0 A65-B32 1997* distributed by ORTEC company.

calibration, using a known standard sample, with the same geometry.

divided by the detection time, which in this case was 24 h (86,400 s).

shown.

178 Sedimentation Engineering

For scintillation system measurement, a sodium iodide scintillation equipment, Bicron 3 × 3 well Labtech brand with shielding lead distributed by Industrial and Medical Physicians S.A, was used. The results processing was done in the radioactive detection program *Maestro-32* 

A radionuclide homogeneous mixture also known as a standard certified sample (EG-ML 733- 99 Isotope Products Laboratories, Burbank, CA, USA, 91504) was used for the equipment energies calibration. That is to say, an active sample containing a series of photon emitting nuclei with known activity and energy has been used. The positions (channel number) of each energy peak are determined accurately, and the efficiency is plotted as a function of the γ rays energy. Besides, a known activity of KCl (Potassium Chloride Sigma P9541-500 g) prepared in the laboratory was used. The efficiency value for 40K was 2.9% and for 137Cs of 5.6%. It is important to note that the efficiency value depends on the sample geometry, size, density, and detector distance. For both detectors used in the gamma analysis, the efficiency varies significantly depending on these parameters. Therefore, each counting geometry requires an efficiency

For the measurement, the samples must be dried, sieved, and weighed. They should be transferred to Marinelli containers (made of polypropylene with a cylindrical shape and an annular space to hold the sample), taking care not to exceed the filling mark and avoiding any areas with empty spaces that may affect the measurement. The detection time was 24 h.

In **Figure 7**, the system described to obtain the gamma spectra of a sample by scintillation is

The spectrum allows to calculate the area under curve of the peak and therefore the net accounts value in 24 h (accounts/24 h). To obtain the counts per second (counts/seconds or cps), the obtained value in the spectrum corresponding to each selected peak area must be

**Figure 7.** Low background scintillation detector NaI (Tl), 325 Lab, D building, Faculty of Chemistry, UNAM.

Finally, to obtain the disintegrations per second (dps = Bq), the obtained counts per second value must be divided by the detection efficiency determined for each radionuclide. That was previously determined with the certified references samples.

The activity in Bq/g, for each sample, is obtained by dividing the activity in Bq, between the weights of each sample in the Marinelli container. In **Table 1**, each sample weights are reported.

#### *2.2.2. Gamma spectrometry with hyperpure germanium detector (HPGe)*

The measurement procedure is similar. In this type of detector, there is a cryostat system that contains a double wall and a vacuum that guarantees thermal insulation. It also has an extension at the top where the detector is cooled with a liquefied gas, generally liquid nitrogen. Before performing the measurement, the liquid nitrogen system must be filled to ensure that it is at the proper working temperature.

For the HPGe detector, the energy calibration is performed using *Gamma Vision program* with radioactive sources of 241Am (60 keV), 137Cs (662 keV), 60Co (1173, 1332 keV), and 40K (1460 keV)) for 900 s (**Figure 11**).

The efficiency calibration is performed with a known specific activity of KCl standard sample (Potassium Chloride Sigma P9541-500 g). The detection efficiency for 40K was 0.25% and for 137Cs was 0.47%. These values are sensibly lower than those obtained with the scintillation

**Figure 8.** Hyperpure germanium detector (HPGe), ORTEC company. A-23 Lab, Physics Institute, UNAM.

detector. The spectra processing is performed in the Maestro-32 Software Version 6.0 program A65-B32 1997 distributed by the ORTEC company.

In this detector, each peak is better solved, which allows a better energy separation and makes it possible to analyze more complex samples, with more radionuclides and nearby energy values, which cannot be solved in scintillation detectors.

The system used can be seen in **Figure 8**. It has a high-voltage power supply, cryostat, preamplifier, amplifier, multi-channel analyzer (MCA), lead shield, and a computer (PC).

### **3. Results**

The RCF values were calculated from the obtained counts in both detectors using the Eq. (1), and considering that the detection time was 24 h = 86,400 s. In **Tables 2** and **3**, the RCF values are reported with their respective experimental error and standard deviation. It is important to note that the considering activity for the calculation of the RCF must be in Bq/g, the sample grams were reported in **Table 1**.

The statistical percentages errors are reported in **Tables 2** and **3** and were calculated according to Eq. (2), also call, the standard deviation of the activity ratio of two radioactive sources [9, 10]:

$$\frac{a}{b} \pm \frac{x}{y} \left(\frac{1}{x} + \frac{1}{y}\right)^{1/2} \tag{2}$$

where *a/b* is the RCF value (%) in each case, *x* is the disintegration per second Cs-137, and *y* is

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If, in addition, the obtained RCF values for each sample in each detector are compared, sev-

• For the North coast, the standard deviation is 3–15% between the two detectors. The standard deviation between both detectors of 15% in Guanabo beach and of 4% for Nautico

• In the South coast, the standard deviation is 6–13% between both detectors. The standard deviation between the two detectors was 13% in Bibijagua beach and 6% de Batabano Gulf.

**2.** The radioactive backgrounds are different; the background is higher in the HPGe detector. **3.** The peaks resolution is sensibly higher in the HPGe detector, each peak is better resolved.

Another interesting aspect that can be noticed is how the RCF values of the southern coast of the island differ from those obtained on the north coast. In all cases, the southern coast has lower RCF values than the north coast. This anomaly can be due to numerous events that they can go from the geological area characteristics and the sediment type, to the winds direction and the proximity to anthropogenic sources. **Figure 9** shows the spectrum obtained with the

In *Maestro program*, it is possible to extract the information about the peaks: the FWHM (Full Width at Half Maximum), the Net and the Gross Area, the Real, Live and Dead Time with the

These differences are expected because both detectors have several differences:

**1.** The detection efficiency is higher in the scintillation detector.

the disintegration per second K-40.

Beach.

eral variations can be observed between them:

scintillation detector for Guanabo beach.

"Peak Info" function, as shown in **Figure 10**.

**Figure 9.** Spectrum obtained with the scintillation detector for Guanabo beach.


**Table 2.** RCF values obtained with the NaI(Tl) detector from the North and South coast of Cuba.


**Table 3.** RCF values obtained with the HPGe detector from the North and South coast of Cuba.

where *a/b* is the RCF value (%) in each case, *x* is the disintegration per second Cs-137, and *y* is the disintegration per second K-40.

If, in addition, the obtained RCF values for each sample in each detector are compared, several variations can be observed between them:


These differences are expected because both detectors have several differences:

**1.** The detection efficiency is higher in the scintillation detector.

detector. The spectra processing is performed in the Maestro-32 Software Version 6.0 program

In this detector, each peak is better solved, which allows a better energy separation and makes it possible to analyze more complex samples, with more radionuclides and nearby energy

The system used can be seen in **Figure 8**. It has a high-voltage power supply, cryostat, pream-

The RCF values were calculated from the obtained counts in both detectors using the Eq. (1), and considering that the detection time was 24 h = 86,400 s. In **Tables 2** and **3**, the RCF values are reported with their respective experimental error and standard deviation. It is important to note that the considering activity for the calculation of the RCF must be in Bq/g, the sample

The statistical percentages errors are reported in **Tables 2** and **3** and were calculated according to Eq. (2), also call, the standard deviation of the activity ratio of two radioactive sources

(2)

*<sup>b</sup>* <sup>±</sup> \_\_*<sup>x</sup> y* ( \_\_1 *<sup>x</sup>* <sup>+</sup> \_\_<sup>1</sup> *y*) 1/2

**Sample Disintegration per second 40K Disintegration per second 137Cs RCF %** Guanabo beach 14.1503 1.6110 11.4 ± 0.09 Nautico beach 8.3413 0.9403 11.3 ± 0.12 Bibijagua beach 11.5162 0.6097 5.3 ± 0.07 Batabano gulf 14.2130 0.7671 5.4 ± 0.06

**Table 2.** RCF values obtained with the NaI(Tl) detector from the North and South coast of Cuba.

**Table 3.** RCF values obtained with the HPGe detector from the North and South coast of Cuba.

**Sample Disintegration per second 40K Disintegration per second 137Cs RCF %** Guanabo beach 0.6091 0.0590 9.7 ± 0.42 Nautico beach 2.5806 0.2805 10.9 ± 0.22 Bibijagua beach 2.8206 0.1715 6.1 ± 0.15 Batabano gulf 3.0632 0.1785 5.8 ± 0.14

plifier, amplifier, multi-channel analyzer (MCA), lead shield, and a computer (PC).

A65-B32 1997 distributed by the ORTEC company.

**3. Results**

180 Sedimentation Engineering

[9, 10]:

grams were reported in **Table 1**.

\_\_*<sup>a</sup>*

values, which cannot be solved in scintillation detectors.


Another interesting aspect that can be noticed is how the RCF values of the southern coast of the island differ from those obtained on the north coast. In all cases, the southern coast has lower RCF values than the north coast. This anomaly can be due to numerous events that they can go from the geological area characteristics and the sediment type, to the winds direction and the proximity to anthropogenic sources. **Figure 9** shows the spectrum obtained with the scintillation detector for Guanabo beach.

In *Maestro program*, it is possible to extract the information about the peaks: the FWHM (Full Width at Half Maximum), the Net and the Gross Area, the Real, Live and Dead Time with the "Peak Info" function, as shown in **Figure 10**.

**Figure 9.** Spectrum obtained with the scintillation detector for Guanabo beach.

**Figure 10.** Spectrum displays the peak information in Maestro program.

It is also interesting to compare the obtained RCF values in Cuba with those obtained in 2011 by Navarrete et al. in marine sediments sampling stations in the Gulf of Mexico. It can be noted that in Mexico, the highest value of RCF was 1.21%; while in Cuba, we found values up to 11% on the North coast [11–13]. **Figures 12** and **13** show the spectra obtained with the Hyperpure Germanium detector (HPGe).

Even though, these last values are not alarming because they constitute a minimum percentage of the natural radioactivity. Nevertheless, it is very interesting and exhorts us to extend this study to other geographical points to establish a global indicator of contamination of the Mexico Gulf and the Caribbean zone.

Now, the spectra obtained in the HPGe detector are shown for two marine sediment samples: one from the North (Guanabo beach) and one from the South coast (Batabano Gulf). The different peak resolutions can be noticed.

> Until now, it has been found that marine sediments are the fundamental repository of contaminants in aquatic ecosystems. The study of these materials is still necessary because if levels above sediment quality international standards are found [14], the quality of water, soils, and crops can be affected. The basic premise used to reduce the contaminants presence in waters, soils, and sediments is the constant monitoring of contaminated areas. This approach should include the long-term pollutants behavior, which is determined by the physic, chemi-

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**Figure 12.** Obtained spectra from the North coast (Guanabo beach) in the HPGe detector.

**Figure 13.** Obtained spectra from the South coast (Batabano gulf) in the HPGe detector.

The obtained results for each Cuban sediment samples did not show alarming values or higher than those established, which make required remediation measures of the zone. It should be noted that for a better understanding of the radioisotopes concentrations metals in the sediments a deeper mineralogical and geochemical characterization of the sediments should be carried out. For example, mass spectrometry methods are generally used to know the isotopic composition of an element, taking into account this premise it can be said that they could also be used

cal, and biochemical reactions in the system [15].

**Figure 11.** Energy calibration spectra for the HPGe detector.

Marine Sediments as Fundamental Repository of Radioactive Contaminants in Aquatic Ecosystems http://dx.doi.org/10.5772/intechopen.72053 183

**Figure 12.** Obtained spectra from the North coast (Guanabo beach) in the HPGe detector.

It is also interesting to compare the obtained RCF values in Cuba with those obtained in 2011 by Navarrete et al. in marine sediments sampling stations in the Gulf of Mexico. It can be noted that in Mexico, the highest value of RCF was 1.21%; while in Cuba, we found values up to 11% on the North coast [11–13]. **Figures 12** and **13** show the spectra obtained with the

Even though, these last values are not alarming because they constitute a minimum percentage of the natural radioactivity. Nevertheless, it is very interesting and exhorts us to extend this study to other geographical points to establish a global indicator of contamination of the

Now, the spectra obtained in the HPGe detector are shown for two marine sediment samples: one from the North (Guanabo beach) and one from the South coast (Batabano Gulf). The dif-

Hyperpure Germanium detector (HPGe).

182 Sedimentation Engineering

**Figure 10.** Spectrum displays the peak information in Maestro program.

Mexico Gulf and the Caribbean zone.

ferent peak resolutions can be noticed.

**Figure 11.** Energy calibration spectra for the HPGe detector.

**Figure 13.** Obtained spectra from the South coast (Batabano gulf) in the HPGe detector.

Until now, it has been found that marine sediments are the fundamental repository of contaminants in aquatic ecosystems. The study of these materials is still necessary because if levels above sediment quality international standards are found [14], the quality of water, soils, and crops can be affected. The basic premise used to reduce the contaminants presence in waters, soils, and sediments is the constant monitoring of contaminated areas. This approach should include the long-term pollutants behavior, which is determined by the physic, chemical, and biochemical reactions in the system [15].

The obtained results for each Cuban sediment samples did not show alarming values or higher than those established, which make required remediation measures of the zone. It should be noted that for a better understanding of the radioisotopes concentrations metals in the sediments a deeper mineralogical and geochemical characterization of the sediments should be carried out.

For example, mass spectrometry methods are generally used to know the isotopic composition of an element, taking into account this premise it can be said that they could also be used for the determination of radionuclides in a precise way, since it is possible to measure the atomic mass directly from each element (radioactive isotopes of the element).

**References**

[1] Huerta Díaz MA. Geochemistry of sediments. In: Iron Sulphides. 2006. http://www.ens.

Marine Sediments as Fundamental Repository of Radioactive Contaminants in Aquatic Ecosystems

http://dx.doi.org/10.5772/intechopen.72053

185

[2] Díaz Asencio M, Alonso-Hernández CM, Bolaños-Álvarez Y. One century sedimentary record of Hg and Pb pollution in the Sagua estuary (Cuba) derived from 210Pb and 137Cs

[3] Burton GA, Landrum PF. Toxicity of sediments. In: Middleton GV, Church MJ, Corigilo M, Hardie LA, Longstaffe FJ, editors. Encyclopedia of Sediments and Sedimentary Rocks.

[4] Navarrete M, Zúñiga M, Espinosa G, Golzarri J. Radioactive contamination factor (RCF) obtained by comparing contaminant radioactivity (137Cs) with natural radioactivity (40K) in marine sediments taken up from Mexican sea waters. World Journal of Nuclear

[5] Alonso-Hernández CM, Cartas Águila H, Díaz-Asencio M, Muñoz-Caravaca A, Martín-Pérez J, Sibello Hernández R. Atmospheric deposition of 137Cs between 1994 and 2002 at

[6] Gelen A, Díaz O, Simón MJ, Herrera E, Soto J, Gómez J, Ródenas C, Beltrán J, Ramírez M. 210Pb dating of sediments from Havana Bay. Journal of Radioanalytical and Nuclear

[7] Allen BG Jr, Baudo R, Beltrami M, Rowland C. Assessing sediment contamination using

[8] Water quality — Sampling — Part 2: Guidance on sampling techniques. 1991. ISO 5667-2:1991

[9] Navarrete Tejero JM, Cabrera L. Introduction to the Study of Radioisotopes. Faculty of

[10] Maheshwar S, Madhuri S. Nuclear Chemistry. Vol. 1. Ane Books India/CRC Press; 2009.

[11] Navarrete JM, Müller G. Natural radioactivity and radioactive contamination in sea water. In: Radioactive Contamination Research Developments, Nova Science Pub.,

[12] Navarrete JM, Espinosa G, Müller G, Golzarri JI, Zúñiga Camacho M. Marine sediments as a radioactive pollution repository in the world. Journal of Radioanalytical and

[13] Navarrete JM, Müller G, Golzarri JI, Espinosa G. Establishment of a radioactive contamination index in seawater from the Gulf and Pacific coasts in Mexico. International

Cienfuegos, Cuba. Journal of Environmental Radioactivity. 2006;**88**(2):199-204

uabc.mx/iio/persogeo.htm (online course); Chapter 06

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six toxicity assays. Journal of Limnology. 2001;**60**(2):263-267

chronology. Marine. Sciences. 2009;**40**(4):321-337

Science and Technology. 2014;**4**:158-162

Chemistry. 2003;**256**(3):561-564

Chemistry, UNAM, 1993

Nuclear Chemistry. 2013;**299**:843-847

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p. 173

2010;**8**:270-274

In recent years, different articles have reported the use of mass spectrometry for the study of radionuclides with a long period of disintegration, obtaining satisfactory results [16, 17]. It is known that due to the nature of the radioactive decay, radiometric methods have a greater statistical variation in the results than those obtained by mass spectrometry. Therefore, a more precise study could be done with this attractive tool.

Finally, it is important to say that a study that allows the establishment of pollutants levels in sediments should be done frequently to regulate these levels, and thus to ensure the quality of the marine ecosystem.

### **4. Conclusions**


### **Author details**

Marisé García Batlle\* and Juan Manuel Navarrete Tejero

\*Address all correspondence to: mgarciabatlle@yahoo.com

Faculty of Chemistry, Inorganic and Nuclear Chemistry Department, National Autonomous University of Mexico, Mexico City, Mexico

### **References**

for the determination of radionuclides in a precise way, since it is possible to measure the

In recent years, different articles have reported the use of mass spectrometry for the study of radionuclides with a long period of disintegration, obtaining satisfactory results [16, 17]. It is known that due to the nature of the radioactive decay, radiometric methods have a greater statistical variation in the results than those obtained by mass spectrometry. Therefore, a

Finally, it is important to say that a study that allows the establishment of pollutants levels in sediments should be done frequently to regulate these levels, and thus to ensure the quality

**1.** Marine sediments are the main repository of radioactive contamination. In the Cuban sediments studied, the contents of 137Cs and 40K could be adequately calculated, showing that sediments are much more receptive and representative than the atmosphere and soils in

**2.** The measurement of the ratio between the anthropogenic pollutant 137Cs compared to the natural radionuclide 40K in marine sediments (RCF) remains a suitable method for envi-

**3.** The radioactive contamination factor (RCF) values obtained in each gamma detector,

**4.** It was found that there are remarkable differences in RCF values between marine sediments form the North coast and those on the South coast. The RCF values for the northern coast are higher than those obtained in samples taken on the southern coast of Cuba.

**5.** Comparing the RCF values of the Cuban marine sediments samples with the RCF values of the study carried out in 2011 Mexico Gulf, superior results were obtained in all cases, being

Faculty of Chemistry, Inorganic and Nuclear Chemistry Department, National Autonomous

approximately ten times higher the RCF values of the Cuban sediments.

atomic mass directly from each element (radioactive isotopes of the element).

more precise study could be done with this attractive tool.

of the marine ecosystem.

the anthropogenic pollutants study.

ronmental radioactive contamination measuring.

showed a 3–15% statistical variation between them.

Marisé García Batlle\* and Juan Manuel Navarrete Tejero

University of Mexico, Mexico City, Mexico

\*Address all correspondence to: mgarciabatlle@yahoo.com

**4. Conclusions**

184 Sedimentation Engineering

**Author details**


[14] Calmano W. Sediment quality assessment: Chemical and biological approaches. In: En Calmano W, Förstner U, editors. Sediments and Toxic Substances. Germany: Springer-

[15] Environmental Protection Agency. Water Quality Assessment: A Screening Procedure for Toxic and Conventional Pollutants in Surface and Ground Water—Part I and II. 1985.

[16] Becker JS, Dietze H-J. Determination of long-lived radionuclides by double focusing sector field ICP mass spectrometry. Advances in Mass Spectrometry. 1998;**14**:681-689 [17] Becker JS. Recent developments in isotope analysis by advanced mass spectrometric techniques. Plenary lecture. Journal of Analytical Atomic Spectrometry. 2005;**20**:1173-1184

Verlag; 1996. pp. 17-35

186 Sedimentation Engineering

EPA/600/6-85/002a

## *Edited by Ata Amini*

The lack of knowledge about sedimentation processes taking place in a watershed or a waterbody hinders practical progress in addressing problem-solving. To assist the reader in putting sediment quantity and quality issues into perspective, sedimentation engineering features the most state-of-the-art contributions from a number of researchers working in the fields of water resources and soil erosion. The book contains 10 chapters selected among a great number of submitted manuscripts. The main topics are sedimentation processes in marshes, harbor estuaries, gulf, hydraulic turbine, and volcanic area. Sediment contamination and few other topics are included as well. The case studies cover a sequence for integrated solutions where watershed management and sedimentation engineering are not decoupled. This book on sedimentation engineering is designed for researchers and professionals and for course use in environmental science.

Published in London, UK © 2018 IntechOpen © semakokal / iStock

Sedimentation Engineering

Sedimentation Engineering